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Supporting Information

Cobalt-Catalyzed C–H Cyanation of (Hetero)arenes and 6-Arylpurines with N-Cyanosuccinimide as a New Cyanating

Agent

Amit B. Pawar†,‡ and Sukbok Chang*†,‡

† Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS), Daejeon, 305-701,

Republic of Korea, Email: [email protected]

‡ Department of Chemistry, Korea Advanced Institute of Science & Technology (KAIST), Daejeon 305-701,

Republic of Korea

Table of Content S-1

1. General Methods S-2

2. General Procedures for the Preparation of Starting Materials S-2

3. Experimental Procedure of the Optimization Study S-6

4. Experimental Procedure of the Co-Catalyzed C‒H Cyanation

4.1. General Procedure for the Co-Catalyzed C‒H Cyanation with N-

cyanosuccinimide

4.2. Spectroscopic Data of Cyanated Compounds Obtained in this Study

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5. H/D Exchange Experiment S-24

6. Kinetic Isotope Effect Study S-25

7. References S-26

8. Appendix

Copies of 1H and 13C NMR Spectral Data of Compounds Obtained in this Study

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Crystallographic Data of 3j, 5g and 7b S-86

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1. General Methods

Unless otherwise stated, all commercial reagents and solvents were used without additional purification. Analytical thin layer chromatography (TLC) was performed on pre-coated silica gel 60 F254 plates. Visualization on TLC was achieved by the use of UV light (254 nm). Column chromatography was undertaken on silica gel (400‒630mesh) using a proper eluent system. 1H NMR was recorded on Agilent Technologies DD2 (600 MHz). Chemical shifts were quoted in parts per million (ppm) referenced to the appropriate solvent peak or 0.0 ppm for tetramethylsilane. The following abbreviations were used to describe peak splitting patterns when appropriate: br = broad, s = singlet, d = doublet, t = triplet, q = quartet, quin = quintet, sext = sextet, sep = septet, dd = doublet of doublet, td = triplet of doublet, ddd = doublet of doublet of doublet, m = multiplet. Coupling constants, J, were reported in hertz unit (Hz). 13C NMR was recorded on Agilent Technologies DD2 (150 MHz) and was fully decoupled by broad band proton decoupling. Chemical shifts were reported in ppm referenced to the center of a triplet at 77.0 ppm of chloroform-d. Infrared (IR) spectra were recorded using diamond ATR module of ALPHA FT-IR Spectrometer from Bruker Co., Ltd. Frequencies are given in reciprocal centimeters (cm-1) and only selected absorbance peaks are reported. High resolution mass spectra were obtained from the Korea Basic Science Institute (Daegu) by using EI method. Materials were obtained from commercial suppliers or prepared according to standard procedures unless otherwise noted. Cp*Co(CO)I2 was synthesized according to the literature.S1 Various N-cyanoimidesS2 were prepared according to the literature procedure. 2-PhenylpyridineS3 substrates were prepared according to reported procedure.

2. General Procedure for the Preparation of Starting Materials

2.1. General Procedure for the Preparation of Arylpyridines

To a solution of arylboronic acid (2.6 mmol) in toluene (7.0 mL), H2O (7.0 mL), ethanol (2.0 mL), Pd(PPh3)4 (0.069 g, 0.06 mmol), Na2CO3 (1.6 g, 15 mmol), and 2-bromopyridine (0.19 mL, 2.0 mmol) were added under argon atmosphere. The reaction mixture was allowed to stir at 95 °C for 18 h, and then cooled to room temperature. Saturated NH4Cl solution (15 mL) was added and the aqueous mixture was extracted with EtOAc (25 mL x 3). The combined organic extracts were dried over Na2SO4, and concentrated under reduced pressure. The crude product

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was purified by silica gel column chromatography with n-hexane/EtOAc to give the desired 2-arylpyridines.

2.2. Preparation of 2-[4-(1,3-dioxolan-2-yl)phenyl]pyridine (1d)(S4)

A two-neck round bottom flask equiped with Dean-Stark distillation apparatus was charged with 4-(pyridin-2-yl)benzaldehyde (0.37 g, 2.0 mmol) and p-toluenesulfonic acid monohydrate (76 mg, 20 mol%). Benzene (20 mL) and ethylene glycol (0.22 mL, 4.0 mmol) were added, and refluxed for 36 h. The reaction mixture was then cooled to room temperature, evaporated under reduced pressure, and poured into saturated aqueous NaHCO3 solution. The water phase was extracted with CH2Cl2 (20 mL x 3) and the combined organic phase was dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (EtOAc/n-hexane, 3:7) to furnish 1d as white solid (0.30 g, 63%).

2.3. Preparation of (E)-ethyl 3-[4-(pyridin-2-yl)phenyl]acrylate (1f)

To a slurry of NaH (0.12 g of 60% suspension in mineral oil, 3.0 mmol) in dry THF (6.0 mL) was added triethyl phosphonoacetate (0.60 mL, 3.0 mmol) dropwise at -15 °C and stirred at same temperature for 30 min. A solution of 4-(pyridin-2-yl)benzaldehyde (0.37 g, 2.0 mmol) in THF (6.0 mL) was introduced into the reaction mixture and stirred at the same temperature for 30 min. It was warmed to room temperature and stirred for another 30 min. After completion of the reaction (TLC), it was quenched with sat. NH4Cl solution (15 mL) and extracted with EtOAc (2 x 20 mL). Combined organic layers were washed with brine (25 mL) and dried over Na2SO4. Evaporation of solvent and then silica gel column chromatography (EtOAc/n-hexane, 3:7) of the residue yielded 1f (0.37 g, 73%) as white solid; m.p. 84 – 85 °C; 1H NMR (600 MHz, CDCl3) δ 8.73 – 8.68 (m, 1H), 8.04 (d, J = 8.3 Hz, 2H), 7.79 – 7.75 (m, 2H), 7.73 (d, J = 16.1 Hz, 1H), 7.64 (d, J = 8.3 Hz, 2H), 7.28 – 7.22 (m, 1H), 6.50 (d, J = 16.0 Hz, 1H), 4.28 (q, J = 7.1 Hz, 2H), 1.35 (t, J = 7.1 Hz, 3H); 13C NMR (150 MHz, CDCl3) δ 166.9, 156.4, 149.8, 143.9, 141.0, 136.8, 135.0, 128.5, 127.3, 122.5, 120.6, 118.7, 60.5, 14.3; IR (diamond) 3070, 2985, 1710, 1628, 1581, 1466, 1176, 984, 775 cm-1; HRMS (EI) m/z calcd. for C16H15NO2 [M]+: 253.1103, found: 253.1102.

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2.4. Preparation of 4-(pyridin-2-yl)benzyl acetate (1ga)

To a solution of [4-(pyridin-2-yl)phenyl]methanol (0.26 g, 1.4 mmol) in CH2Cl2 (2.0 mL) were added triethylamine (0.40 mL, 2.8 mmol) and acetic anhydride (Ac2O, 1.0 mL) at room temperature. After stirring for 12 h, the reaction mixture was quenched with water (20 mL). and extracted with CH2Cl2 (20 mL x 2). The comdined organic layers were washed with brine (20 mL) and dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude product was further purified by silica gel column chromatography (EtOAc/n-hexane, 2:8) to furnish 1ga as colourless liquid (0.25 g, 80%); 1H NMR (600 MHz, CDCl3) δ 8.70 (d, J = 4.8 Hz, 1H), 7.99 (d, J = 7.9 Hz, 2H), 7.77 – 7.68 (m, 2H), 7.46 (d, J = 7.8 Hz, 2H), 7.27 – 7.20 (m, 1H), 5.16 (s, 2H), 2.12 (s, 3H); 13C NMR (150 MHz, CDCl3) δ 170.8, 156.9, 149.6, 139.3, 136.8, 136.7, 128.5, 127.1, 122.2, 120.5, 65.9, 21.0; IR (diamond) 3285, 2950, 1734, 1587, 1466, 1435, 1376, 1224, 1016, 776 cm-1; HRMS (EI) m/z calcd. for C14H13NO2 [M]+: 227.0946, found: 227.0944.

2.5. Preparation of 2-{4-[(tert-butyldimethylsilyloxy)methyl]phenyl}pyridine (1gb)

To a solution of [4-(pyridin-2-yl)phenyl]methanol (0.37 g, 2.0 mmol) in CH2Cl2 (4.0 mL) were added imidazole (0.27 g, 4.0 mmol), TBDMSCl (0.45 g, 3.0 mmol) and DMAP (50 mg, 20 mol %) at room temperature. After stirring for 12 h, the reaction mixture was quenched with water (20 mL). The organic layer was separated and aqueous phase was extracted with CH2Cl2 (20 mL x 2). The comdined organic layers were washed with brine (20 mL), dried over Na2SO4, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (EtOAc/n-hexane, 1:9) to afford 1gb as white solid (0.50 g, 83%); m.p. 72 – 73 °C; 1H NMR (600 MHz, CDCl3) δ 8.68 (d, J = 4.9 Hz, 1H), 7.96 (d, J = 8.1 Hz, 2H), 7.81 – 7.64 (m, 2H), 7.43 (d, J = 8.0 Hz, 2H), 7.24 – 7.15 (m, 1H), 4.80 (s, 2H), 0.96 (s, 9H), 0.11 (s, 6H); 13C NMR (150 MHz, CDCl3) δ 157.4, 149.6, 142.4, 138.1, 136.6, 126.8, 126.4, 121.9, 120.4, 64.8, 25.9, 18.4, -5.2; IR (diamond) 2953, 2925, 2882, 2852, 1585, 1466, 1434, 1296, 1252, 1207, 1083, 833, 775 cm-1; HRMS (EI) m/z calcd. for C18H25NOSi [M]+: 299.1705, found: 299.1704.

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2.6. Preparation of 2-{4-[(methoxymethoxy)methyl]phenyl}pyridine (1gc)

To a solution of [4-(pyridin-2-yl)phenyl]methanol (0.30 g, 1.6 mmol) in CH2Cl2 (4.0 mL) were added diisopropylethylamine (0.56 mL, 3.2 mmol), DMAP (40 mg, 20 mol%) and MOMCl (0.18 mL, 3.3 mmol) at 0 °C. After stirring for 15 min at the same temperature, the recation mixture was refluxed for 5 h. After completion of the reaction, it was cooled to room temperature and quenched with water (20 mL). The organic layer was separated. The aqueous phase was extracted with CH2Cl2 (20 mL x 2). The comdined organic layers were washed brine (20 mL), dried over Na2SO4, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (EtOAc/n-hexane, 1:9) to afford 1gc as colorless oil (0.27 g, 74%); 1H NMR (600 MHz, CDCl3) δ 8.69 (d, J = 4.6 Hz, 1H), 7.99 (d, J = 8.0 Hz, 2H), 7.78 – 7.70 (m, 2H), 7.47 (d, J = 8.0 Hz, 2H), 7.25 – 7.19 (m, 1H), 4.74 (s, 2H), 4.66 (s, 2H), 3.43 (s, 3H); 13C NMR (150 MHz, CDCl3) δ 157.2, 149.7, 138.8, 138.7, 136.7, 128.2, 126.9, 122.1, 120.5, 95.7, 68.8, 55.4; IR (diamond) 2929, 2881, 1586, 1561, 1434, 1376, 1210, 1147, 1099, 1042, 775 cm-1; HRMS (EI) m/z calcd. for C14H15NO2 [M]+: 229.1103, found: 229.1100.

2.7. Preparation of 2-{4-[(4-methoxybenzyloxy)methyl]phenyl}pyridine (1gd)

To a solution of [4-(pyridin-2-yl)phenyl]methanol (0.15 g, 0.81 mmol) in dry DMF (4 mL) were added NaH (48 mg of 60% suspension in mineral oil, 1.2 mmol), Bu4NI (30 mg, 10 mol%) and PMBCl (98 μL, 0.97 mmol) at 0 °C. After stirring for 15 min at the same temperature, the reaction mixture was warmed to room temperature. After stirring for 12 h, the reaction mixture was quenched with water (20 mL) and extracted with CH2Cl2 (20 mL x 2). The combined organic layers were wased with brine (20 mL), dried over Na2SO, and evaporated under reduced pressure. The residue was purified by silica gel column chromatography (EtOAc/n-hexane, 1:9) to afford 1gd as colourless liquid (0.16 g, 63%); 1H NMR (600 MHz, CDCl3) δ 8.71 – 8.67 (m, 1H), 7.98 (d, J = 8.2 Hz, 2H), 7.78 – 7.70 (m, 2H), 7.47 (d, J = 8.2 Hz, 2H), 7.32 – 7.28 (m, 2H), 7.25 – 7.20 (m, 1H), 6.93 – 6.86 (m, 2H), 4.59 (s, 2H), 4.51 (s, 2H), 3.81 (s, 3H); 13C NMR (150 MHz, CDCl3) δ 159.2, 157.2, 149.6, 139.2, 138.7, 136.7, 130.3, 129.4, 128.1, 126.9, 122.1, 120.5, 113.8, 71.8, 71.4, 55.3; IR (diamond) 3003, 2854, 2834, 1610, 1585, 1561, 1244, 1078, 1030, 775 cm-1; HRMS (EI) m/z calcd. for C20H19NO2 [M]+: 305.1416, found: 305.1418.

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3. Experimental Procedure of the Optimization Study

To a screw capped vial with a spinvane triangular-shaped Teflon stirbar were added 2-phenylpyridine (1a, 15.5 mg, 0.10 mmol), cyanating agent (2a-2d, 0.15 mmol), catalyst, Ag salt, additive, and solvent (0.5 mL) under argon atmosphere. The reaction mixture was stirred

in a pre-heated oil bath at 120 C for 12 h. The reaction mixture was cooled to room temperature, filtered through a pad of celite and then washed with EtOAc (10 mL x 3). Solvents were removed under reduced pressure and crude yield was measured by 1H NMR using an internal standard (1,1,2,2-tetrachloroethane).

Table S1. Optimization of the Co-Catalyzed C−H Cyanation Reaction

Entry Catalyst (mol %) Ag salt (mol %)

CN source

Additives (mol %)

Solvent Yield (%)a

1 Cp*Co(CO)I2 (10) AgNTf2 (20) 2a - 1,2-DCE 31

2 Cp*Co(CO)I2 (10) AgNTf2 (20) 2a K2CO3 (20) 1,2-DCE 31

3 Cp*Co(CO)I2 (10) AgNTf2 (20) 2a Na2CO3 (20) 1,2-DCE 25

4 Cp*Co(CO)I2 (10) AgNTf2 (20) 2a Li2CO3 (20) 1,2-DCE 40

5 Cp*Co(CO)I2 (10) AgNTf2 (20) 2a Ag2CO3 (20) 1,2-DCE 22

6 Cp*Co(CO)I2 (10) AgNTf2 (20) 2a KOAc (20) 1,2-DCE 60

7 Cp*Co(CO)I2 (10) AgNTf2 (20) 2a NaOAc (20) 1,2-DCE 58

8 Cp*Co(CO)I2 (10) AgNTf2 (20) 2a CsOAc (20) 1,2-DCE 57

9 Cp*Co(CO)I2 (10) AgNTf2 (20) 2a LiOAc (20) 1,2-DCE 57

10 Cp*Co(CO)I2 (10) AgNTf2 (20) 2a Cu(OAc)2 (20) 1,2-DCE 25

11 Cp*Co(CO)I2 (10) AgNTf2 (20) 2a AgOAc (20) 1,2-DCE 66

12 Cp*Co(CO)I2 (10) AgNTf2 (20) 2b AgOAc (20) 1,2-DCE 42

13 Cp*Co(CO)I2 (10) AgNTf2 (20) 2c AgOAc (20) 1,2-DCE 74

14 Cp*Co(CO)I2 (10) AgNTf2 (20) 2d AgOAc (20) 1,2-DCE 80(74)

15b Cp*Co(CO)I2 (10) AgNTf2 (20) 2d AgOAc (20) 1,2-DCE 72

16c Cp*Co(CO)I2 (10) AgNTf2 (20) 2d AgOAc (20) 1,2-DCE 57

17 Cp*Co(CO)I2 (10) AgNTf2 (20) 2d AgOTf (20) 1,2-DCE 23

18 Cp*Co(CO)I2 (10) AgNTf2 (20) 2d AgOTs (20) 1,2-DCE 29

19 Cp*Co(CO)I2 (10) AgNTf2 (20) 2d AgOAc (20) 1,4-Dioxane 67

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20 Cp*Co(CO)I2 (10) AgNTf2 (20) 2d AgOAc (20) THF 60

21 Cp*Co(CO)I2 (10) AgNTf2 (20) 2d AgOAc (20) Acetone 38

22 Cp*Co(CO)I2 (10) AgNTf2 (20) 2d AgOAc (20) o-Xylene 30

23 Cp*Co(CO)I2 (10) AgNTf2 (20) 2d AgOAc (20) DMF N.R.

24 Cp*Co(CO)I2 (10) AgSbF6 (20) 2d AgOAc (20) 1,2-DCE 61

25 Cp*Co(CO)I2 (5) AgNTf2 (10) 2d AgOAc (10) 1,2-DCE 67

26 - AgNTf2 (20) 2d AgOAc (20) 1,2-DCE N.R.

27 Cp*Co(CO)I2 (10) - 2d AgOAc (20) 1,2-DCE N.R.

28 Co(OAc)2 (10) AgNTf2 (20) 2d AgOAc (20) 1,2-DCE N.R.

29 Co(acac)3 (10) AgNTf2 (20) 2d AgOAc (20) 1,2-DCE N.R.

30 Co(TPP) (10) AgNTf2 (20) 2d AgOAc (20) 1,2-DCE N.R.

Reaction conditions: 1a (0.10 mmol), 2a–2d (0.15 mmol), catalyst, additive and solvent (0.5 mL) at the 120 C

for 12 h. a NMR yields are given and isolated yield is shown in parenthesis. b Reaction carried out at 110 C. c Run for 9 h. N.R. = no reaction.

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4. Experimental Procedure of the Co-Catalyzed C‒H Cyanation

4.1. General Procedure for the Co-Catalyzed C‒H Cyanation with N-Cyanosuccinimide

To a screw capped vial with a spinvane triangular-shaped Teflon stirbar were added arene (0.10 mmol), N-cyanosuccinimide (2d, 18.6 mg, 0.15 mmol), Cp*Co(CO)I2 (4.8 mg, 10 mol %), AgNTf2 (7.8 mg, 20 mol %), AgOAc (3.3 mg, 20 mol %), and 1,2-dichloroethane (0.5

mL) under argon atmosphere. The reaction mixture was stirred at 120 C for 12 h, cooled to room temerature, filtered through a pad of celite and then washed with EtOAc (10 mL x 3). The organic layer was washed with 1N NaOH (15 mL) followed by H2O (15 mL), dried over Na2SO4 and filtered. Solvents were removed under reduced pressure and the residue was purified by column chromatography on silica gel (n-hexane/EtOAc) to give the desired cyanated product.

4.2. Spectroscopic Data of Cyanated Compounds Obtained in this Study.

2-(Pyridin-2-yl)benzonitrile (Scheme 2, 3aa)S5

White solid; m.p. 47 – 48 °C; 1H NMR (600 MHz, CDCl3) δ 8.81 – 8.75 (m, 1H), 7.86 – 7.82 (m, 2H), 7.82 – 7.77 (m, 2H), 7.70 (td, J = 7.7, 1.4 Hz, 1H), 7.51 (td, J = 7.7, 1.1 Hz, 1H), 7.36 (ddd, J = 7.4, 4.8, 1.1 Hz, 1H); 13C NMR (150 MHz, CDCl3) δ 155.2, 149.9, 143.4, 136.7, 134.1, 132.8, 129.9, 128.7, 123.3, 123.2, 118.6, 111.0.

5-Methyl-2-(pyridin-2-yl)benzonitrile (Scheme 2, 3ab)S5

White solid; m.p. 76 – 77 °C; 1H NMR (600 MHz, CDCl3) δ 8.76 (d, J = 4.5 Hz, 1H), 7.82 (td, J = 7.7, 1.8 Hz, 1H), 7.79 – 7.70 (m, 2H), 7.60 (brs, 1H), 7.49 (d, J = 7.8 Hz, 1H), 7.34 (dd, J = 7.4, 4.8 Hz, 1H), 2.44 (s, 3H); 13C NMR (150 MHz, CDCl3) δ 155.2, 149.7, 140.5, 139.1, 136.8, 134.4, 133.7, 129.9, 123.11, 123.09, 118.8, 110.8, 20.8.

5-(tert-Butyl)-2-(pyridin-2-yl)benzonitrile (Scheme 2, 3ac)S6

Colorless liquid; 1H NMR (600 MHz, CDCl3) δ 8.76 (d, J = 4.4 Hz, 1H), 7.83 (td, J = 7.7, 1.8 Hz, 1H), 7.81 – 7.76 (m, 3H), 7.71 (dd, J = 8.3, 2.1 Hz, 1H), 7.34 (ddd, J = 7.5, 4.9, 1.3 Hz,

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1H), 1.37 (s, 9H); 13C NMR (150 MHz, CDCl3) δ 155.2, 152.4, 149.8, 140.5, 136.8, 131.1, 130.2, 129.7, 123.08, 123.07, 119.2, 110.6, 34.8, 31.0.

4-(Pyridin-2-yl)-[1,1'-biphenyl]-3-carbonitrile (Scheme 2, 3ad)S5

White solid; m.p. 68 – 69 °C; 1H NMR (600 MHz, CDCl3) δ 8.80 (d, J = 4.8 Hz, 1H), 8.02 (d, J = 1.9 Hz, 1H), 7.95 (d, J = 8.1 Hz, 1H), 7.91 (dd, J = 8.1, 1.9 Hz, 1H), 7.89 – 7.83 (m, 2H), 7.63 (d, J = 7.6 Hz, 2H), 7.51 (t, J = 7.6 Hz, 2H), 7.44 (t, J = 7.4 Hz, 1H), 7.40 – 7.35 (m, 1H); 13C NMR (150 MHz, CDCl3) δ 154.8, 149.9, 142.0, 141.8, 138.3, 136.9, 132.6, 131.4, 130.5, 129.1, 128.5, 127.0, 123.3, 123.2, 118.7, 111.5.

5-(Dimethylamino)-2-(pyridin-2-yl)benzonitrile (Scheme 2, 3ae)

Colorless solid; m.p. 77 – 78 °C; 1H NMR (600 MHz, CDCl3) δ 8.73 – 8.64 (m, 1H), 7.81 – 7.68 (m, 3H), 7.24 (ddd, J = 6.7, 4.9, 1.8 Hz, 1H), 7.00 (d, J = 2.8 Hz, 1H), 6.95 (dd, J = 8.8, 2.8 Hz, 1H), 3.04 (s, 6H); 13C NMR (150 MHz, CDCl3) δ 155.5, 149.9, 149.6, 136.5, 130.7, 130.4, 122.4, 122.0, 119.7, 116.5, 116.0, 111.3, 40.1; IR (diamond) 3002, 2916, 2895, 2223, 1602, 1543, 1468, 1369, 1230, 989, 789 cm-1; HRMS (EI) m/z calcd. for C14H13N3 [M]+: 223.1109, found: 223.1109.

5-(Methylthio)-2-(pyridin-2-yl)benzonitrile (Scheme 2, 3af)

White solid; m.p. 50 – 51 °C; 1H NMR (600 MHz, CDCl3) δ 8.76 (d, J = 4.3 Hz, 1H), 7.83 (td, J = 7.7, 1.8 Hz, 1H), 7.79 – 7.75 (m, 2H), 7.58 (d, J = 2.1 Hz, 1H), 7.52 (dd, J = 8.3, 2.1 Hz, 1H), 7.39 – 7.30 (m, 1H), 2.55 (s, 3H); 13C NMR (150 MHz, CDCl3) δ 154.6, 149.7, 141.0, 139.3, 137.0, 130.5, 130.2, 130.1, 123.2, 123.0, 118.4, 111.5, 15.3; IR (diamond) 3048, 2987, 2918, 2225, 1589. 1565, 1460, 1182, 780 cm-1; HRMS (EI) m/z calcd. for C13H10N2S [M]+: 226.0565, found: 226.0567.

5-Methoxy-2-(pyridin-2-yl)benzonitrile (Scheme 2, 3ba)S5

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White solid; m.p. 105 – 106 °C; 1H NMR (600 MHz, CDCl3) δ 8.75 (d, J = 4.6 Hz, 1H), 7.86 – 7.72 (m, 3H), 7.32 (ddd, J = 7.4, 4.8, 1.2 Hz, 1H), 7.27 (d, J = 2.7 Hz, 1H), 7.22 (dd, J = 8.7, 2.7 Hz, 1H), 3.89 (s, 3H); 13C NMR (150 MHz, CDCl3) δ 159.6, 154.9, 149.6, 136.9, 135.8, 131.4, 122.9, 122.8, 119.4, 118.6, 118.5, 111.8, 55.7.

5-(Benzyloxy)-2-(pyridin-2-yl)benzonitrile (Scheme 2, 3bb)S6

White solid; m.p. 84 – 85 °C; 1H NMR (600 MHz, CDCl3) δ 8.75 (d, J = 4.6 Hz, 1H), 7.86 – 7.69 (m, 3H), 7.47 – 7.40 (m, 4H), 7.39 – 7.34 (m, 2H), 7.32 (dd, J = 7.4, 4.9 Hz, 1H), 7.29 (dd, J = 8.7, 2.7 Hz, 1H), 5.15 (s, 2H); 13C NMR (150 MHz, CDCl3) δ 158.7, 154.9, 149.7, 136.8, 136.2, 135.7, 131.4, 128.8, 128.4, 127.5, 122.9, 122.8, 120.2, 119.6, 118.5, 111.8, 70.5.

5-Phenoxy-2-(pyridin-2-yl)benzonitrile (Scheme 2, 3bc)

White solid; m.p. 45 – 46 °C; 1H NMR (600 MHz, CDCl3) δ 8.76 (d, J = 4.7 Hz, 1H), 7.85 – 7.80 (m, 2H), 7.78 (d, J = 7.9 Hz, 1H), 7.42 (t, J = 7.9 Hz, 2H), 7.36 – 7.29 (m, 3H), 7.23 (t, J = 7.4 Hz, 1H), 7.08 (d, J = 8.0 Hz, 2H); 13C NMR (150 MHz, CDCl3) δ 158.1, 155.4, 154.7, 149.8, 137.7, 136.9, 131.7, 130.2, 124.8, 123.1, 123.0, 122.7, 122.6, 119.8, 118.1, 112.1; IR (diamond) 3053, 3008, 2985, 2227, 1584, 142, 1225, 951, 788 cm-1; HRMS (EI) m/z calcd. for C18H12N2O [M]+: 272.0950, found: 272.0946.

3-Cyano-N,N-dimethyl-4-(pyridin-2-yl)benzamide (Scheme 2, 3ca)

White solid; m.p. 94 – 95 °C; 1H NMR (600 MHz, CDCl3) δ 8.79 (d, J = 5.4 Hz, 1H), 7.91 (d, J = 8.1 Hz, 1H), 7.89 – 7.85 (m, 2H), 7.81 (d, J = 7.9 Hz, 1H), 7.75 (dd, J = 8.0, 1.7 Hz, 1H), 7.40 (dd, J = 7.5, 4.8 Hz, 1H), 3.15 (s, 3H), 3.03 (s, 3H); 13C NMR (150 MHz, CDCl3) δ 168.9, 154.4, 150.0, 144.3, 136.9, 132.7, 131.4, 130.2, 123.7, 123.2, 117.9, 111.3, 39.5, 35.5; IR (diamond) 3051, 2922, 2852, 2229, 1620, 1582, 1400, 1170, 794 cm-1; HRMS (EI) m/z calcd. for C15H13N3j [M]+: 251.1059, found: 251.1058.

S-11

5-Acetyl-2-(pyridin-2-yl)benzonitrile (Scheme 2, 3cb)

White solid; m.p. 102 – 103 °C; 1H NMR (600 MHz, CDCl3) δ 8.81 (d, J = 4.8 Hz, 1H), 8.37 (brs, 1H), 8.24 (d, J = 8.2 Hz, 1H), 7.99 (d, J = 8.2 Hz, 1H), 7.93 – 7.81 (m, 2H), 7.44 – 7.39 (m, 1H), 2.68 (s, 3H); 13C NMR (150 MHz, CDCl3) δ 195.5, 154.0, 150.1, 146.8, 137.0, 136.9, 134.2, 132.1, 130.5, 124.0, 123.4, 117.9, 111.7, 26.6; IR (diamond) 3075, 3059, 2924, 2226, 1684, 1570, 1466, 1259, 785 cm-1; HRMS (EI) m/z calcd. for C14H10N2O [M]+: 222.0793, found: 222.0794.

Methyl 3-cyano-4-(pyridin-2-yl)benzoate (Scheme 2, 3cc)S5

White solid; m.p. 91 – 92 °C; 1H NMR (600 MHz, CDCl3) δ 8.81 (dt, J = 4.8, 1.3 Hz, 1H), 8.47 (d, J = 1.8 Hz, 1H), 8.33 (dd, J = 8.2, 1.8 Hz, 1H), 7.96 (d, J = 8.2 Hz, 1H), 7.88 (td, J = 7.6, 1.8 Hz, 1H), 7.86 – 7.82 (m, 1H), 7.41 (ddd, J = 7.3, 4.8, 1.4 Hz, 1H), 3.99 (s, 3H); 13C NMR (150 MHz, CDCl3) δ 165.0, 154.2, 150.1, 147.0, 136.9, 135.4, 133.5, 130.7, 130.5, 123.9, 123.4, 117.8, 111.5, 52.7.

5-(1,3-Dioxolan-2-yl)-2-(pyridin-2-yl)benzonitrile (Scheme 2, 3d)

White solid; m.p. 103 – 104 °C; 1H NMR (600 MHz, CDCl3) δ 8.78 (d, J = 4.5 Hz, 1H), 7.93 (s, 1H), 7.90 – 7.81 (m, 2H), 7.81 – 7.76 (m, 2H), 7.36 (dd, J = 7.5, 4.8 Hz, 1H), 5.90 (s, 1H), 4.17 – 4.04 (m, 4H); 13C NMR (150 MHz, CDCl3) δ 154.9, 150.0, 143.9, 139.4, 136.1, 132.2, 130.9, 130.1, 123.4, 123.2, 118.5, 111.1, 102.1, 65.4; IR (diamond) 2958, 2893, 2850, 2226, 1589, 1470, 1098, 947, 785 cm-1; HRMS (EI) m/z calcd. for C15H12N2O2 [M]+: 252.0899, found: 252.0896.

2-(Pyridin-2-yl)-5-(trifluoromethyl)benzonitrile (Scheme 2, 3e)S7

S-12

White solid; m.p. 65 – 66 °C; 1H NMR (600 MHz, CDCl3) δ 8.82 (d, J = 4.7 Hz, 1H), 8.07 (brs, 1H), 8.03 (d, J = 8.2 Hz, 1H), 7.94 (d, J = 8.2 Hz, 1H), 7.90 (td, J = 7.7, 1.7 Hz, 1H), 7.84 (d, J = 7.8 Hz, 1H), 7.43 (dd, J = 7.5, 4.8 Hz, 1H); 13C NMR (150 MHz, CDCl3) δ 153.7, 150.2, 146.5, 137.0, 131.3 (q, J C-F = 33.9 Hz), 131.0 (d, J C-F = 3.8 Hz), 130.7, 129.4 (q, J C-F = 3.6 Hz), 124.1, 123.3, 122.9 (d, J C-F = 271.3 Hz), 117.3, 111.9.

(E)-Ethyl 3-(3-cyano-4-(pyridin-2-yl)phenyl)acrylate (Scheme 2, 3f)

White solid; m.p. 138 – 139 °C; 1H NMR (600 MHz, CDCl3) δ 8.79 (dt, J = 4.8, 1.3 Hz, 1H), 7.93 (d, J = 1.8 Hz, 1H), 7.91 (d, J = 8.2 Hz, 1H), 7.86 (td, J = 7.6, 1.8 Hz, 1H), 7.84 – 7.81 (m, 2H), 7.69 (d, J = 16.0 Hz, 1H), 7.38 (ddd, J = 7.3, 4.8, 1.3 Hz, 1H), 6.54 (d, J = 16.0 Hz, 1H), 4.30 (q, J = 7.1 Hz, 2H), 1.36 (t, J = 7.1 Hz, 3H); 13C NMR (150 MHz, CDCl3) δ 166.1, 154.4, 150.0, 144.2, 141.3, 136.9, 135.3, 133.5, 131.7, 130.6, 123.6, 123.1, 121.2, 118.1, 111.8, 60.9, 14.2; IR (diamond) 3076, 2986, 2873, 2223, 1712, 1634, 1465, 1181, 783 cm-1; HRMS (EI) m/z calcd. for C17H14N2O2 [M]+: 278.1055, found: 278.1056.

3-Cyano-4-(pyridin-2-yl)benzyl acetate (Scheme 2, 3ga)

N

CNO

O White solid; m.p. 44 – 45 °C; 1H NMR (600 MHz, CDCl3) δ 8.78 (d, J = 4.2 Hz, 1H), 7.88 – 7.83 (m, 2H), 7.81 – 7.77 (m, 2H), 7.69 – 7.63 (m, 1H), 7.37 (ddd, J = 7.5, 4.9, 1.2 Hz, 1H), 5.18 (s, 2H), 2.15 (s, 3H); 13C NMR (150 MHz, CDCl3) δ 170.5, 154.7, 150.0, 143.1, 137.2, 136.8, 133.3, 132.3, 130.2, 123.4, 123.1, 118.4, 111.3, 64.6, 20.8; IR (diamond) 3048, 2992, 2921, 2229, 1739, 1586, 1249, 1027, 751 cm-1; HRMS (EI) m/z calcd. for C15H12N2O2 [M]+: 252.0899, found: 252.0898.

5-[(tert-Butyldimethylsilyloxy)methyl]-2-(pyridin-2-yl)benzonitrile (Scheme 2, 3gb)

White solid; m.p. 40 – 41 °C; 1H NMR (600 MHz, CDCl3) δ 8.77 (d, J = 4.8 Hz, 1H), 7.86 – 7.74 (m, 4H), 7.62 (d, J = 8.1 Hz, 1H), 7.35 (ddd, J = 7.4, 4.9, 1.2 Hz, 1H), 4.81 (s, 2H), 0.96 (s, 9H), 0.13 (s, 6H); 13C NMR (150 MHz, CDCl3) δ 155.2, 149.9, 142.7, 142.0, 136.7, 131.4, 130.3, 129.9, 123.16, 123.13, 118.9, 110.8, 63.7, 25.9, 18.4, -5.3; IR (diamond) 2951, 2927,

S-13

2855, 2223, 1585, 1460, 1252, 1088, 833, 774 cm-1; HRMS (EI) m/z calcd. for C19H24N2OSi [M]+: 324.1658, found: 324.1655.

5-[(Methoxymethoxy)methyl]-2-(pyridin-2-yl)benzonitrile (Scheme 2, 3gc)

Pale yellow oil; 1H NMR (600 MHz, CDCl3) δ 8.79 – 8.75 (m, 1H), 7.86 – 7.75 (m, 4H), 7.67 (dd, J = 8.1, 1.8 Hz, 1H), 7.36 (ddd, J = 7.5, 4.8, 1.2 Hz, 1H), 4.75 (s, 2H), 4.68 (s, 2H), 3.43 (s, 3H); 13C NMR (150 MHz, CDCl3) δ 155.0, 149.9, 142.6, 139.4, 136.8, 132.9, 131.8, 130.0, 123.3, 123.2, 118.6, 111.1, 96.0, 67.7, 55.6; IR (diamond) 2928, 2886, 2225, 1586, 1463, 1214, 1044, 789 cm-1; HRMS (EI) m/z calcd. for C15H14N2O2 [M]+: 254.1055, found: 254.1056.

5-[(4-Methoxybenzyloxy)methyl]-2-(pyridin-2-yl)benzonitrile (Scheme 2, 3gd)

Pale yellow oil; 1H NMR (600 MHz, CDCl3) δ 8.77 (dt, J = 4.8, 1.3 Hz, 1H), 7.85 – 7.81 (m, 2H), 7.81 – 7.77 (m, 2H), 7.66 (dd, J = 8.1, 1.7 Hz, 1H), 7.35 (ddd, J = 7.5, 4.8, 1.2 Hz, 1H), 7.33 – 7.28 (m, 2H), 6.95 – 6.86 (m, 2H), 4.59 (s, 2H), 4.54 (s, 2H), 3.82 (s, 3H); 13C NMR (150 MHz, CDCl3) δ 159.4, 155.1, 149.9, 142.6, 139.8, 136.8, 132.9, 131.8, 130.0, 129.6, 129.5, 123.3, 123.2, 118.7, 114.0, 111.0, 72.3, 70.2, 55.3; IR (diamond) 2854, 2835, 2224, 1610, 1511, 1244, 1085, 789 cm-1; HRMS (EI) m/z calcd. for C21H18N2O2 [M]+: 330.1368, found: 330.1366.

3-(Pyridin-2-yl)-2-naphthonitrile (Scheme 2, 3h)S5

White solid; m.p. 154 – 155 °C; 1H NMR (600 MHz, CDCl3) δ 8.82 (d, J = 4.8 Hz, 1H), 8.39 (s, 1H), 8.28 (s, 1H), 7.99 – 7.90 (m, 2H), 7.86 (d, J = 4.2 Hz, 2H), 7.72 – 7.58 (m, 2H), 7.42 – 7.33 (m, 1H); 13C NMR (150 MHz, CDCl3) δ 155.5, 149.9, 137.7, 136.8, 136.1, 134.6, 131.8, 129.7, 129.4, 128.5, 128.04, 128.02, 123.3, 123.1, 118.9, 108.8.

S-14

5-Chloro-2-(pyridin-2-yl)benzonitrile (Scheme 2, 3ia)S7

White solid; m.p. 165 – 166 °C; 1H NMR (600 MHz, CDCl3) δ 8.78 (d, J = 4.9 Hz, 1H), 7.88 – 7.76 (m, 4H), 7.67 (dd, J = 8.5, 2.2 Hz, 1H), 7.44 – 7.34 (m, 1H); 13C NMR (150 MHz, CDCl3) δ 154.0, 150.0, 141.7, 137.0, 135.0, 133.6, 133.2, 131.3, 123.6, 123.1, 117.4, 112.5.

5-Bromo-2-(pyridin-2-yl)benzonitrile (Scheme 2, 3ib)S6

White solid; m.p. 145 – 146 °C; 1H NMR (600 MHz, CDCl3) δ 8.78 (d, J = 4.3 Hz, 1H), 7.93 (d, J = 2.0 Hz, 1H), 7.86 (td, J = 7.8, 1.7 Hz, 1H), 7.82 (dd, J = 8.5, 2.0 Hz, 1H), 7.81 – 7.78 (m, 1H), 7.77 – 7.73 (m, 1H), 7.39 (dd, J = 7.5, 4.8 Hz, 1H); 13C NMR (150 MHz, CDCl3) δ 154.1, 150.0, 142.1, 137.0, 136.4, 136.1, 131.4, 123.6, 123.1, 122.6, 117.3, 112.7.

5-Fluoro-2-(pyridin-2-yl)benzonitrile (Scheme 2, 3ic)S5,7

White solid; m.p. 133 – 134 °C; 1H NMR (600 MHz, CDCl3) δ 8.77 (d, J = 4.9 Hz, 1H), 7.89 – 7.81 (m, 2H), 7.77 (d, J = 7.9 Hz, 1H), 7.50 (dd, J = 8.1, 2.6 Hz, 1H), 7.41 (td, J = 8.3, 2.7 Hz, 1H), 7.37 (dd, J = 7.5, 4.9 Hz, 1H); 13C NMR (150 MHz, CDCl3) δ 162.0 (d, J C-F = 251.9 Hz), 154.2, 149.9, 139.9, 136.9, 132.1 (d, J C-F = 8.5 Hz), 123.4, 123.1, 120.7 (d, J C-F = 24.8 Hz), 120.5 (d, J C-F = 21.2 Hz), 117.4 (d, J C-F = 2.4 Hz), 112.5 (d, J C-F = 9.4 Hz).

5-(Methylsulfonyl)-2-(pyridin-2-yl)benzonitrile (Scheme 2, 3j)

Colorless solid; m.p. 130 – 131 °C; 1H NMR (600 MHz, CDCl3) δ 8.83 (d, J = 4.7 Hz, 1H), 8.38 (d, J = 1.9 Hz, 1H), 8.24 (dd, J = 8.3, 1.9 Hz, 1H), 8.10 (d, J = 8.3 Hz, 1H), 7.91 (td, J = 7.7, 1.8 Hz, 1H), 7.87 (d, J = 7.9 Hz, 1H), 7.45 (ddd, J = 7.5, 4.8, 1.2 Hz, 1H), 3.14 (s, 3H); 13C NMR (150 MHz, CDCl3) δ 153.3, 150.3, 148.0, 141.2, 137.2, 133.2, 131.3, 124.4, 123.5, 116.9, 112.5, 44.5; IR (diamond) 3058, 3012, 2919, 2236, 1709, 1144, 765 cm-1; HRMS (EI) m/z calcd. for C13H10N2O2S [M]+: 258.0463, found: 258.0466.

S-15

4-Methoxy-2-(pyridin-2-yl)benzonitrile (Scheme 2, 3ka)S6

White solid; m.p. 70 – 71 °C; 1H NMR (600 MHz, CDCl3) δ 8.77 (dt, J = 4.8, 1.3 Hz, 1H), 7.87 – 7.79 (m, 2H), 7.71 (d, J = 8.6 Hz, 1H), 7.41 – 7.32 (m, 2H), 7.01 (dd, J = 8.6, 2.6 Hz, 1H), 3.92 (s, 3H); 13C NMR (150 MHz, CDCl3) δ 162.8, 155.2, 149.9, 145.6, 136.8, 135.7, 123.4, 123.3, 119.1, 115.1, 115.0, 102.7, 55.7.

4-Methyl-2-(pyridin-2-yl)benzonitrile (Scheme 2, 3kb)S5

White solid; m.p. 59 – 60 °C; 1H NMR (600 MHz, CDCl3) δ 8.77 (dt, J = 4.9, 1.3 Hz, 1H), 7.83 (td, J = 7.6, 1.8 Hz, 1H), 7.81 – 7.77 (m, 1H), 7.71 – 7.65 (m, 2H), 7.35 (ddd, J = 7.4, 4.8, 1.3 Hz, 1H), 7.31 (dd, J = 7.9, 1.7 Hz, 1H), 2.48 (s, 3H); 13C NMR (150 MHz, CDCl3) δ 155.4, 149.9, 143.8, 143.3, 136.7, 134.0, 130.7, 129.5, 123.3, 123.2, 118.9, 108.0, 21.8.

4-Acetyl-2-(pyridin-2-yl)benzonitrile (Scheme 2, 3kc)S8

N

CN

O

White solid; m.p. 131 – 132 °C; 1H NMR (600 MHz, CDCl3) δ 8.81 (dt, J = 4.8, 1.3 Hz, 1H), 8.41 (d, J = 1.7 Hz, 1H), 8.06 (dd, J = 8.1, 1.7 Hz, 1H), 7.92 (d, J = 8.0 Hz, 1H), 7.88 (td, J = 7.7, 1.8 Hz, 1H), 7.86 – 7.83 (m, 1H), 7.41 (ddd, J = 7.4, 4.8, 1.2 Hz, 1H), 2.70 (s, 3H); 13C NMR (150 MHz, CDCl3) δ 196.5, 154.3, 150.1, 144.0, 140.0, 137.0, 134.5, 129.6, 127.9, 123.7, 123.2, 117.9, 114.8, 26.8.

2-(5-Acetylpyridin-2-yl)benzonitrile (Scheme 2, 3l)

White solid; m.p. 121 – 122 °C; 1H NMR (600 MHz, CDCl3) δ 9.31 (d, J = 2.3 Hz, 1H), 8.38 (dd, J = 8.2, 2.2 Hz, 1H), 7.92 – 7.87 (m, 2H), 7.84 (dd, J = 7.7, 1.3 Hz, 1H), 7.74 (td, J = 7.7, 1.3 Hz, 1H), 7.57 (td, J = 7.7, 1.2 Hz, 1H), 2.70 (s, 3H); 13C NMR (150 MHz, CDCl3) δ 196.2, 158.7, 150.0, 142.2, 136.5, 134.4, 132.9, 131.5, 130.1, 129.6, 123.0, 118.4, 111.3, 26.8; IR

S-16

(diamond) 3280, 3213, 3090, 3063, 2954, 1728, 1632, 1587, 1524, 1475, 1442, 1215, 1077, 1021, 942 cm-1; HRMS (EI) m/z calcd. for C14H10N2O [M]+: 222.0793, found: 222.0793.

2-(4-Methylpyridin-2-yl)benzonitrile (Scheme 2, 3ma)S6

White solid; m.p. 55 – 56 °C; 1H NMR (600 MHz, CDCl3) δ 8.62 (d, J = 5.0 Hz, 1H), 7.82 (dd, J = 7.9, 1.2 Hz, 1H), 7.79 (dd, J = 7.8, 1.3 Hz, 1H), 7.68 (td, J = 7.7, 1.4 Hz, 1H), 7.59 (brs, 1H), 7.50 (td, J = 7.6, 1.3 Hz, 1H), 7.20 – 7.15 (m, 1H), 2.45 (s, 3H); 13C NMR (150 MHz, CDCl3) δ 155.1, 149.7, 148.0, 143.7, 134.0, 132.7, 129.9, 128.6, 124.3, 124.1, 118.7, 111.1, 21.2.

2-(5-Methylpyridin-2-yl)benzonitrile (Scheme 2, 3mb)S6

White solid; m.p. 79 – 80 °C; 1H NMR (600 MHz, CDCl3) δ 8.60 (brs, 1H), 7.83 (dd, J = 8.0, 1.2 Hz, 1H), 7.79 (dd, J = 7.8, 1.4 Hz, 1H), 7.71 – 7.61 (m, 3H), 7.48 (td, J = 7.6, 1.3 Hz, 1H), 2.42 (s, 3H); 13C NMR (150 MHz, CDCl3) δ 152.5, 150.4, 143.5, 137.2, 134.0, 133.1, 132.7, 129.8, 128.4, 122.7, 118.8, 110.9, 18.3.

2-(1H-Pyrazol-1-yl)benzonitrile (Scheme 2, 3n)S7

Colorless oil; 1H NMR (600 MHz, CDCl3) δ 8.15 (d, J = 2.6 Hz, 1H), 7.83 – 7.76 (m, 3H), 7.74 – 7.68 (m, 1H), 7.43 (t, J = 7.6 Hz, 1H), 6.55 (brs, 1H); 13C NMR (150 MHz, CDCl3) δ 142.2, 142.0, 134.4, 134.0, 129.5, 127.2, 124.3, 116.9, 108.5, 105.3.

2-(Pyrimidin-2-yl)benzonitrile (Scheme 2, 3o)S5

Colorless solid; m.p. 138 – 139 °C; 1H NMR (600 MHz, CDCl3) δ 8.93 (d, J = 4.8 Hz, 2H), 8.38 (d, J = 7.9 Hz, 1H), 7.86 (d, J = 7.7 Hz, 1H), 7.72 (t, J = 7.6 Hz, 1H), 7.58 (t, J = 7.6 Hz,

S-17

1H), 7.34 (t, J = 4.8 Hz, 1H); 13C NMR (150 MHz, CDCl3) δ 162.9, 157.3, 140.3, 135.1, 132.5, 130.4, 130.2, 120.1, 118.9, 111.9.

Benzo[h]quinoline-10-carbonitrile (Scheme 2, 3p)S5

White solid; m.p. 133 – 134 °C; 1H NMR (600 MHz, CDCl3) δ 9.14 (dd, J = 4.3, 1.8 Hz, 1H), 8.22 (dd, J = 8.1, 1.7 Hz, 1H), 8.16 (d, J = 7.3 Hz, 1H), 8.12 (d, J = 8.0 Hz, 1H), 7.83 (d, J = 8.8 Hz, 1H), 7.79 (d, J = 8.8 Hz, 1H), 7.73 (t, J = 7.7 Hz, 1H), 7.63 (dd, J = 8.0, 4.3 Hz, 1H); 13C NMR (150 MHz, CDCl3) δ 148.5, 144.5, 136.2, 135.7, 134.1, 132.7, 130.8, 127.4, 127.2, 127.1, 127.0, 123.0, 120.7, 109.1. 2-(Pyridin-2-yl)thiophene-3-carbonitrile (Scheme 3, 5a)

White solid; m.p. 72 – 73 °C; 1H NMR (600 MHz, CDCl3) δ 8.64 (d, J = 4.6 Hz, 1H), 8.24 (d, J = 8.0 Hz, 1H), 7.83 (td, J = 7.8, 1.8 Hz, 1H), 7.43 (d, J = 5.3 Hz, 1H), 7.35 – 7.28 (m, 2H); 13C NMR (150 MHz, CDCl3) δ 153.6, 149.8, 149.6, 137.3, 130.8, 127.7, 123.9, 120.1, 115.9, 105.9; IR (diamond) 311, 2921, 2851, 2224, 1578, 1462, 947, 782 cm-1; HRMS (EI) m/z calcd. for C10H6N2S [M]+: 186.0252, found: 186.0249.

3-(Pyridin-2-yl)thiophene-2-carbonitrile (Scheme 3, 5ba)

White solid; m.p. 38 – 39 °C; 1H NMR (600 MHz, CDCl3) δ 8.75 – 8.70 (m, 1H), 7.95 (d, J = 7.9 Hz, 1H), 7.82 (td, J = 7.7, 1.8 Hz, 1H), 7.69 (d, J = 5.0 Hz, 1H), 7.62 (d, J = 5.2 Hz, 1H), 7.36 – 7.30 (m, 1H); 13C NMR (150 MHz, CDCl3) δ 150.9, 150.0, 149.9, 137.1, 131.7, 128.3, 123.6, 121.9, 114.7, 106.2; IR (diamond) 3079, 2921, 2850, 2209, 1582, 1463, 1150, 990 cm-1; HRMS (EI) m/z calcd. for C10H6N2S [M]+: 186.0252, found: 186.0251.

2-(Pyridin-2-yl)furan-3-carbonitrile (Scheme 3, 5bb)

Pale yellow solid; m.p. 81 – 82 °C; 1H NMR (600 MHz, CDCl3) δ 8.76 (d, J = 4.8 Hz, 1H), 7.91 (d, J = 7.9 Hz, 1H), 7.83 (td, J = 7.8, 1.8 Hz, 1H), 7.55 (d, J = 2.0 Hz, 1H), 7.34 (dd, J =

S-18

7.5, 4.8 Hz, 1H), 6.76 (d, J = 1.9 Hz, 1H); 13C NMR (150 MHz, CDCl3) δ 158.5, 150.2, 146.8, 143.2, 136.9, 124.1, 120.1, 114.3, 114.0, 94.8; IR (diamond) 3115, 2922, 2227, 1505, 1216, 887 cm-1; HRMS (EI) m/z calcd. for C10H6N2O [M]+: 170.0480, found: 170.0478.

1-(Pyrimidin-2-yl)-1H-pyrrole-2-carbonitrile (Scheme 3, 5c)S9

White solid; m.p. 118 – 119 °C; 1H NMR (600 MHz, CDCl3) δ 8.75 (d, J = 4.8 Hz, 2H), 7.99 (dd, J = 3.1, 1.7 Hz, 1H), 7.23 (t, J = 4.8 Hz, 1H), 7.09 (dd, J = 3.7, 1.7 Hz, 1H), 6.38 (t, J = 3.4 Hz, 1H); 13C NMR (150 MHz, CDCl3) δ 158.6, 155.1, 126.1, 125.0, 118.8, 114.0, 111.8, 102.9.

2-(Pyridin-2-yl)benzo[b]thiophene-3-carbonitrile (Scheme 3, 5da)

White solid; m.p. 159 – 160 °C; 1H NMR (600 MHz, CDCl3) δ 8.74 – 8.67 (m, 1H), 8.43 (d, J = 8.0 Hz, 1H), 8.00 (d, J = 8.0 Hz, 1H), 7.92 – 7.85 (m, 2H), 7.56 – 7.51 (m, 1H), 7.51 – 7.46 (m, 1H), 7.41 – 7.33 (m, 1H); 13C NMR (150 MHz, CDCl3) δ 155.0, 150.0, 149.7, 139.5, 138.3, 137.3, 126.7, 126.0, 124.6, 122.8, 122.6, 121.2, 115.1, 101.9; IR (diamond) 3056, 2921, 2851, 2218, 1582, 1431, 991, 753 cm-1; HRMS (EI) m/z calcd. for C14H8N2S [M]+: 236.0408, found: 236.0409.

2-(Pyridin-2-yl)benzofuran-3-carbonitrile (Scheme 3, 5db)

White solid; m.p. 126 – 127 °C; 1H NMR (600 MHz, CDCl3) δ 8.85 (d, J = 4.2 Hz, 1H), 8.11 (d, J = 7.9 Hz, 1H), 7.89 (td, J = 7.8, 1.7 Hz, 1H), 7.80 (d, J = 7.6 Hz, 1H), 7.64 (d, J = 8.2 Hz, 1H), 7.48 (td, J = 7.8, 1.4 Hz, 1H), 7.45 – 7.38 (m, 2H); 13C NMR (150 MHz, CDCl3) δ 159.9, 153.9, 150.4, 146.8, 137.0, 127.19, 127.16, 124.97, 124.95, 121.3, 120.5, 113.7, 112.1, 91.2; IR (diamond) 2921, 2851, 2224, 1777, 1452, 1158, 742 cm-1; HRMS (EI) m/z calcd. for C14H8N2O [M]+: 220.0637, found: 220.0636.

S-19

4-(Pyridin-2-yl)dibenzo[b,d]thiophene-3-carbonitrile (Scheme 3, 5ea)

Colorless; m.p. 141 – 142 °C; 1H NMR (600 MHz, CDCl3) δ 8.91 – 8.88 (m, 1H), 8.26 (d, J = 8.1 Hz, 1H), 8.24 – 8.20 (m, 1H), 8.01 (d, J = 7.9 Hz, 1H), 7.94 (td, J = 7.7, 1.8 Hz, 1H), 7.90 – 7.85 (m, 2H), 7.58 – 7.49 (m, 2H), 7.49 – 7.42 (m, 1H); 13C NMR (150 MHz, CDCl3) δ 154.3, 149.6, 142.3, 140.1, 139.8, 138.4, 137.1, 134.1, 129.5, 128.4, 124.9, 124.5, 123.9, 122.7, 122.5, 121.5, 119.0, 108.4; IR (diamond) 2919, 2850, 2214, 1583, 1373, 758 cm-1; HRMS (EI) m/z calcd. for C18H10N2S [M]+: 286.0565, found: 286.0563.

4-(Pyridin-2-yl)dibenzo[b,d]furan-3-carbonitrile (Scheme 3, 5eb)

White solid; m.p. 138 – 139 °C; 1H NMR (600 MHz, CDCl3) δ 8.91 (brs, 1H), 8.06 (d, J = 8.0 Hz, 1H), 8.04 (d, J = 7.8 Hz, 1H), 8.01 – 7.97 (m, 1H), 7.95 (td, J = 7.6, 1.7 Hz, 1H), 7.81 (d, J = 8.0 Hz, 1H), 7.63 – 7.60 (m, 1H), 7.59 – 7.53 (m, 1H), 7.49 – 7.40 (m, 2H); 13C NMR (150 MHz, CDCl3) δ 157.4, 153.0, 151.2, 149.9, 136.8, 129.2, 128.9, 128.7, 128.3, 125.5, 123.8, 123.7, 122.8, 121.5, 121.0, 118.7, 112.3, 109.7; IR (diamond) 3057, 2923, 2219, 1628, 1405, 1192, 750 cm-1; HRMS (EI) m/z calcd. for C18H10N2O [M]+: 270.0793, found: 270.0791.

1-(Pyridin-2-yl)-1H-indole-2-carbonitrile (Scheme 3, 5fa)S10

White solid; m.p. 74 – 75 °C; 1H NMR (600 MHz, CDCl3) δ 8.70 (dd, J = 5.0, 1.9 Hz, 1H), 7.96 (td, J = 7.8, 1.9 Hz, 1H), 7.78 (d, J = 8.5 Hz, 1H), 7.71 (d, J = 8.0 Hz, 1H), 7.60 (d, J = 8.1 Hz, 1H), 7.46 – 7.40 (m, 2H), 7.40 – 7.37 (m, 1H), 7.31 – 7.27 (m, 1H); 13C NMR (150 MHz, CDCl3) δ 149.7, 149.6, 138.8, 137.1, 126.9, 126.8, 122.8, 122.7, 122.3, 118.8, 117.3, 113.7, 112.2, 109.0.

S-20

1-(Pyrimidin-2-yl)-1H-indole-2-carbonitrile (Scheme 3, 5fb)S10

White solid; m.p. 121 – 122 °C; 1H NMR (600 MHz, CDCl3) δ 8.81 (d, J = 5.0 Hz, 2H), 8.67 (d, J = 8.5 Hz, 1H), 7.66 (d, J = 8.0 Hz, 1H), 7.48 (t, J = 7.8 Hz, 1H), 7.46 – 7.43 (m, 1H), 7.31 (t, J = 7.6 Hz, 1H), 7.24 – 7.17 (m, 1H); 13C NMR (150 MHz, CDCl3) δ 158.2, 156.4,

136.4, 127.6, 127.4, 123.4, 121.9, 120.8, 117.9, 116.0, 114.1, 108.8.

4-Oxo-1-(pyrimidin-2-yl)-4,5,6,7-tetrahydro-1H-indole-2-carbonitrile (Scheme 3, 5g)

Colorless solid; m.p. 216 – 218 °C; 1H NMR (600 MHz, CDCl3) δ 8.86 (d, J = 4.8 Hz, 2H), 7.42 (s, 1H), 7.39 (t, J = 4.9 Hz, 1H), 3.27 (t, J = 6.3 Hz, 2H), 2.57 (t, J = 6.3 Hz, 2H), 2.27 – 2.10 (m, 2H); 13C NMR (150 MHz, CDCl3) δ 193.4, 158.7, 155.3, 148.0, 122.9, 121.0, 120.0, 113.7, 105.6, 37.7, 25.3, 23.2; IR (diamond) 3228, 2955, 2923, 2216, 1678, 1410, 1215, 824 cm-1; HRMS (EI) m/z calcd. for C13H10N4O [M]+: 238.0855, found: 238.0853.

2-(9-Phenyl-9H-purin-6-yl)benzonitrile (Scheme 4, 7a)

White solid; m.p. 198 – 200 °C; 1H NMR (600 MHz, CDCl3) δ 9.22 (s, 1H), 8.48 (d, J = 7.8 Hz, 1H), 8.45 (s, 1H), 7.94 (d, J = 7.6 Hz, 1H), 7.81 (t, J = 7.7 Hz, 1H), 7.77 (d, J = 7.8 Hz, 2H), 7.69 – 7.59 (m, 3H), 7.53 (t, J = 7.5 Hz, 1H); 13C NMR (150 MHz, CDCl3) δ 153.7, 153.0, 152.3, 144.3, 138.1, 134.9, 134.1, 132.5, 132.0, 131.9, 130.3, 130.0, 128.8, 123.7, 118.3, 112.4; IR (diamond) 3095, 3083, 3048, 2923, 2223, 1590, 1507, 1331, 1182, 927, 755 cm-1; HRMS (EI) m/z calcd. for C18H11N5 [M]+: 297.1014, found: 297.1011.

S-21

2-(9-Ethyl-9H-purin-6-yl)benzonitrile (Scheme 4, 7b)

Colorless solid; m.p. 165 – 166 °C; 1H NMR (600 MHz, CDCl3) δ 9.16 (s, 1H), 8.45 (d, J = 7.9 Hz, 1H), 8.20 (s, 1H), 7.92 (d, J = 7.7 Hz, 1H), 7.78 (t, J = 7.7 Hz, 1H), 7.62 (t, J = 7.7 Hz, 1H), 4.42 (q, J = 7.4 Hz, 2H), 1.63 (t, J = 7.4 Hz, 3H); 13C NMR (150 MHz, CDCl3) δ 153.0, 152.4, 152.2, 144.8, 138.3, 134.9, 132.4, 132.0, 131.5, 130.1, 118.4, 112.3, 39.2, 15.3; IR (diamond) 2968, 2923, 2223, 1577, 1324, 1214, 958, 770 cm-1; HRMS (EI) m/z calcd. for C14H11N5 [M]+: 249.1014, found: 249.1013.

2-(9-Butyl-9H-purin-6-yl)benzonitrile (Scheme 4, 7c)

White solid; m.p. 94 – 95 °C; 1H NMR (600 MHz, CDCl3) δ 9.15 (s, 1H), 8.46 (d, J = 7.9 Hz, 1H), 8.17 (s, 1H), 7.92 (d, J = 7.7 Hz, 1H), 7.78 (t, J = 7.7 Hz, 1H), 7.62 (t, J = 7.7 Hz, 1H), 4.36 (t, J = 7.3 Hz, 2H), 1.97 (quin, J = 7.4 Hz, 2H), 1.42 (sext, J = 7.4 Hz, 2H), 1.00 (t, J = 7.4 Hz, 3H); 13C NMR (150 MHz, CDCl3) δ 153.0, 152.6, 152.2, 145.3, 138.3, 134.9, 132.4, 132.0, 131.4, 130.1, 118.4, 112.2, 43.9, 31.9, 19.9, 13.5; IR (diamond) 2957, 2925, 2871, 2217, 1576, 1328, 1208, 760 cm-1; HRMS (EI) m/z calcd. for C16H15N5 [M]+: 277.1327, found: 277.1325.

2-(9-Benzyl-9H-purin-6-yl)benzonitrile (Scheme 4, 7d)

N

N

N

N

CN

Ph

White solid; m.p. 155 – 157 °C; 1H NMR (600 MHz, CDCl3) δ 9.19 (s, 1H), 8.46 (d, J = 7.8 Hz, 1H), 8.14 (s, 1H), 7.91 (d, J = 7.7 Hz, 1H), 7.77 (t, J = 7.7 Hz, 1H), 7.61 (t, J = 7.6 Hz, 1H), 7.43 – 7.31 (m, 5H), 5.52 (s, 2H); 13C NMR (150 MHz, CDCl3) δ 153.1, 152.6, 152.5, 145.1, 138.1, 135.0, 134.8, 132.4, 132.0, 131.3, 130.2, 129.2, 128.7, 127.9, 118.4, 112.3, 47.52.; IR (diamond) 3054, 2921, 2221, 1580, 1501, 1213, 765 cm-1; HRMS (EI) m/z calcd. for C19H13N5 [M]+: 311.1171, found: 311.1169

S-22

2-(9-Isopropyl-9H-purin-6-yl)-5-methoxybenzonitrile (Scheme 4, 7e)

White solid; m.p. 116 – 118 °C; 1H NMR (600 MHz, CDCl3) δ 9.10 (s, 1H), 8.52 (d, J = 8.8 Hz, 1H), 8.20 (s, 1H), 7.40 (d, J = 2.7 Hz, 1H), 7.32 – 7.25 (m, 1H), 5.00 (sep, J = 6.8 Hz, 1H), 3.92 (s, 3H), 1.70 (d, J = 6.8 Hz, 6H).; 13C NMR (150 MHz, CDCl3) δ 160.6, 152.7, 152.0, 151.8, 142.6, 133.7, 131.4, 130.7, 120.1, 118.5, 113.3, 55.8, 47.6, 22.5; IR (diamond) 3107, 2922, 2850, 2226, 1601, 1181, 1057, 802 cm-1; HRMS (EI) m/z calcd. for C16H15N5O [M]+: 293.1277, found: 293.1276.

5-Acetyl-2-(9-isopropyl-9H-purin-6-yl) (Scheme 4, 7f)

Yellow solid; m.p. 122 – 124 °C; 1H NMR (600 MHz, CDCl3) δ 9.17 (s, 1H), 8.63 (d, J = 8.2 Hz, 1H), 8.47 (d, J = 1.8 Hz, 1H), 8.31 (dd, J = 8.3, 1.9 Hz, 1H), 8.26 (s, 1H), 5.03 (sep, J = 6.8 Hz, 1H), 2.70 (s, 3H), 1.72 (d, J = 6.9 Hz, 6H); 13C NMR (150 MHz, CDCl3) δ 195.5, 152.4, 151.9, 151.6, 143.5, 141.9, 137.8, 134.7, 132.5, 132.0, 131.7, 117.7, 112.9, 47.8, 26.7, 22.5; IR (diamond) 2988, 2922, 2852, 2212, 1688, 1578, 1223, 934 cm-1; HRMS (EI) m/z calcd. for C17H15N5O [M]+: 305.1277, found: 305.1277.

5-Chloro-2-(9-isopropyl-9H-purin-6-yl) (Scheme 4, 7g)

White solid; m.p. 165 – 166 °C; 1H NMR (600 MHz, CDCl3) δ 9.13 (s, 1H), 8.51 (d, J = 8.5 Hz, 1H), 8.23 (s, 1H), 7.88 (d, J = 2.2 Hz, 1H), 7.74 (dd, J = 8.5, 2.2 Hz, 1H), 5.02 (sep, J =

S-23

6.9 Hz, 1H), 1.71 (d, J = 6.8 Hz, 6H); 13C NMR (150 MHz, CDCl3) δ 152.3, 151.9, 151.6, 143.2, 136.7, 136.4, 134.6, 133.3, 132.7, 131.7, 117.2, 113.7, 47.8, 22.5; IR (diamond) 3103, 3042, 2970, 2925, 2228, 1553, 1217, 934 cm-1; HRMS (EI) m/z calcd. for C15H12ClN5 [M]+: 297.0781, found: 297.0780.

2-(7-Isopropyl-7H-pyrrolo[2,3-d]pyrimidin-4-yl)benzonitrile (Scheme 4, 7h)

White solid; m.p. 141 – 143 °C; 1H NMR (600 MHz, CDCl3) δ 9.02 (s, 1H), 7.89 (dd, J = 7.5, 1.4 Hz, 2H), 7.75 (td, J = 7.6, 1.4 Hz, 1H), 7.60 (td, J = 7.4, 1.4 Hz, 1H), 7.42 (d, J = 3.7 Hz, 1H), 6.59 (d, J = 3.6 Hz, 1H), 5.21 (sep, J = 6.8 Hz, 1H), 1.57 (d, J = 6.8 Hz, 6H); 13C NMR (150 MHz, CDCl3) δ 154.6, 150.9, 150.9, 141.4, 134.4, 132.5, 130.5, 129.4, 126.2, 118.1, 116.9, 112.1, 99.7, 46.2, 22.7; IR (diamond) 2970, 2924, 2224, 1558, 1357, 1226, 924, 742 cm-1; HRMS (EI) m/z calcd. for C16H14N4 [M]+: 262.1218, found: 262.1218.

5. H/D

To a drie(18.5 mAgOAc under artemeratuorganic under reanalysis

Figure S

9.09.5

8.6

546

8.6

568

Exchang

ed screw camg, 0.10 mm

(3.3 mg, 2rgon atmospure, filteredlayer was w

educed pressof the crud

MeO

S1. Crude 1H

8.08.5

1.02

1.02

0.98

0.97

7.7

114

7.7

144

7.9

424

7.9

576

8.6

444

8.6

464

8.6

488

8.6

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ge Experim

apped vial wmol), Cp*C20 mol%), phere. The r

d through a washed withsure and the

de mixture.

N

1ba

H NMR of

6.57.07.5

2.00

1.00

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924

6.9

950

6.9

996

7.0

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7.6

601

7.6

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ment

with a spinvCo(CO)I2 (4CD3OD (16reaction mipad of celi

h brine (15e extents of

1

C

CD3OD

(4.0 equiv)

a H/D expe

5.56.0

S-24

vane triangu4.8 mg, 106 μL, 0.40 ixture was site and then

5 mL) and df deuterium

AgOAc (20 mol 1,2-DCE, 120 °C,

Cp*Co(CO)I 2 (10 mAgNTf2 (20 mo

eriment of 1

4.04.55.0f1 (ppm)

ular-shaped 0 mol %), A

mmol) andstirred at 12n washed wdried over Nincorporati

MeO%) 12 h

mol %)l %)

ba with CD

3.03.50

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Teflon stirbAgNTf2 (7d 1,2-dichlo20 °C for 12with EtOAcNa2SO4. Soion was me

N

H/D

H/D

51% D

[D]n-1ba

D3jD.

12.02.5

bar were ad.8 mg, 20 oroethane (2 h, cooled c (10 mL xolvent was reasured by 1

51% D

0.51.0.5

dded 1ba mol %)

(0.5 mL) to room 3). The removed 1H NMR

-0.50.0

0.0

004

S-25

6. Kinetic Isotope Effect Study

6.1. Parallel Experiments

2-Phenylpyridine (1a) (15.5 mg, 0.10 mmol) or [D5]-2-phenylpyridine ([D5]-1a) (16.0 mg, 0.10 mmol) were added to two separate dried screw capped vials with a spinvane triangular-shaped Teflon stirbar along with N-cyanosuccinimide (2d) (18.6 mg, 0.15 mmol), Cp*Co(CO)I2 (10 mol %), AgNTf2 (20 mol %), AgOAc (20 mol%) and 1,2-dichloroethane (0.5 mL) under argon atmosphere. Each of the reaction mixture was stirred at 120 °C for 10 min. Then it was cooled to room temerature, filtered through a pad of silica and the silica pad was washed with EtOAc (10 mL x 2). The solvent was removed under reduced pressure and the residue was analyzed by 1H NMR by using 1,1,2,2-tetrachloroethane (0.10 mmol) as internal standard. Product yield of 3aa was 26% and that of [D4]-3aa was 24% leading to KIE value of 1.1.

6.2. Competitive experiment

To a dried screw capped vial with a spinvane triangular-shaped Teflon stirbar were added 2-phenylpyridine (1a) (15.5 mg, 0.10 mmol), [D5]-2-phenylpyridine ([D5]-1a) (16.0 mg, 0.10 mmol), N-cyanosuccinimide (2d) (37.2 mg, 0.30 mmol), Cp*Co(CO)I2 (10 mol %), AgNTf2 (20 mol %), AgOAc (20 mol%) and 1,2-dichloroethane (1.0 mL) under argon atmosphere. The reaction mixture was stirred at 120 °C for 100 min, cooled to room temerature, filtered through a pad of silica and then washed with EtOAc (15 mL x 2). Solvent was removed under reduced pressure and the residue was purified by column chromatography on silica gel (EtOAc/n-hexane, 3:7) to give a mixture of desired products 3aa + [D4]-3aa. The ratio of 3aa/[D4]-3aa was determined by 1H NMR analysis to give a KIE value of 1.2.

Figure Sand [D5]

7. Refe

(S1) (a)

(b)

Ino

(S2) Ste

(S3) (a)

Go

J.;

Y.

(S4) Ra

(S5) Ki

(S6) Xu

9.09.5

S2. 1H NMR]-2-phenylpy

erences

) Sun, B.; Y

) Frith, S. A

org. Chem.

ephens, R. W

) Grohmann

oodhue, C. E

Iwasawa, N

-X.; Li, J.-H

ao, M. L. N

im, J.; Chan

u, H.; Liu, P

8.08.50

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R of a mixtuyridine ([D5

Yoshino, T.

A.; Spencer

Commun. 2

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n, C.; Wan

E.; Yu, J.-Q

N. J. Am. C

H. Eur. J. O

.; Dhanorka

ng, S. J. Am

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[D4]-3a

D

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D

+

46%

ure of 3aa a]-1a) in one

; Matsunag

r, J. Inorg.

2004, 7, 117

er L. A. Syn

ng, H.; Glo

Q. J. Am. Ch

Chem. Soc.

Org. Chem. 2

ar, R. J. Eur

. Chem. Soc

.-H.; Han, F

5.56.0.5

7.2

673

7.3

500

7.3

580

7.3

624

N

CN

aa

S-26

and [D4]-3ae vessel.

ga, S.; Kana

Synth. 199

74.

nth. Commu

orius, F. O

hem. Soc. 2

2011, 133,

2007, 1457

r. J. Org. Ch

c. 2010, 132

F.-S. Org. L

44.55.0f1 (ppm)

aa from a re

ai, M. Adv. S

0, 28, 273.

un. 1991, 21

Org. Lett. 20

006, 128, 1

1251. (d)

.

hem. 2014,

2, 10272.

ett. 2013, 1

3.03.54.0

action of 2-

Synth. Cata

(c) Li, W.

, 2025.

013, 15, 30

2634. (c) M

Deng, C.-L

5214.

5, 3354.

12.02.5

-phenylpyrid

al. 2014, 35

; Weng, L.

014. (b) C

Mizuno, H.;

L.; Guo, S.-M

0.51.01.5

dine (1a)

56, 1491.

; Jin, G.

hen, X.;

Takaya,

M.; Xie,

-0.50.0

-0.0

003

S-27

(S7) Jin, J.; Wen, Q.; Lu, P.; Wang, Y. Chem. Commun. 2012, 9933.

(S8) Peng, J.; Zhao, J.; Hu, Z.; Liang, D.; Huang, J.; Zhu, Q. Org. Lett. 2012, 14, 4966.

(S9) Xu, S.; Huang, X.; Hong, X.; Xu, B. Org. Lett. 2012, 14, 4614.

(S10) Kou, X.; Zhao, M.; Qiao, X.; Zhu, Y.; Tong, X.; Shen, Z. Chem. Eur. J. 2013, 19, 16880.

S-28

Appendix I

Copies of 1H and 13C NMR Spectral Data

of Compounds Obtained in this Study

S-29

(E)-Ethyl 3-(4-(pyridin-2-yl)phenyl)acrylate (1f)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

3.00

2.04

1.02

1.61

2.06

1.14

1.88

2.01

0.94

0.00

0

1.33

91.

351

1.36

3

4.26

44.

276

4.28

84.

300

6.49

06.

517

7.25

07.

254

7.25

77.

261

7.26

57.

268

7.63

17.

645

7.75

97.

762

8.02

98.

043

8.70

38.

705

8.70

88.

711

8.71

38.

715

0102030405060708090100110120130140150160170180190f1 (ppm)

14.3

3

60.5

4

76.7

9 c

dc

l377

.00

cd

cl3

77.2

1 c

dc

l3

118

.72

120.

57

122.

52

127.

29

128.

47

134.

99

136.

81

140.

97

143.

94

149.

82

156.

40

166.

92

NEtO

O 1f

S-30

4-(Pyridin-2-yl)benzyl acetate (1ga)

-0.0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

3.01

2.10

1.00

2.04

2.12

2.08

0.99

0.00

1

2.12

2

5.16

4

7.22

77.

236

7.23

97.

247

7.26

27.

457

7.47

07.

712

7.72

57.

736

7.73

97.

749

7.75

27.

762

7.76

57.

982

7.99

58.

698

8.70

6

0102030405060708090100110120130140150160170180190f1 (ppm)

20.9

7

65.9

1

76.7

9 c

dc

l377

.00

cd

cl3

77.2

1 c

dc

l3

120.

55

122.

23

127.

09

128.

53

136.

68

136.

78

139.

27

149.

65

156.

90

170.

80

S-31

2-{4-[(tert-Butyldimethylsilyloxy)methyl]phenyl}pyridine (1gb)

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

5.90

9.20

2.12

1.00

2.01

2.05

2.04

0.95

-0.0

000.

115

0.95

5

4.80

3

7.19

47.

198

7.20

27.

205

7.20

97.

213

7.21

77.

255

7.42

27.

436

7.70

87.

719

7.72

27.

730

7.73

37.

956

7.96

9

8.67

88.

686

-100102030405060708090100110120130140150160170180190f1 (ppm)

-5.2

1

18.4

3

25.9

6

64.7

7

76.7

9 c

dc

l377

.00

cd

cl3

77.2

1 c

dc

l3

120.

37

121.

90

126.

39

126.

77

136.

64

138.

09

142.

35

149.

63

157.

40

S-32

2-{4-[(Methoxymethoxy)methyl]phenyl}pyridine (1gc)

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.04

2.17

2.13

1.04

2.12

2.16

2.13

1.00

-0.0

00

3.43

1

4.66

04.

736

7.21

47.

217

7.22

27.

225

7.22

87.

233

7.23

67.

260

7.46

27.

476

7.71

87.

732

7.74

47.

747

7.75

77.

760

7.98

27.

995

8.68

88.

695

0102030405060708090100110120130140150160170180190f1 (ppm)

55.3

9

68.8

4

76.7

9 c

dc

l377

.00

cd

cl3

77.2

1 c

dc

l3

95.7

4

120.

46

122.

07

126.

95

128.

16

136.

69

138.

72

138.

81

149.

67

157.

16

S-33

2-{4-[(4-Methoxybenzyloxy)methyl]phenyl}pyridine (1gd)

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

3.13

2.15

2.16

2.01

1.00

2.00

2.06

2.11

2.10

1.01

-0.0

00

3.81

1

4.51

14.

590

6.88

66.

891

6.89

46.

901

6.90

56.

910

7.29

67.

310

7.46

17.

474

7.72

97.

732

7.73

57.

975

7.98

9

8.68

48.

686

8.68

98.

692

8.69

48.

697

0102030405060708090100110120130140150160170180f1 (ppm)

55.2

7

71.4

471

.76

76.7

9 c

dc

l377

.00

cd

cl3

77.2

1 c

dc

l3

113

.82

120.

48

122.

05

126.

93

128.

1112

9.4

513

0.2

6

136.

71

138.

71

139.

23

149.

65

157.

22

159.

23

S-34

2-(Pyridin-2-yl)benzonitrile (3aa)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

1.05

1.08

1.09

2.08

2.10

1.00

0.0

002

7.2

682

7.3

493

7.3

511

7.3

574

7.3

592

7.3

617

7.3

635

7.3

699

7.3

716

7.4

963

7.4

982

7.5

090

7.5

108

7.5

218

7.5

237

7.6

817

7.6

840

7.6

946

7.6

969

7.7

074

7.7

097

7.7

790

7.7

921

7.7

970

7.7

993

7.8

100

7.8

123

7.8

264

7.8

293

7.8

394

7.8

421

7.8

526

7.8

551

8.7

745

8.7

762

8.7

783

8.7

826

8.7

843

8.7

863

0102030405060708090100110120130140150160170180190f1 (ppm)

76.7

888

cd

cl3

77.0

009

cd

cl3

77.2

128

cd

cl3

111

.00

79

118.

620

012

3.1

559

123.

264

9

128.

679

312

9.9

088

132.

758

413

4.0

566

136.

752

8

143.

419

2

149.

875

0

155.

183

2

122.2122.6123.0123.4123.824.2f1 (ppm)

123

.15

59

123

.26

49

S-35

5-Methyl-2-(pyridin-2-yl)benzonitrile (3ab)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.13

1.00

1.01

0.96

1.98

1.01

0.99

2.44

1

7.26

37.

327

7.33

57.

340

7.34

87.

488

7.50

17.

602

7.74

27.

755

7.76

47.

777

7.81

07.

813

7.82

37.

826

7.83

57.

838

8.75

88.

765

0102030405060708090100110120130140150160170180190f1 (ppm)

20.

845

76.

789

cd

cl3

77.

001

cd

cl3

77.

213

cd

cl3

110.

789

118.

827

123

.08

71

23.1

10

129

.87

31

33.7

24

134

.42

01

36.8

51

139

.13

41

40.5

48

149

.73

3

155

.16

5

123.00123.05123.10123.15123.20f1 (ppm)

123

.087

123

.110

S-36

5-(tert-Butyl)-2-(pyridin-2-yl)benzonitrile (3ac)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

9.04

1.00

1.03

2.95

1.01

1.05

1.36

8

7.26

37.

329

7.33

17.

337

7.33

97.

341

7.34

37.

349

7.35

17.

715

7.71

87.

780

7.78

77.

788

7.79

47.

798

7.83

0

8.76

08.

767

0102030405060708090100110120130140150160170180f1 (ppm)

30.

983

34.

807

76.

788

cd

cl3

77.

000

cd

cl3

77.

212

cd

cl3

110.

623

119.

202

123

.07

51

23.0

86

129

.72

31

30.1

99

131

.11

9

136

.82

5

140

.46

3

149

.77

81

52.3

62

155

.17

2

7.37.47.57.67.77.8f1 (ppm)

1.00

1.03

2.95

1.01

7.2

637

.329

7.3

317

.337

7.3

397

.341

7.3

437

.349

7.3

51

7.7

017

.705

7.7

157

.718

7.7

807

.787

7.7

887

.794

7.7

98

S-37

4-(Pyridin-2-yl)-[1,1'-biphenyl]-3-carbonitrile (3ad)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

1.03

1.03

2.15

2.14

2.09

1.09

1.09

1.00

1.04

7.26

37.

366

7.37

17.

375

7.38

07.

385

7.38

97.

426

7.43

87.

450

7.49

27.

505

7.51

87.

623

7.63

67.

847

7.85

67.

860

7.86

57.

868

7.87

87.

881

7.90

27.

906

7.91

67.

919

7.94

37.

957

8.02

08.

023

8.80

08.

808

0102030405060708090100110120130140150160170180190f1 (ppm)

76.

789

cd

cl3

77.

000

cd

cl3

77.

212

cd

cl3

111.

496

118.

732

123

.16

91

23.3

29

127

.03

51

28.5

26

129

.15

41

30.4

71

131

.38

61

32.5

96

136

.90

61

38.3

45

141

.79

21

41.9

78

149

.90

1

154

.85

3

S-38

5-(Dimethylamino)-2-(pyridin-2-yl)benzonitrile (3ae)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

6.15

1.04

0.98

1.00

3.02

0.96

-0.0

00

3.03

8

6.94

46.

949

6.95

96.

964

7.00

27.

007

7.23

07.

233

7.23

87.

241

7.24

47.

249

7.25

27.

264

7.72

77.

732

7.74

27.

745

7.74

77.

750

7.75

97.

762

8.70

58.

713

0102030405060708090100110120130140150160170180190f1 (ppm)

40.

118

76.

788

cd

cl3

77.

000

cd

cl3

77.

211

cd

cl3

111.

267

116.

032

116.

546

119.

729

122

.02

31

22.3

64

130

.45

51

30.7

08

136

.53

1

149

.59

51

49.8

91

155

.55

5

S-39

5-(Methylthio)-2-(pyridin-2-yl)benzonitrile (3af)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

3.07

1.00

1.01

0.95

2.02

1.06

1.02

2.54

7

7.26

47.

336

7.34

47.

346

7.34

97.

357

7.51

17.

515

7.52

57.

529

7.58

27.

586

7.77

27.

787

7.81

87.

821

7.83

17.

834

7.84

47.

847

8.75

68.

763

0102030405060708090100110120130140150160170180190f1 (ppm)

15.

292

76.

789

cd

cl3

77.

001

cd

cl3

77.

213

cd

cl3

111.

546

118.

410

122

.98

11

23.2

02

130

.07

81

30.2

48

130

.51

2

136

.98

31

39.3

09

141

.04

8

149

.72

5

154

.58

7

121122123124125126127128129130131f1 (ppm)

122.

981

123.

202

130.

078

130.

248

130.

512

S-40

5-Methoxy-2-(pyridin-2-yl)benzonitrile (3ba)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

3.02

1.00

0.93

1.01

3.05

1.04

3.88

8

7.21

17.

216

7.22

67.

230

7.26

37.

271

7.27

57.

312

7.31

47.

320

7.32

27.

325

7.32

77.

333

7.33

57.

754

7.76

77.

790

7.80

57.

808

7.81

87.

821

7.83

3

8.74

38.

751

0102030405060708090100110120130140150160170180f1 (ppm)

55.

747

76.

789

cd

cl3

77.

001

cd

cl3

77.

212

cd

cl3

111.

761

118.

530

118.

583

119.

380

122

.84

11

22.9

28

131

.40

01

35.8

00

136

.90

8

149

.62

3

154

.86

6

159

.60

2

118.4118.6118.8119.0119.2119.4f1 (ppm)

118.

530

118.

583

119.

380

122.6122.75122.85122.95123.05f1 (ppm)

122.

841

122.

928

S-41

5-(Benzyloxy)-2-(pyridin-2-yl)benzonitrile (3bb)

-0.0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

2.09

1.05

1.00

1.93

3.95

3.05

1.01

5.14

9

7.26

37.

278

7.28

27.

292

7.29

77.

309

7.31

77.

321

7.32

97.

348

7.35

37.

364

7.37

67.

403

7.41

67.

428

7.43

57.

447

7.45

07.

749

7.76

27.

784

7.79

97

.811

7.81

47.

824

7.82

7

8.74

28.

750

0102030405060708090100110120130140150160170180190f1 (ppm)

70.

526

76.

788

cd

cl3

77.

001

cd

cl3

77.

213

cd

cl3

111.

794

118.

543

119.

565

120

.17

41

22.8

45

122

.88

81

27.4

55

128

.38

81

28.7

59

131

.41

41

35.7

19

136

.16

21

36.8

20

149

.70

9

154

.89

1

158

.66

8

7.257.307.357.407.457.50f1 (ppm)

1.0

5

1.0

0

1.9

3

3.9

5

7.26

287.

2777

7.28

227.

2923

7.29

687.

3089

7.31

697.

3211

7.32

947.

3482

7.35

267.

3644

7.37

627.

4032

7.41

597.

4280

7.43

497.

4466

7.44

98

S-42

5-Phenoxy-2-(pyridin-2-yl)benzonitrile (3bc)

-0.0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

1.96

1.00

2.98

1.96

1.02

2.05

1.00

7.07

67.

089

7.21

67.

229

7.24

17.

263

7.30

67.

311

7.32

17.

325

7.33

77.

341

7.34

57.

350

7.35

87.

410

7.42

37.

436

7.77

07.

783

7.81

47.

824

7.82

87.

834

7.83

7

8.75

88.

765

0102030405060708090100110120130140150160170180f1 (ppm)

76.7

88 c

dcl

377

.000

cd

cl3

77.2

12 c

dcl

3

112

.084

118

.148

119

.841

122.

616

122.

678

123.

008

123.

093

124.

841

130.

224

131.

669

136.

928

137.

743

149.

767

154.

664

155.

435

158.

106

S-43

3-Cyano-N,N-dimethyl-4-(pyridin-2-yl)benzamide (3ca)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

3.04

3.04

1.00

1.01

1.00

1.92

1.01

0.96

0.0

004

3.0

271

3.1

489

7.2

702

7.3

851

7.3

929

7.3

973

7.4

056

7.7

559

7.7

588

7.8

201

7.8

614

7.8

647

7.8

698

7.9

082

7.9

217

8.7

888

8.7

978

0102030405060708090100110120130140150160170180f1 (ppm)

35.4

857

39.4

719

76.7

881

cd

cl3

77.0

000

cd

cl3

77.2

117

cd

cl3

111

.31

22

117.

928

9

123.

246

712

3.6

815

130.

180

713

1.4

409

132.

718

113

6.9

444

144.

264

7

150.

054

5

154.

416

3

168.

897

3

S-44

5-Acetyl-2-(pyridin-2-yl)benzonitrile (3cb)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

3.16

1.02

2.08

1.09

1.06

1.00

1.07

2.67

7

7.26

47.

406

7.41

37.

416

7.41

87.

426

7.85

57.

871

7.88

47.

982

7.99

68.

236

8.25

08.

372

8.80

88.

816

0102030405060708090100110120130140150160170180190200210f1 (ppm)

26.

634

76.

789

cd

cl3

77.

001

cd

cl3

77.

212

cd

cl3

111.

670

117.

906

123

.40

11

23.9

92

130

.46

81

32.0

98

134

.22

61

36.9

52

137

.03

5

146

.84

61

50.1

06

154

.05

2

195

.53

6

S-45

Methyl 3-cyano-4-(pyridin-2-yl)benzoate (3cc)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

3.14

1.00

2.07

1.03

1.02

0.95

0.96

-0.0

00

3.9

90

7.2

667

.397

7.3

997

.405

7.4

077

.409

7.4

117

.417

7.4

197

.850

7.8

527

.952

7.9

66

8.3

228

.336

8.4

708

.473

8.8

028

.804

8.8

078

.810

8.8

128

.815

0102030405060708090100110120130140150160170180f1 (ppm)

52.

709

76.

788

cd

cl3

77.

000

cd

cl3

77.

212

cd

cl3

111.

481

117.

827

123

.38

91

23.9

19

130

.24

01

30.7

02

133

.53

91

35.3

58

136

.95

3

146

.96

01

50.1

33

154

.20

4

164

.97

3

S-46

5-(1,3-Dioxolan-2-yl)-2-(pyridin-2-yl)benzonitrile (3d)

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

4.13

0.96

1.00

1.96

2.02

0.96

0.99

0.00

1

4.05

74.

067

4.07

84.

084

4.09

04.

106

4.11

24.

120

4.12

44.

125

4.12

84.

133

4.14

44.

154

7.26

67.

354

7.36

27.

366

7.37

47.

780

7.79

37.

839

7.84

27.

865

7.87

87.

930

8.77

68.

784

0102030405060708090100110120130140150160170180f1 (ppm)

65.

419

76.

788

cd

cl3

77.

000

cd

cl3

77.

212

cd

cl3

102

.13

7

111.

088

118.

456

123

.24

01

23.4

21

130

.05

81

30.9

111

32.1

64

136

.81

51

39.3

91

143

.93

1

149

.97

2

154

.87

2

112114116118120122124126128130132f1 (ppm)

111.

088

118.

456

123.

240

123.

421

130.

058

130.

911

132.

164

S-47

2-(Pyridin-2-yl)-5-(trifluoromethyl)benzonitrile (3e)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

1.01

1.00

1.04

1.02

1.03

0.96

1.00

7.26

37.

422

7.43

07.

434

7.44

27.

850

7.89

57.

897

7.95

08.

020

8.03

48.

064

8.06

8

8.81

28.

820

0102030405060708090100110120130140150160170180f1 (ppm)

76.7

879

cd

cl3

77.0

001

cd

cl3

77.2

115

cd

cl3

111

.934

611

7.3

502

123.

309

712

4.06

38

129.

408

712

9.43

25

130.

724

313

0.98

41

131.

009

713

1.03

50

137.

040

8

146.

511

215

0.20

66

153.

751

9

7.27.37.47.57.67.77.87.98.08.1f1 (ppm)

1.01

1.00

1.04

1.02

1.03

0.96

7.2

63

7.4

227

.430

7.4

347

.442

7.8

377

.850

7.8

827

.885

7.8

957

.897

7.9

087

.910

7.9

367

.950

8.0

208

.034

8.0

648

.068

120121122123124125126f1 (ppm)

12

0.2

23

7

12

2.0

32

8

12

3.3

09

7

12

3.8

42

11

24.

06

38

12

5.6

51

4

129.0129.5130.0130.5131.0131.52.0f1 (ppm)

12

9.3

85

61

29.

40

87

12

9.4

32

51

29.

45

61

13

0.7

24

31

30.

95

54

13

0.9

84

11

31.

00

97

13

1.0

35

01

31.

06

06

13

1.1

80

41

31.

40

57

13

1.6

31

5

S-48

(E)-Ethyl 3-[3-cyano-4-(pyridin-2-yl)phenyl]acrylate (3f)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

3.12

2.12

1.05

1.00

1.06

2.08

1.05

1.02

1.02

0.97

0.00

0

1.34

61.

358

1.37

0

1.65

6

4.28

04.

292

4.30

44.

316

6.52

96.

555

7.26

77.

382

7.38

47.

386

7.39

27.

394

7.67

37.

700

7.83

27.

902

7.93

07.

933

8.78

58.

787

8.79

08.

793

8.79

68.

798

0102030405060708090100110120130140150160170180f1 (ppm)

14.

253

60.

872

76.

788

cd

cl3

77.

000

cd

cl3

77.

212

cd

cl3

111.

820

118.

107

121

.19

91

23.1

45

123

.63

3

130

.56

01

31.6

75

133

.46

91

35.2

63

136

.89

01

41.3

03

144

.19

1

150

.04

3

154

.36

4

166

.13

3

S-49

3-Cyano-4-(pyridin-2-yl)benzyl acetate (3ga)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

2.99

2.10

1.00

1.04

1.95

2.05

0.97

0.00

0

2.15

4

5.18

1

7.26

87.

357

7.35

97.

366

7.36

87.

370

7.37

27.

378

7.38

07.

677

7.79

57.

798

7.80

17.

844

7.84

77.

852

7.86

5

8.77

68.

783

0102030405060708090100110120130140150160170180190f1 (ppm)

20.

839

64.

569

76.

788

cd

cl3

77.

000

cd

cl3

77.

212

cd

cl3

111.

304

118.

370

123

.15

01

23.4

22

130

.211

132

.25

81

33.3

36

136

.83

31

37.2

04

143

.111

149

.97

1

154

.74

5

170

.51

5

S-50

5-[(tert-Butyldimethylsilyloxy)methyl]-2-(pyridin-2-yl)benzonitrile (3gb)

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

6.10

9.66

2.15

1.04

1.09

4.16

1.00

-0.0

000.

135

0.96

3

4.80

9

7.26

37.

334

7.33

67.

343

7.34

57.

347

7.34

97.

355

7.35

77.

618

7.63

27.

765

7.76

77.

777

7.79

07.

812

7.81

67.

819

7.82

57.

828

7.83

17.

841

7.84

48.

767

8.77

5

-100102030405060708090100110120130140150160170180f1 (ppm)

-5.3

01

18.

377

25.

888

63.

727

76.

788

cd

cl3

77.

000

cd

cl3

77.

211

cd

cl3

110.

847

118.

888

123

.14

51

23.1

69

129

.85

91

30.2

89

131

.37

7

136

.75

4

142

.02

61

42.7

43

149

.89

7

155

.20

9

123.00123.05123.10123.15123.20123.25f1 (ppm)

12

3.1

45

12

3.1

69

S-51

5-[(Methoxymethoxy)methyl]-2-(pyridin-2-yl)benzonitrile (3gc)

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

2.95

2.10

2.05

1.03

1.08

4.14

1.00

-0.0

00

3.43

2

4.67

84.

749

7.34

77.

349

7.35

57.

357

7.35

97.

361

7.36

77.

369

7.79

57.

811

7.81

47.

837

7.83

97.

852

8.77

18.

773

8.77

58.

779

8.78

18.

783

0102030405060708090100110120130140150160170180f1 (ppm)

55.

563

67.

669

76.

789

cd

cl3

77.

001

cd

cl3

77.

212

cd

cl3

95.

991

111.

070

118.

614

123

.17

11

23.3

02

130

.03

41

31.7

94

132

.88

21

36.8

08

139

.35

61

42.5

91

149

.92

9

154

.97

7

122122.7122.9123.1123.3123.5123.7f1 (ppm)

123.

171

123.

302

S-52

5-[(4-Methoxybenzyloxy)methyl]-2-(pyridin-2-yl)benzonitrile (3gd)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

3.04

2.12

2.14

2.04

2.05

1.05

1.10

2.04

2.11

1.00

-0.0

00

3.82

3

4.54

54.

591

6.90

86.

911

6.91

96.

922

7.26

17.

296

7.31

07.

788

7.79

07.

791

7.79

37.

826

7.83

9

8.76

88.

770

8.77

28.

776

8.77

88.

780

0102030405060708090100110120130140150160170180f1 (ppm)

55.

302

70.

208

72.

331

76.

788

cd

cl3

76.

999

cd

cl3

77.

211

cd

cl3

111.

031

113.

960

118.

667

123

.17

71

23.2

75

129

.48

61

29.6

46

130

.02

91

31.7

95

132

.88

81

36.7

94

139

.81

51

42.5

57

149

.93

4

155

.06

2

159

.45

2

123124125126127128129130131132133f1 (ppm)

123

.177

123

.275

129

.486

129

.646

130

.029

131

.795

132

.888

S-53

3-(Pyridin-2-yl)-2-naphthonitrile (3h)

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

1.00

1.02

1.02

1.98

2.08

1.00

0.99

0.98

0.00

1

7.26

27.

363

7.37

07.

378

7.38

57.

616

7.62

87.

641

7.66

07.

672

7.68

47.

861

7.86

87.

926

7.93

97.

950

7.96

48.

279

8.39

4

8.81

48.

822

0102030405060708090100110120130140150160170180f1 (ppm)

76.

788

cd

cl3

77.

000

cd

cl3

77.

212

cd

cl3

108

.77

7

118.

940

123

.06

71

23.3

03

128

.01

91

28.0

43

128

.53

41

29.4

30

129

.68

51

31.8

34

134

.56

81

36.5

13

136

.79

81

37.7

30

149

.90

2

155

.52

5

127.8127.9128.0128.1128.2128.3128.4128.5128.6128.7f1 (ppm)

128.

019

128.

043

128.

534

S-54

5-Chloro-2-(pyridin-2-yl)benzonitrile (3ia)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

1.00

0.98

1.85

1.98

1.02

7.26

37.

369

7.37

77.

381

7.38

97.

671

7.67

57.

774

7.77

97.

794

7.81

97.

834

7.85

3

8.77

38.

781

0102030405060708090100110120130140150160170180f1 (ppm)

76.

788

cd

cl3

77.

000

cd

cl3

77.

212

cd

cl3

112.

462

117.

386

123

.11

01

23.6

08

131

.32

31

33.1

59

133

.60

11

35.0

01

137

.01

81

41.7

26

149

.97

4

154

.05

3

S-55

5-Bromo-2-(pyridin-2-yl)benzonitrile (3ib)

-0.0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

1.00

1.02

1.00

0.98

1.00

0.90

1.03

7.26

37.

375

7.38

37.

388

7.39

67.

745

7.75

97.

796

7.81

57.

818

7.92

97.

932

8.77

48.

781

0102030405060708090100110120130140150160170180f1 (ppm)

76.

789

cd

cl3

77.

001

cd

cl3

77.

212

cd

cl3

112.

691

117.

268

122

.64

81

23.0

79

123

.63

4

131

.41

91

36.0

86

136

.45

31

37.0

31

142

.15

1

150

.00

1

154

.10

1

122124126128130132134136138f1 (ppm)

122

.648

123

.079

123

.634

131

.419

136

.086

136

.453

137

.031

S-56

5-Fluoro-2-(pyridin-2-yl)benzonitrile (3ic)

-0.0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

1.02

1.03

0.97

1.00

2.03

1.00

7.26

37.

360

7.36

87.

372

7.38

07.

396

7.40

17.

410

7.41

57.

424

7.42

97.

492

7.49

67.

505

7.51

07.

761

7.77

57.

832

7.83

57.

845

7.84

87.

858

7.86

27.

872

8.76

58.

773

0102030405060708090100110120130140150160170180f1 (ppm)

76.

789

cd

cl3

77.

001

cd

cl3

77.

212

cd

cl3

112.

438

112.

501

117.

432

117.

445

120

.43

11

20.5

71

120

.63

21

20.7

97

123

.09

61

23.4

10

132

.12

21

32.1

78

136

.95

61

39.8

69

149

.93

0

154

.21

9

161

.16

11

62.8

32

S-57

5-(Methylsulfonyl)-2-(pyridin-2-yl)benzonitrile (3j)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

3.19

1.04

1.04

1.06

1.06

1.04

0.95

1.00

-0.0

00

3.13

7

7.26

67.

442

7.44

47.

450

7.45

27.

454

7.45

67.

462

7.46

47.

874

8.09

78.

110

8.22

98.

232

8.38

08.

383

8.82

38.

831

0102030405060708090100110120130140150160170180f1 (ppm)

44.

469

76.

788

cd

cl3

77.

000

cd

cl3

77.

212

cd

cl3

112.

545

116.

915

123

.46

01

24.3

86

131

.26

91

33.2

43

137

.15

71

41.1

80

147

.99

01

50.3

37

153

.30

7

N

CNS

3j

Me

O

O

S-58

4-Methoxy-2-(pyridin-2-yl)benzonitrile (3ka)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

3.20

1.05

2.02

1.00

1.02

1.02

0.98

0.00

0

3.92

4

6.99

77.

001

7.01

17.

015

7.26

67.

351

7.35

47.

356

7.36

17.

366

7.37

17.

374

7.70

77.

721

7.81

57.

817

7.81

97.

841

8.76

28.

764

8.76

68.

770

8.77

28.

774

0102030405060708090100110120130140150160170180f1 (ppm)

55.

711

76.

788

cd

cl3

77.

000

cd

cl3

77.

212

cd

cl3

102

.69

5

115.

047

115.

117

119.

061

123

.32

11

23.4

20

135

.69

71

36.7

93

145

.58

5

149

.89

7

155

.15

7

162

.83

7

114.0114.5115.0115.5116.0f1 (ppm)

115

.04

711

5.1

17

122.2122.6123.0123.4123.8124.2f1 (ppm)

12

3.3

21

12

3.4

20

S-59

4-Methyl-2-(pyridin-2-yl)benzonitrile (3kb)

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

3.06

1.01

1.00

1.96

0.99

1.03

0.97

0.00

0

2.48

4

7.26

67.

304

7.30

67.

317

7.32

07.

340

7.34

27.

348

7.35

07.

352

7.35

47.

360

7.36

27.

669

7.67

07.

678

7.69

27.

799

7.83

4

8.76

38.

766

8.76

88.

772

8.77

48.

776

0102030405060708090100110120130140150160170180f1 (ppm)

21.

798

76.

788

cd

cl3

77.

000

cd

cl3

77.

212

cd

cl3

108

.00

1

118.

936

123

.21

81

23.3

01

129

.52

91

30.7

02

133

.96

11

36.7

41

143

.34

51

43.8

28

149

.89

7

155

.36

4

122.7122.9123.1123.3123.5123.7f1 (ppm)

123.

218

123.

301

S-60

4-Acetyl-2-(pyridin-2-yl)benzonitrile (3kc)

-0.0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

3.06

1.00

1.00

1.02

0.99

1.04

0.99

0.97

-0.0

00

2.69

6

7.26

57.

400

7.40

37.

408

7.41

17.

413

7.41

57.

421

7.42

37.

850

7.90

97.

922

8.05

9

8.40

58.

407

8.80

48.

806

8.80

88.

812

8.81

48.

816

0102030405060708090100110120130140150160170180190200210f1 (ppm)

26.

848

76.

789

cd

cl3

77.

001

cd

cl3

77.

212

cd

cl3

114

.82

411

7.8

97

123

.22

31

23.7

61

127

.89

01

29.6

15

134

.53

21

37.0

19

140

.04

11

43.9

90

150

.09

6

154

.33

6

196

.49

3

S-61

2-(5-Acetylpyridin-2-yl)benzonitrile (3l)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5

f1 (ppm)

3.05

1.02

1.05

0.98

2.02

1.02

1.00

2.69

8

7.26

37.

574

7.88

57.

898

7.90

27.

916

8.37

38.

377

8.38

78.

390

9.31

19.

315

0102030405060708090100110120130140150160170180190200210f1 (ppm)

26.

830

76.

788

cd

cl3

77.

000

cd

cl3

77.

211

cd

cl3

111.

282

118.

369

123

.01

8

129

.55

81

30.0

71

131

.46

11

32.9

34

134

.38

51

36.5

21

142

.20

0

150

.01

2

158

.69

1

196

.15

8

N

CN3l

O

S-62

2-(4-Methylpyridin-2-yl)benzonitrile (3ma)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

3.06

1.00

1.03

0.98

1.05

0.97

1.00

0.97

0.0

00

2.4

55

7.1

73

7.1

76

7.1

82

7.1

85

7.2

66

7.4

82

7.4

84

7.4

94

7.4

96

7.5

07

7.5

09

7.5

87

7.6

66

7.6

69

7.6

79

7.6

81

7.6

92

7.6

94

7.7

85

7.7

88

7.7

98

7.8

01

7.8

14

7.8

16

7.8

27

7.8

29

8.6

20

8.6

28

0102030405060708090100110120130140150160170180f1 (ppm)

21.

155

76.

789

cd

cl3

77.

001

cd

cl3

77.

213

cd

cl3

111.

085

118.

675

124

.14

71

24.2

59

128

.57

61

29.9

19

132

.71

91

34.0

29

143

.68

51

48.0

22

149

.66

0

155

.14

7

124125126127128129f1 (ppm)

124.

147

124.

259

128.

576

S-63

2-(5-Methylpyridin-2-yl)benzonitrile (3mb)

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

3.08

1.00

2.96

0.95

0.99

0.96

-0.0

00

2.41

5

7.26

57.

468

7.47

07.

481

7.48

37.

494

7.49

67.

630

7.63

47.

643

7.64

77.

662

7.66

47.

675

7.67

87.

687

7.69

07.

692

7.77

77.

780

7.79

07.

793

7.81

97.

821

7.83

27.

834

8.60

2

0102030405060708090100110120130140150160170180f1 (ppm)

18.

258

76.

789

cd

cl3

77.

001

cd

cl3

77.

212

cd

cl3

110.

944

118.

795

122

.66

4

128

.41

51

29.8

02

132

.74

61

33.1

23

134

.02

61

37.2

41

143

.55

1

150

.40

01

52.4

86

S-64

2-(1H-Pyrazol-1-yl)benzonitrile (3n)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

0.94

1.00

1.02

2.99

0.95

6.5

485

6.5

518

6.5

553

7.2

629

7.4

330

7.4

458

7.7

108

7.7

770

7.7

898

7.7

939

7.8

078

7.8

172

8.1

458

8.1

501

0102030405060708090100110120130140150160170180f1 (ppm)

76.

789

cd

cl3

77.

000

cd

cl3

77.

212

cd

cl3

105

.34

9

108

.46

2

116.

949

124

.29

61

27.1

94

129

.511

133

.95

61

34.4

24

142

.04

71

42.2

38

141.6141.8142.0142.2142.4142.6f1 (ppm)

142.

047

142.

238

S-65

2-(Pyrimidin-2-yl)benzonitrile (3o)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

1.05

1.02

1.04

0.99

1.00

2.03

7.26

37.

327

7.33

57.

343

7.56

77.

580

7.59

27.

708

7.72

17.

734

7.85

17.

864

8.36

98.

382

8.92

28.

930

0102030405060708090100110120130140150160170180f1 (ppm)

76.

789

cd

cl3

77.

000

cd

cl3

77.

212

cd

cl3

111.

900

118.

876

120

.11

7

130

.20

71

30.4

34

132

.52

81

35.0

58

140

.30

4

157

.32

9

162

.86

5

S-66

Benzo[h]quinoline-10-carbonitrile (3p)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

1.01

0.99

1.04

1.00

1.00

0.95

1.00

1.00

7.26

37.

730

7.78

37.

797

7.82

28.

112

8.12

58.

150

8.16

28.

216

8.21

9

9.13

29.

135

9.14

09.

143

0102030405060708090100110120130140150160170180f1 (ppm)

76.

788

cd

cl3

77.

000

cd

cl3

77.

212

cd

cl3

109

.02

5

120

.73

51

23.0

33

126

.97

41

27.0

79

127

.23

41

27.3

65

130

.78

01

32.6

76

134

.07

61

35.6

71

136

.24

0

144

.51

7

148

.48

4

126.8126.9127.0127.1127.2127.3127.4127.5127.6f1 (ppm)

126.

974

127.

079

127.

234

127.

365

S-67

3-(Pyridin-2-yl)thiophene-2-carbonitrile (5a)

-0.0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

1.05

1.01

1.03

1.07

1.04

1.00

-0.0

00

7.26

47.

315

7.32

37.

328

7.33

67.

614

7.62

27.

688

7.69

77.

939

7.95

2

8.72

58.

727

8.72

98.

733

8.73

58.

737

0102030405060708090100110120130140150160170180f1 (ppm)

76.

788

cd

cl3

77.

000

cd

cl3

77.

212

cd

cl3

106

.23

6

114.

690

121

.89

61

23.6

08

128

.35

01

31.7

15

137

.07

4

149

.94

61

49.9

77

150

.93

2

149.90149.95150.00f1 (ppm)

149.

946

149.

977

S-68

2-(Pyridin-2-yl)thiophene-3-carbonitrile (5ba)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

1.99

0.98

1.03

0.98

1.00

7.26

47.

300

7.30

87.

315

7.32

07.

324

7.42

17.

430

7.81

57.

825

7.82

8

8.23

88.

251

8.63

88.

646

0102030405060708090100110120130140150160170180f1 (ppm)

76.7

89 c

dc

l377

.001

cd

cl3

77.2

12 c

dc

l3

105

.88

4

115.

876

120

.07

912

3.9

23

127

.72

513

0.8

35

137

.33

3

149

.60

614

9.8

28

153

.59

8

149150151152153154f1 (ppm)

149.

606

149.

828

153.

598

S-69

2-(Pyridin-2-yl)furan-3-carbonitrile (5bb)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

0.98

1.03

1.00

1.03

1.00

1.02

6.76

36.

766

7.26

37.

326

7.33

47.

338

7.34

67.

553

7.55

67.

825

7.82

87.

838

7.84

17.

903

7.91

7

8.76

08.

768

0102030405060708090100110120130140150160170180f1 (ppm)

76.7

88 c

dc

l377

.000

cd

cl3

77.2

11 c

dc

l3

94.8

30

113.

991

114.

261

120

.15

3

124

.15

2

136

.88

9

143

.23

714

6.8

29

150

.18

2

158

.49

2

113114115116117118119120121122123124125f1 (ppm)

113.

991

114.

261

120.

153

124.

152

S-70

1-(Pyrimidin-2-yl)-1H-pyrrole-2-carbonitrile (5c)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

1.03

1.01

1.04

1.00

2.00

6.37

46.

380

6.38

6

7.08

17.

084

7.08

87.

090

7.22

67.

234

7.24

27.

267

7.99

07.

993

7.99

67.

998

8.74

28.

750

0102030405060708090100110120130140150160170180f1 (ppm)

76.7

88 c

dc

l377

.000

cd

cl3

77.2

12 c

dc

l3

102

.88

8

111.

758

114.

043

118.

844

124

.97

612

6.1

24

155

.13

5

158

.57

6

S-71

2-(Pyridin-2-yl)benzo[b]thiophene-3-carbonitrile (5da)

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

1.07

1.07

1.07

2.07

1.01

1.00

0.99

-0.0

00

7.36

57.

366

7.37

37.

374

7.37

87.

379

7.38

67.

387

7.47

17.

473

7.48

57.

496

7.49

87.

521

7.52

37.

535

7.54

67.

548

7.88

97.

903

7.99

4

8.42

78.

440

8.71

18.

712

8.71

58.

719

8.72

18.

723

0102030405060708090100110120130140150160170180f1 (ppm)

76.7

89 c

dc

l377

.001

cd

cl3

77.2

12 c

dc

l3

101

.90

7

115.

143

121

.21

612

2.6

00

122

.85

112

4.6

33

126

.05

212

6.6

76

137

.31

813

8.3

06

139

.45

7

149

.70

514

9.9

96

154

.98

7

13613814014214414614815015215456f1 (ppm)

137.

318

138.

306

139.

457

149.

705

149.

996

154.

987

10105110115120125f1 (ppm)

101.

907

115.

143

121.

216

122.

600

122.

851

124.

633

126.

052

126.

676

S-72

2-(Pyridin-2-yl)benzofuran-3-carbonitrile (5db)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

2.01

1.00

1.01

0.97

1.02

1.00

1.08

7.26

47.

400

7.40

77.

412

7.41

57.

420

7.42

87.

441

7.46

27.

465

7.47

67.

478

7.48

87.

491

7.63

07.

644

7.79

37.

805

7.87

47.

877

7.88

77.

890

7.90

07.

903

8.10

58.

118

8.84

58.

851

0102030405060708090100110120130140150160170180f1 (ppm)

76.7

88 c

dc

l377

.000

cd

cl3

77.2

12 c

dc

l3

91.2

51

112.

075

113.

669

120

.52

212

1.3

36

124

.95

312

4.9

70

127

.16

312

7.1

86

136

.99

6

146

.78

515

0.4

22

153

.87

3

159

.89

7

125.0125.5126.0126.5127.0f1 (ppm)

124.

953

124.

970

127.

163

127.

186

S-73

4-(Pyridin-2-yl)dibenzo[b,d]thiophene-3-carbonitrile (5ea)

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

1.05

2.15

2.04

1.07

1.02

1.07

1.09

1.00

0.00

0

7.26

07.

447

7.44

97.

455

7.45

77.

460

7.46

27.

468

7.47

07.

508

7.51

07.

520

7.52

27.

532

7.53

57.

538

7.54

77.

550

7.56

07.

562

7.86

97.

874

7.88

78.

006

8.25

68.

269

8.89

18.

893

8.89

58.

900

8.90

28.

904

0102030405060708090100110120130140150160170180f1 (ppm)

76.

788

cd

cl3

77.

000

cd

cl3

77.

212

cd

cl3

108

.43

9

118.

978

121

.49

21

22.5

24

122

.65

71

23.9

37

124

.55

01

24.8

73

128

.38

01

29.5

07

134

.07

81

37.0

60

138

.36

01

39.7

92

140

.08

21

42.3

44

149

.64

1

154

.33

4

110115120125130135140145150155f1 (ppm)

108.439

118.978

121.492

122.524

122.657

123.937

124.550

124.873

128.380

129.507

134.078

137.060

138.360

139.792

140.082

142.344

149.641

154.334

SN

CN

5ea

S-74

4-(Pyridin-2-yl)dibenzo[b,d]furan-3-carbonitrile (5eb)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

2.00

1.02

1.00

0.98

1.95

1.99

1.06

7.41

97.

421

7.43

27.

444

7.44

67.

450

7.45

67.

458

7.46

07.

463

7.46

87.

471

7.54

97.

551

7.56

17.

563

7.56

57.

575

7.57

77.

607

7.62

17.

800

7.81

37.

937

7.94

07.

950

7.95

37.

963

7.96

67.

981

7.99

48.

029

8.04

28.

053

8.06

78.

913

0102030405060708090100110120130140150160170180f1 (ppm)

76.7

89 c

dc

l377

.001

cd

cl3

77.2

13 c

dc

l3

109

.73

311

2.27

112

0.9

61

121

.55

512

2.8

18

123

.71

312

3.8

27

128

.69

812

8.9

37

129

.24

5

136

.76

3

149

.85

815

1.1

65

152

.95

615

7.3

55

118119120121122123124125126127128129130f1 (ppm)

118

.661

120

.961

121

.555

122

.818

123

.713

123

.827

125

.530

128

.285

128

.698

128

.937

129

.245

S-75

1-(Pyridin-2-yl)-1H-indole-2-carbonitrile (5fa)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

1.07

1.04

2.02

1.04

1.04

1.04

1.06

1.00

0.00

0

7.25

67.

270

7.28

37.

295

7.37

57.

383

7.38

77.

396

7.41

17.

423

7.42

67.

428

7.43

77.

439

7.59

87.

611

7.70

77.

720

7.76

97.

783

7.94

17.

944

7.95

47.

957

7.96

77.

970

8.69

18.

694

8.69

98.

703

0102030405060708090100110120130140150160170180f1 (ppm)

76.7

89 c

dc

l377

.000

cd

cl3

77.2

12 c

dc

l3

109

.05

211

2.24

411

3.68

111

7.34

811

8.79

312

2.3

03

122

.68

412

2.7

70

126

.82

912

6.9

19

137

.03

913

8.8

51

149

.62

714

9.6

57

S-76

1-(Pyrimidin-2-yl)-1H-indole-2-carbonitrile (5fb)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

1.00

1.04

0.93

1.04

1.03

1.01

1.97

7.20

17.

209

7.21

77.

263

7.29

77.

309

7.32

27.

447

7.47

07.

483

7.49

67.

652

7.66

5

8.65

98.

673

8.80

38.

812

0102030405060708090100110120130140150160170180f1 (ppm)

76.7

88 c

dc

l377

.000

cd

cl3

77.2

12 c

dc

l3

108

.79

4

114.

101

116.

050

117.

856

120

.85

312

1.8

82

123

.38

712

7.4

06

127

.63

2

136

.43

4

156

.39

915

8.1

77

120121122123124125126127128f1 (ppm)

120.

853

121.

882

123.

387

127.

406

127.

632

S-77

4-Oxo-1-(pyrimidin-2-yl)-4,5,6,7-tetrahydro-1H-indole-2-carbonitrile (5g)

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

2.21

2.22

2.18

1.00

0.89

1.99

0.00

0

2.17

62.

187

2.19

72.

208

2.21

92.

564

2.57

42.

585

3.26

33.

273

3.28

4

7.26

77.

377

7.38

57.

393

7.41

5

8.85

68.

864

0102030405060708090100110120130140150160170180190200210f1 (ppm)

23.2

4625

.321

37.6

63

76.7

89 c

dc

l377

.001

cd

cl3

77.2

12 c

dc

l3

105

.60

1

113.

158

119.

953

120

.97

012

2.9

29

148

.03

0

155

.33

915

8.7

13

193

.42

8

N

NN

CN

O

5g

S-78

2-(9-Phenyl-9H-purin-6-yl)benzonitrile (7a)

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

1.03

3.12

2.04

1.08

1.00

0.95

1.01

0.94

-0.0

00

7.26

67.

517

7.53

07.

542

7.62

47.

637

7.65

07.

663

7.76

77.

780

7.80

17.

814

7.82

67.

937

7.95

08.

450

8.47

68.

489

9.21

7

0102030405060708090100110120130140150160170180f1 (ppm)

76.7

89 c

dc

l377

.001

cd

cl3

77.2

13 c

dc

l3

112.

364

118.

318

123

.711

128

.77

613

0.0

49

130

.29

613

2.0

28

132

.50

613

4.9

50

138

.08

3

144

.27

9

152

.27

915

2.9

92

153

.72

2

129130131132133134135f1 (ppm)

128.

776

130.

049

130.

296

131.

903

132.

028

132.

506

134.

109

134.

950

N

N

N

NPh

CN

7a

S-79

2-(9-Ethyl-9H-purin-6-yl)benzonitrile (7b)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.22

2.19

1.07

1.09

1.00

0.99

1.03

0.95

-0.0

00

1.61

81.

631

1.64

3

4.40

14.

414

4.42

64.

438

7.27

37.

605

7.61

87.

631

7.77

07.

781

7.79

57.

911

7.92

48.

196

8.44

08.

453

9.15

6

0102030405060708090100110120130140150160170180f1 (ppm)

15.3

23

39.1

86

76.7

8977

.000

77.2

12

112.

257

118.

376

130.

099

131.

554

131.

958

132.

443

134.

903

138.

274

144.

843

152.

164

152.

426

152.

989

152.0152.2152.4152.6152.8153.0153.2f1 (ppm)

152.

164

152.

426

152.

989

130.0130.5131.0131.5132.0132.5f1 (ppm)

130.

099

131.

554

131.

958

132.

443

S-80

2-(9-Butyl-9H-purin-6-yl)benzonitrile (7c)

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.01

2.12

2.06

2.02

1.02

1.04

0.98

1.01

1.00

0.92

-0.0

00

0.98

81.

000

1.01

31.

414

1.42

71.

440

1.94

11.

953

1.96

61.

979

1.99

1

4.34

44.

356

4.36

8

7.27

27.

604

7.61

77.

630

7.76

87.

781

7.79

47.

911

7.92

48.

167

8.45

08.

464

9.15

3

0102030405060708090100110120130140150160170180f1 (ppm)

13.4

61

19.9

03

31.8

81

43.9

24

76.7

88 c

dc

l377

.000

cd

cl3

77.2

12 c

dc

l3

112.

255

118.

392

130

.09

813

1.4

35

131

.97

813

2.4

29

134

.92

313

8.2

62

145

.29

5

152

.18

615

2.5

96

152

.95

6

136138140142144146148150152154f1 (ppm)

134.

923

138.

262

145.

295

152.

186

152.

596

152.

956

118120122124126128130132f1 (ppm)

118.

392

130.

098

131.

435

131.

978

132.

429

S-81

2-(9-Benzyl-9H-purin-6-yl)benzonitrile (7d)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

2.16

4.95

1.06

1.09

1.00

1.03

1.03

0.99

-0.0

00

5.51

8

7.26

47.

346

7.35

37.

358

7.36

57.

369

7.38

07.

391

7.39

97.

404

7.60

07.

613

7.62

67.

759

7.77

27.

785

7.90

77.

920

8.14

58.

450

8.46

3

9.18

6

0102030405060708090100110120130140150160170180f1 (ppm)

47.5

20

76.7

88 c

dc

l377

.000

cd

cl3

77.2

12 c

dc

l3

112.

266

118.

387

127

.94

412

8.7

36

129

.22

513

0.1

61

132

.02

613

2.4

44

134

.85

313

4.9

64

138

.15

3

145

.12

9

152

.49

015

2.6

08

153

.10

9

152152.4152.6152.8153.0153.253.4f1 (ppm)

152.

490

152.

608

153.

109

128129130131132133134135f1 (ppm)

127.

944

128.

736

129.

225

130.

161

131.

306

132.

026

132.

444

134.

853

134.

964

N

N

N

N

CN

7dPh

S-82

2-(9-Isopropyl-9H-purin-6-yl)-5-methoxybenzonitrile (7e)

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

6.58

3.01

1.08

0.96

0.95

1.00

1.00

0.93

-0.0

00

1.69

01.

702

3.92

4

4.98

14.

992

5.00

45.

015

5.02

6

7.26

87.

273

7.27

77.

287

7.29

27.

396

7.40

0

8.19

9

8.51

18.

525

9.10

1

0102030405060708090100110120130140150160170180f1 (ppm)

22.5

12

47.5

68

55.8

02

76.7

88 c

dc

l377

.000

cd

cl3

77.2

12 c

dc

l3

113.

304

118.

506

120

.09

0

130

.65

813

1.4

48

133

.68

6

142

.58

0

151

.84

115

2.0

33

152

.68

2

160

.61

2

N

N

N

N

CN

7e

OMe

S-83

5-Acetyl-2-(9-isopropyl-9H-purin-6-yl)benzonitrile (7f)

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

6.74

3.05

1.09

1.01

1.06

0.99

1.00

0.93

-0.0

01

1.71

21.

724

2.70

2

4.99

75.

008

5.02

05.

031

5.04

25.

054

5.06

5

7.27

3

8.26

08.

304

8.30

78.

318

8.32

18.

464

8.46

78.

620

8.63

49.

168

0102030405060708090100110120130140150160170180190200210f1 (ppm)

22.4

94

26.6

91

47.8

33

76.7

88 c

dc

l377

.000

cd

cl3

77.2

12 c

dc

l3

112.

919

117.

695

131

.68

513

1.9

72

132

.52

813

4.7

55

137

.80

714

1.9

07

143

.51

215

1.5

96

151

.91

215

2.4

27

195

.52

6

S-84

5-Chloro-2-(9-isopropyl-9H-purin-6-yl)benzonitrile (7g)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

6.35

1.02

0.93

1.00

1.03

0.91

0.00

0

1.70

11.

712

4.98

24.

994

5.00

55.

016

5.02

85.

039

5.05

0

7.26

97.

738

7.74

87.

752

7.88

37.

887

8.23

18.

507

8.52

2

9.13

3

0102030405060708090100110120130140150160170180f1 (ppm)

22.5

03

47.7

65

76.7

88 c

dc

l376

.999

cd

cl3

77.2

11 c

dc

l3

113.

698

117.

210

131

.67

513

2.7

38

133

.32

413

4.6

33

136

.41

313

6.6

84

143

.17

7

151

.62

515

1.8

73

152

.30

6

150.8151.2151.6152.0152.4152.8f1 (ppm)

151.

625

151.

873

152.

306

131132133134135136137f1 (ppm)

131.

675

132.

738

133.

324

134.

633

136.

413

136.

684

N

N

N

N

CN

7g

Cl

S-85

2-(7-Isopropyl-7H-pyrrolo[2,3-d]pyrimidin-4-yl)benzonitrile (7h)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

6.22

1.03

0.96

0.99

1.00

1.03

1.89

0.88

0.00

0

1.57

31.

585

5.19

25.

204

5.21

55.

227

5.23

85.

249

5.26

1

6.59

16.

597

7.27

07.

419

7.42

57.

594

7.59

67.

608

7.60

97.

732

7.74

57.

747

7.75

87.

760

7.88

37.

886

7.89

67.

898

9.03

1

0102030405060708090100110120130140150160170180f1 (ppm)

22.6

96

46.2

42

76.7

93 c

dc

l377

.005

cd

cl3

77.2

16 c

dc

l3

99.7

22

112.

098

116.

894

118.

117

126

.24

312

9.4

32

130

.46

413

2.5

28

134

.44

0

141

.41

6

150

.91

315

0.9

39

154

.57

1

150.86150.88150.90150.92150.94150.96150.98151.00f1 (ppm)

150.

913

150.

939

S-86

Appendix II

Crystallographic Data

Figure S

S3: Crystal XRD image of 3j

S-87

S-88

Table S2. Crystal data and structure refinement for 3j.

Identification code 3j

Empirical formula C13H10N2O2S

Formula weight 258.29

Temperature 273(2) K

Wavelength 0.71073 Å

Crystal system Monoclinic

Space group P2(1)/c

Unit cell dimensions a = 11.9124(16) Å = 90°.

b = 7.5041(10) Å = 111.533(5)°.

c = 14.670(2) Å = 90°.

Volume 1219.9(3) Å3

Z 4

Density (calculated) 1.406 Mg/m3

Absorption coefficient 0.260 mm-1

F(000) 536

Crystal size 0.10 x 0.10 x 0.08 mm3

Theta range for data collection 2.87 to 31.75°.

Index ranges -16<=h<=17, -10<=k<=11, -21<=l<=16

Reflections collected 35311

Independent reflections 4009 [R(int) = 0.0726]

Completeness to theta = 25.00° 99.9 %

Absorption correction Semi-empirical from equivalents

Max. and min. transmission 0.9795 and 0.9745

Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 4009 / 0 / 163

Goodness-of-fit on F2 1.033

Final R indices [I>2sigma(I)] R1 = 0.0543, wR2 = 0.1185

R indices (all data) R1 = 0.1170, wR2 = 0.1396

Largest diff. peak and hole 0.303 and -0.391 e.Å-3

S-89

Table S3. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x

103) for 3j. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

____________________________________________________________________________

x y z U(eq)

____________________________________________________________________________

S(1) 1144(1) 1105(1) 3935(1) 41(1)

O(1) 1558(1) 1889(3) 3226(1) 69(1)

O(2) 243(1) 2006(2) 4193(1) 55(1)

N(1) 5204(1) 1043(2) 8551(1) 42(1)

N(2) 2683(2) -1226(3) 8165(1) 57(1)

C(1) 6138(2) 1007(3) 9403(1) 49(1)

C(2) 7284(2) 497(3) 9503(1) 50(1)

C(3) 7494(2) -29(3) 8683(2) 51(1)

C(4) 6541(2) -33(3) 7790(1) 43(1)

C(5) 5417(1) 525(2) 7755(1) 34(1)

C(6) 4368(1) 593(2) 6809(1) 32(1)

C(7) 4518(2) 1176(2) 5960(1) 36(1)

C(8) 3556(2) 1309(2) 5074(1) 37(1)

C(9) 2415(1) 813(2) 5032(1) 34(1)

C(10) 2236(1) 186(2) 5856(1) 36(1)

C(11) 3206(1) 88(2) 6744(1) 32(1)

C(12) 618(2) -1049(3) 3557(2) 60(1)

C(13) 2960(2) -607(3) 7572(1) 39(1)

____________________________________________________________________________

S-90

Table S4. Bond lengths [Å] and angles [°] for 3j.

_____________________________________________________

S(1)-O(1) 1.4315(16)

S(1)-O(2) 1.4323(14)

S(1)-C(12) 1.749(2)

S(1)-C(9) 1.7718(16)

N(1)-C(1) 1.335(2)

N(1)-C(5) 1.340(2)

N(2)-C(13) 1.137(2)

C(1)-C(2) 1.373(3)

C(2)-C(3) 1.374(3)

C(3)-C(4) 1.383(2)

C(4)-C(5) 1.386(2)

C(5)-C(6) 1.489(2)

C(6)-C(7) 1.391(2)

C(6)-C(11) 1.405(2)

C(7)-C(8) 1.387(2)

C(8)-C(9) 1.388(2)

C(9)-C(10) 1.385(2)

C(10)-C(11) 1.391(2)

C(11)-C(13) 1.447(2)

O(1)-S(1)-O(2) 119.31(10)

O(1)-S(1)-C(12) 109.18(12)

O(2)-S(1)-C(12) 107.65(10)

O(1)-S(1)-C(9) 107.67(8)

O(2)-S(1)-C(9) 107.01(8)

C(12)-S(1)-C(9) 105.14(9)

C(1)-N(1)-C(5) 116.81(16)

N(1)-C(1)-C(2) 124.07(19)

C(1)-C(2)-C(3) 118.69(17)

C(2)-C(3)-C(4) 118.67(18)

C(3)-C(4)-C(5) 118.74(18)

N(1)-C(5)-C(4) 123.00(15)

N(1)-C(5)-C(6) 116.11(14)

C(4)-C(5)-C(6) 120.88(15)

C(7)-C(6)-C(11) 118.16(14)

C(7)-C(6)-C(5) 120.37(14)

C(11)-C(6)-C(5) 121.47(14)

S-91

C(8)-C(7)-C(6) 121.88(15)

C(7)-C(8)-C(9) 118.77(16)

C(10)-C(9)-C(8) 120.98(15)

C(10)-C(9)-S(1) 118.70(12)

C(8)-C(9)-S(1) 120.21(13)

C(9)-C(10)-C(11) 119.66(15)

C(10)-C(11)-C(6) 120.52(15)

C(10)-C(11)-C(13) 116.84(14)

C(6)-C(11)-C(13) 122.60(15)

N(2)-C(13)-C(11) 174.05(19)

_____________________________________________________________

Symmetry transformations used to generate equivalent atoms:

S-92

Table S5. Anisotropic displacement parameters (Å2x 103) for 3j. The anisotropic

displacement factor exponent takes the form: -22[ h2 a*2U11 + ... + 2 h k a* b* U12 ]

____________________________________________________________________________

__

U11 U22 U33 U23 U13 U12

____________________________________________________________________________

__

S(1) 31(1) 52(1) 35(1) 2(1) 5(1) 5(1)

O(1) 48(1) 108(1) 45(1) 28(1) 9(1) 6(1)

O(2) 37(1) 57(1) 64(1) -6(1) 10(1) 12(1)

N(1) 43(1) 47(1) 32(1) -5(1) 10(1) 0(1)

N(2) 54(1) 79(1) 41(1) 2(1) 21(1) -14(1)

C(1) 54(1) 52(1) 33(1) -7(1) 7(1) -2(1)

C(2) 45(1) 51(1) 38(1) 2(1) -4(1) -6(1)

C(3) 32(1) 59(1) 54(1) 6(1) 7(1) 2(1)

C(4) 36(1) 52(1) 38(1) 1(1) 12(1) 1(1)

C(5) 33(1) 34(1) 31(1) 0(1) 9(1) -3(1)

C(6) 30(1) 34(1) 30(1) -3(1) 9(1) -1(1)

C(7) 30(1) 45(1) 34(1) 0(1) 12(1) -5(1)

C(8) 35(1) 46(1) 31(1) 2(1) 13(1) -1(1)

C(9) 30(1) 38(1) 30(1) -2(1) 7(1) 2(1)

C(10) 28(1) 42(1) 37(1) -2(1) 12(1) -2(1)

C(11) 33(1) 35(1) 32(1) -2(1) 14(1) 0(1)

C(12) 44(1) 65(1) 57(1) -24(1) 4(1) 2(1)

C(13) 34(1) 49(1) 35(1) -1(1) 12(1) -2(1)

____________________________________________________________________________

__

S-93

Table S6. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 10 3)

for 3j.

____________________________________________________________________________

____

x y z U(eq)

____________________________________________________________________________

____

H(1A) 6001 1355 9977 59

H(2A) 7920 508 10128 60

H(3A) 8279 -382 8728 61

H(4A) 6655 -411 7212 51

H(7A) 5304 1493 5990 44

H(8A) 3674 1731 4505 45

H(10A) 1454 -175 5814 43

H(12A) -94 -987 2950 89

H(12B) 399 -1630 4068 89

H(12C) 1251 -1740 3443 89

____________________________________________________________________________

____

S-94

Table S7. Torsion angles [°] for 3j.

________________________________________________________________

C(5)-N(1)-C(1)-C(2) 0.8(3)

N(1)-C(1)-C(2)-C(3) -0.7(3)

C(1)-C(2)-C(3)-C(4) -0.3(3)

C(2)-C(3)-C(4)-C(5) 1.2(3)

C(1)-N(1)-C(5)-C(4) 0.1(3)

C(1)-N(1)-C(5)-C(6) -179.37(16)

C(3)-C(4)-C(5)-N(1) -1.1(3)

C(3)-C(4)-C(5)-C(6) 178.35(17)

N(1)-C(5)-C(6)-C(7) 139.95(17)

C(4)-C(5)-C(6)-C(7) -39.6(2)

N(1)-C(5)-C(6)-C(11) -39.6(2)

C(4)-C(5)-C(6)-C(11) 140.92(18)

C(11)-C(6)-C(7)-C(8) 1.6(3)

C(5)-C(6)-C(7)-C(8) -177.93(16)

C(6)-C(7)-C(8)-C(9) -1.2(3)

C(7)-C(8)-C(9)-C(10) -0.4(3)

C(7)-C(8)-C(9)-S(1) 175.68(13)

O(1)-S(1)-C(9)-C(10) 175.54(15)

O(2)-S(1)-C(9)-C(10) 46.14(16)

C(12)-S(1)-C(9)-C(10) -68.13(16)

O(1)-S(1)-C(9)-C(8) -0.63(18)

O(2)-S(1)-C(9)-C(8) -130.03(15)

C(12)-S(1)-C(9)-C(8) 115.70(16)

C(8)-C(9)-C(10)-C(11) 1.5(3)

S(1)-C(9)-C(10)-C(11) -174.66(13)

C(9)-C(10)-C(11)-C(6) -1.0(3)

C(9)-C(10)-C(11)-C(13) -179.00(16)

C(7)-C(6)-C(11)-C(10) -0.5(2)

C(5)-C(6)-C(11)-C(10) 179.04(15)

C(7)-C(6)-C(11)-C(13) 177.38(16)

C(5)-C(6)-C(11)-C(13) -3.1(3)

C(10)-C(11)-C(13)-N(2) 24(2)

C(6)-C(11)-C(13)-N(2) -154.4(19)

________________________________________________________________


Figure S

S4: Crystal XRD imag

e of 5g

S-95

S-96

Table S8. Crystal data and structure refinement for 5g.

Identification code 5g

Empirical formula C13 H10 N4 O




Crystal system Triclinic

Space group P-1

Unit cell dimensions a = 6.9373(6) Å = 85.814(4)°.

b = 8.2261(7) Å = 78.171(4)°.

c = 9.7516(8) Å = 89.197(4)°.

Volume 543.22(8) Å3

Z 2



F(000) 248



Index ranges -9<=h<=9, -10<=k<=10, -12<=l<=12












S-97

Table S9. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x

103) for 5g. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

____________________________________________________________________________

____

x y z U(eq)

____________________________________________________________________________

____

O(1) -1893(1) 1785(1) 8855(1) 31(1)

N(1) 419(1) 2726(1) 4115(1) 17(1)

N(2) 2986(1) 1750(1) 2442(1) 22(1)

N(3) 1105(1) 4080(1) 1899(1) 24(1)

N(4) -3722(2) 4596(1) 2911(1) 29(1)

C(1) 1250(2) 564(1) 7998(1) 22(1)

C(2) -548(2) 1582(1) 7859(1) 21(1)

C(3) -579(1) 2248(1) 6433(1) 18(1)

C(4) 950(1) 2024(1) 5307(1) 17(1)

C(5) 2853(1) 1209(1) 5419(1) 20(1)

C(6) 3095(2) 1166(1) 6949(1) 22(1)

C(7) -2097(1) 3125(1) 5932(1) 20(1)

C(8) -1466(1) 3408(1) 4510(1) 18(1)

C(9) 1585(1) 2862(1) 2730(1) 17(1)

C(10) 2210(2) 4202(1) 596(1) 26(1)

C(11) 3754(2) 3154(1) 166(1) 24(1)

C(12) 4085(2) 1933(1) 1139(1) 24(1)

C(13) -2612(2) 4090(1) 3560(1) 21(1)

S-98

Table S10. Bond lengths [Å] and angles [°] for 5g.

_____________________________________________________

O(1)-C(2) 1.2206(12)

N(1)-C(4) 1.3758(12)

N(1)-C(8) 1.4060(12)

N(1)-C(9) 1.4231(11)

N(2)-C(9) 1.3266(13)

N(2)-C(12) 1.3405(13)

N(3)-C(9) 1.3241(13)

N(3)-C(10) 1.3409(13)

N(4)-C(13) 1.1485(14)

C(1)-C(2) 1.5160(14)

C(1)-C(6) 1.5289(14)

C(2)-C(3) 1.4613(13)

C(3)-C(4) 1.3825(13)

C(3)-C(7) 1.4162(13)

C(4)-C(5) 1.4923(13)

C(5)-C(6) 1.5327(13)

C(7)-C(8) 1.3691(13)

C(8)-C(13) 1.4215(14)

C(10)-C(11) 1.3815(15)

C(11)-C(12) 1.3802(15)

C(4)-N(1)-C(8) 107.94(8)

C(4)-N(1)-C(9) 127.26(8)

C(8)-N(1)-C(9) 124.67(8)

C(9)-N(2)-C(12) 114.48(9)

C(9)-N(3)-C(10) 114.81(9)

C(2)-C(1)-C(6) 112.29(8)

O(1)-C(2)-C(3) 122.66(10)

O(1)-C(2)-C(1) 122.49(9)

C(3)-C(2)-C(1) 114.82(8)

C(4)-C(3)-C(7) 108.49(8)

C(4)-C(3)-C(2) 122.59(9)

C(7)-C(3)-C(2) 128.86(9)

N(1)-C(4)-C(3) 107.99(8)

N(1)-C(4)-C(5) 127.43(8)

C(3)-C(4)-C(5) 124.55(9)

C(4)-C(5)-C(6) 108.88(8)

S-99

C(1)-C(6)-C(5) 113.00(8)

C(8)-C(7)-C(3) 106.77(8)

C(7)-C(8)-N(1) 108.82(8)

C(7)-C(8)-C(13) 125.83(9)

N(1)-C(8)-C(13) 124.90(9)

N(3)-C(9)-N(2) 128.92(9)

N(3)-C(9)-N(1) 115.10(8)

N(2)-C(9)-N(1) 115.98(8)

N(3)-C(10)-C(11) 122.38(10)

C(12)-C(11)-C(10) 116.65(9)

N(2)-C(12)-C(11) 122.72(9)

N(4)-C(13)-C(8) 172.16(11)

_____________________________________________________________


S-100

Table S11. Anisotropic displacement parameters (Å2x 103) for 5g. The anisotropic


____________________________________________________________________________

__

U11 U22 U33 U23 U13 U12

____________________________________________________________________________

__

O(1) 28(1) 40(1) 18(1) 2(1) 6(1) 7(1)

N(1) 15(1) 19(1) 15(1) 0(1) -1(1) 3(1)

N(2) 22(1) 24(1) 16(1) -1(1) 0(1) 5(1)

N(3) 22(1) 26(1) 20(1) 4(1) -1(1) 4(1)

N(4) 25(1) 35(1) 27(1) 3(1) -6(1) 7(1)

C(1) 22(1) 26(1) 18(1) 3(1) -3(1) 2(1)

C(2) 20(1) 23(1) 16(1) 0(1) 0(1) -1(1)

C(3) 17(1) 20(1) 16(1) -1(1) 0(1) 1(1)

C(4) 17(1) 17(1) 15(1) -1(1) -2(1) 1(1)

C(5) 17(1) 25(1) 17(1) 0(1) -2(1) 5(1)

C(6) 19(1) 29(1) 18(1) 1(1) -4(1) 3(1)

C(7) 16(1) 22(1) 19(1) -1(1) 0(1) 3(1)

C(8) 15(1) 19(1) 19(1) -1(1) -1(1) 2(1)

C(9) 17(1) 20(1) 15(1) -1(1) -2(1) -1(1)

C(10) 25(1) 32(1) 18(1) 6(1) -2(1) 2(1)

C(11) 22(1) 33(1) 15(1) -1(1) 0(1) -1(1)

C(12) 23(1) 30(1) 18(1) -4(1) 1(1) 5(1)

C(13) 19(1) 22(1) 22(1) 0(1) -1(1) 3(1)

____________________________________________________________________________

__

S-101


for 5g.

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____

x y z U(eq)

____________________________________________________________________________

____

H(1A) 995 -584 7846 27

H(1B) 1482 597 8964 27

H(5A) 3961 1817 4801 24

H(5B) 2859 86 5117 24

H(6A) 4212 442 7064 27

H(6B) 3421 2275 7163 27

H(7A) -3317 3453 6477 24

H(10A) 1922 5039 -56 31

H(11A) 4547 3267 -754 29

H(12A) 5136 1193 875 29

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____

S-102

Table S13. Torsion angles [°] for 5g.

________________________________________________________________

C(6)-C(1)-C(2)-O(1) -149.55(10)

C(6)-C(1)-C(2)-C(3) 32.63(12)

O(1)-C(2)-C(3)-C(4) 179.62(10)

C(1)-C(2)-C(3)-C(4) -2.56(14)

O(1)-C(2)-C(3)-C(7) -3.47(17)

C(1)-C(2)-C(3)-C(7) 174.35(10)

C(8)-N(1)-C(4)-C(3) 0.46(11)

C(9)-N(1)-C(4)-C(3) 176.41(9)

C(8)-N(1)-C(4)-C(5) -177.45(9)

C(9)-N(1)-C(4)-C(5) -1.50(16)

C(7)-C(3)-C(4)-N(1) -0.52(11)

C(2)-C(3)-C(4)-N(1) 176.94(9)

C(7)-C(3)-C(4)-C(5) 177.46(9)

C(2)-C(3)-C(4)-C(5) -5.07(15)

N(1)-C(4)-C(5)-C(6) 159.83(9)

C(3)-C(4)-C(5)-C(6) -17.76(13)

C(2)-C(1)-C(6)-C(5) -57.01(12)

C(4)-C(5)-C(6)-C(1) 47.69(11)

C(4)-C(3)-C(7)-C(8) 0.38(11)

C(2)-C(3)-C(7)-C(8) -176.88(10)

C(3)-C(7)-C(8)-N(1) -0.10(11)

C(3)-C(7)-C(8)-C(13) 172.49(9)

C(4)-N(1)-C(8)-C(7) -0.22(11)

C(9)-N(1)-C(8)-C(7) -176.30(8)

C(4)-N(1)-C(8)-C(13) -172.89(9)

C(9)-N(1)-C(8)-C(13) 11.03(15)

C(10)-N(3)-C(9)-N(2) -0.73(17)

C(10)-N(3)-C(9)-N(1) 179.92(9)

C(12)-N(2)-C(9)-N(3) 2.09(16)

C(12)-N(2)-C(9)-N(1) -178.57(8)

C(4)-N(1)-C(9)-N(3) -154.87(10)

C(8)-N(1)-C(9)-N(3) 20.44(14)

C(4)-N(1)-C(9)-N(2) 25.70(14)

C(8)-N(1)-C(9)-N(2) -158.99(9)

C(9)-N(3)-C(10)-C(11) -1.18(16)

N(3)-C(10)-C(11)-C(12) 1.51(17)

C(9)-N(2)-C(12)-C(11) -1.59(16)

S-103

C(10)-C(11)-C(12)-N(2) -0.02(17)

C(7)-C(8)-C(13)-N(4) -17.6(9)

N(1)-C(8)-C(13)-N(4) 153.8(8)

________________________________________________________________


Figure S

S5: Crystal XRD imag

e of 7b

S-104

S-105

Table S14. Crystal data and structure refinement for 7b.

Identification code 7b

Empirical formula C14 H11 N5




Crystal system Triclinic

Space group P-1

Unit cell dimensions a = 7.9667(3) Å = 109.198(2)°.

b = 8.6666(4) Å = 107.554(2)°.

c = 9.6847(4) Å = 92.006(2)°.

Volume 595.36(4) Å3

Z 2



F(000) 260



Index ranges -12<=h<=12, -13<=k<=13, -15<=l<=15












S-106

Table S15. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters

(Å2x 103) for 7b. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

____________________________________________________________________________

____

x y z U(eq)

____________________________________________________________________________

____

N(3) 5401(1) 6287(1) 9142(1) 22(1)

N(2) 7034(1) 4620(1) 7630(1) 22(1)

N(4) 2145(1) 3563(1) 5655(1) 25(1)

N(5) 2214(1) 5565(1) 7870(1) 22(1)

N(1) 9576(1) 1733(1) 7878(1) 34(1)

C(7) 5719(1) 2395(1) 5152(1) 19(1)

C(10) 3948(1) 5429(1) 7973(1) 19(1)

C(9) 3897(1) 4175(1) 6598(1) 19(1)

C(2) 7109(1) 1437(1) 5323(1) 20(1)

C(1) 8448(1) 1673(1) 6791(1) 24(1)

C(11) 6881(1) 5816(1) 8867(1) 23(1)

C(8) 5538(1) 3758(1) 6476(1) 18(1)

C(12) 1223(1) 4430(1) 6467(1) 26(1)

C(3) 7212(2) 137(1) 4049(1) 26(1)

C(6) 4467(2) 2002(1) 3683(1) 25(1)

C(13) 1540(2) 6678(2) 9013(1) 27(1)

C(5) 4584(2) 715(2) 2425(1) 29(1)

C(4) 5950(2) -224(2) 2604(1) 30(1)

C(14) 769(2) 8046(2) 8515(2) 35(1)

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____

S-107

Table S16. Bond lengths [Å] and angles [°] for 7b.

_____________________________________________________

N(3)-C(10) 1.3309(13)

N(3)-C(11) 1.3340(14)

N(2)-C(11) 1.3429(13)

N(2)-C(8) 1.3466(13)

N(4)-C(12) 1.3114(14)

N(4)-C(9) 1.3869(13)

N(5)-C(12) 1.3631(15)

N(5)-C(10) 1.3663(13)

N(5)-C(13) 1.4620(13)

N(1)-C(1) 1.1438(15)

C(7)-C(6) 1.3919(14)

C(7)-C(2) 1.4099(14)

C(7)-C(8) 1.4788(14)

C(10)-C(9) 1.4031(14)

C(9)-C(8) 1.3977(14)

C(2)-C(3) 1.3965(14)

C(2)-C(1) 1.4423(15)

C(3)-C(4) 1.3818(17)

C(6)-C(5) 1.3853(15)

C(13)-C(14) 1.5048(17)

C(5)-C(4) 1.3851(18)

C(10)-N(3)-C(11) 111.60(9)

C(11)-N(2)-C(8) 118.51(9)

C(12)-N(4)-C(9) 103.48(9)

C(12)-N(5)-C(10) 105.45(9)

C(12)-N(5)-C(13) 126.60(9)

C(10)-N(5)-C(13) 127.95(9)

C(6)-C(7)-C(2) 117.88(9)

C(6)-C(7)-C(8) 119.83(9)

C(2)-C(7)-C(8) 122.27(9)

N(3)-C(10)-N(5) 127.46(9)

N(3)-C(10)-C(9) 126.42(9)

N(5)-C(10)-C(9) 106.12(9)

N(4)-C(9)-C(8) 133.66(9)

N(4)-C(9)-C(10) 109.96(9)

C(8)-C(9)-C(10) 116.32(9)

S-108

C(3)-C(2)-C(7) 120.55(10)

C(3)-C(2)-C(1) 116.03(9)

C(7)-C(2)-C(1) 123.37(9)

N(1)-C(1)-C(2) 173.31(12)

N(3)-C(11)-N(2) 128.49(10)

N(2)-C(8)-C(9) 118.60(9)

N(2)-C(8)-C(7) 118.10(9)

C(9)-C(8)-C(7) 123.30(9)

N(4)-C(12)-N(5) 115.00(10)

C(4)-C(3)-C(2) 120.30(10)

C(5)-C(6)-C(7) 121.18(10)

N(5)-C(13)-C(14) 112.16(10)

C(4)-C(5)-C(6) 120.57(10)

C(3)-C(4)-C(5) 119.53(10)

_____________________________________________________________


S-109

Table S17. Anisotropic displacement parameters (Å2x 103) for 7b. The anisotropic


____________________________________________________________________________

__

U11 U22 U33 U23 U13 U12

____________________________________________________________________________

__

N(3) 22(1) 22(1) 20(1) 3(1) 7(1) 4(1)

N(2) 19(1) 21(1) 21(1) 2(1) 6(1) 4(1)

N(4) 18(1) 23(1) 26(1) 5(1) 3(1) 3(1)

N(5) 19(1) 24(1) 26(1) 8(1) 10(1) 7(1)

N(1) 30(1) 36(1) 30(1) 7(1) 7(1) 12(1)

C(7) 20(1) 17(1) 19(1) 4(1) 8(1) 1(1)

C(10) 18(1) 19(1) 21(1) 7(1) 8(1) 5(1)

C(9) 18(1) 17(1) 19(1) 4(1) 5(1) 3(1)

C(2) 21(1) 18(1) 21(1) 4(1) 9(1) 2(1)

C(1) 23(1) 22(1) 26(1) 5(1) 12(1) 7(1)

C(11) 19(1) 22(1) 21(1) 2(1) 5(1) 3(1)

C(8) 19(1) 17(1) 18(1) 4(1) 6(1) 3(1)

C(12) 18(1) 25(1) 30(1) 9(1) 6(1) 3(1)

C(3) 31(1) 21(1) 28(1) 4(1) 16(1) 6(1)

C(6) 27(1) 24(1) 21(1) 6(1) 6(1) 4(1)

C(13) 27(1) 31(1) 30(1) 10(1) 17(1) 12(1)

C(5) 35(1) 27(1) 18(1) 3(1) 6(1) -1(1)

C(4) 41(1) 22(1) 24(1) 0(1) 16(1) 1(1)

C(14) 39(1) 31(1) 35(1) 9(1) 14(1) 15(1)

____________________________________________________________________________

__

S-110


for 7b.

____________________________________________________________________________

____

x y z U(eq)

____________________________________________________________________________

____

H(11A) 7969 6402 9648 27

H(12A) -42 4277 6104 31

H(3A) 8153 -502 4178 32

H(6A) 3515 2627 3540 30

H(13A) 2522 7165 10014 33

H(13B) 610 6037 9175 33

H(5A) 3720 475 1431 35

H(4A) 6020 -1111 1739 36

H(14A) 333 8760 9310 53

H(14B) -219 7571 7534 53

H(14C) 1692 8699 8375 53

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____

S-111

Table S19. Torsion angles [°] for 7b.

________________________________________________________________

C(11)-N(3)-C(10)-N(5) 178.95(10)

C(11)-N(3)-C(10)-C(9) -0.07(16)

C(12)-N(5)-C(10)-N(3) -179.80(11)

C(13)-N(5)-C(10)-N(3) -0.15(18)

C(12)-N(5)-C(10)-C(9) -0.62(11)

C(13)-N(5)-C(10)-C(9) 179.04(10)

C(12)-N(4)-C(9)-C(8) 176.61(12)

C(12)-N(4)-C(9)-C(10) -0.38(12)

N(3)-C(10)-C(9)-N(4) 179.84(10)

N(5)-C(10)-C(9)-N(4) 0.64(12)

N(3)-C(10)-C(9)-C(8) 2.26(16)

N(5)-C(10)-C(9)-C(8) -176.93(9)

C(6)-C(7)-C(2)-C(3) -0.07(15)

C(8)-C(7)-C(2)-C(3) 178.62(10)

C(6)-C(7)-C(2)-C(1) -177.46(10)

C(8)-C(7)-C(2)-C(1) 1.24(16)

C(3)-C(2)-C(1)-N(1) 0.7(11)

C(7)-C(2)-C(1)-N(1) 178.2(10)

C(10)-N(3)-C(11)-N(2) -1.51(17)

C(8)-N(2)-C(11)-N(3) 0.68(18)

C(11)-N(2)-C(8)-C(9) 1.75(15)

C(11)-N(2)-C(8)-C(7) -177.30(10)

N(4)-C(9)-C(8)-N(2) -179.86(11)

C(10)-C(9)-C(8)-N(2) -3.01(14)

N(4)-C(9)-C(8)-C(7) -0.87(18)

C(10)-C(9)-C(8)-C(7) 175.98(9)

C(6)-C(7)-C(8)-N(2) -149.17(10)

C(2)-C(7)-C(8)-N(2) 32.16(14)

C(6)-C(7)-C(8)-C(9) 31.83(15)

C(2)-C(7)-C(8)-C(9) -146.84(11)

C(9)-N(4)-C(12)-N(5) -0.03(13)

C(10)-N(5)-C(12)-N(4) 0.43(13)

C(13)-N(5)-C(12)-N(4) -179.24(10)

C(7)-C(2)-C(3)-C(4) 0.11(17)

C(1)-C(2)-C(3)-C(4) 177.68(11)

C(2)-C(7)-C(6)-C(5) -0.23(16)

C(8)-C(7)-C(6)-C(5) -178.96(10)

S-112

C(12)-N(5)-C(13)-C(14) -72.70(15)

C(10)-N(5)-C(13)-C(14) 107.71(13)

C(7)-C(6)-C(5)-C(4) 0.51(18)

C(2)-C(3)-C(4)-C(5) 0.16(18)

C(6)-C(5)-C(4)-C(3) -0.47(18)

________________________________________________________________


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