Cu-Catalyzed Electrophilic Amination of Internal Alkynes ... · PDF file1 Cu-Catalyzed...

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Cu-Catalyzed Electrophilic Amination of Internal Alkynes via

Hydroalumination

Hongju Yoon, Yuna Kim and Yunmi Lee*

Department of Chemistry, Kwangwoon University, Seoul 01897, Republic Korea

Supporting Information

General. 1H NMR spectra were recorded on a 400 MHz spectrometer. Chemical shifts are reported in

ppm from tetramethylsilane, with the solvent resonance as the internal standard (CDCl3: δ 7.27 ppm).

Data are reported as follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet,

m = multiplet), coupling constants (Hz), and integration. 13C NMR spectra were recorded on a 100 MHz

spectrometer with complete proton decoupling. Chemical shifts are reported in ppm from

tetramethylsilane with the solvent resonance as the internal standard (CDCl3: δ 77.00 ppm). High-

resolution mass spectra (HRMS) were obtained using an electrospray ionization (ESI) time-of-flight

mass spectrometer. Melting points were determined using a melting point apparatus and are uncorrected.

Unless otherwise noted, all reactions were carried out with distilled solvents under an atmosphere of dry

N2 in oven-dried (130 oC) glassware. Tetrahydrofuran was purified by distillation from sodium

benzophenone ketyl immediately prior to use unless otherwise specified. All work-up and purification

procedures were carried out with reagent grade solvents in air. A variety of N,N-dialkyl-O-benzoyl

hydroxylamines1 and internal alkynes

2 were prepared according to reported experimental procedures.

(1) (a) T. J. Barker, E. R. Jarvo, J. Am. Chem. Soc. 2009, 131, 15598. (b) A. M. Berman, J. S. Johnson, J. Org.

Chem. 2006, 71, 219. (c) A. M. Berman, J. S. Johnson, J. Org. Chem. 2005, 70, 364. (d) A. M. Berman, A. M.; J.

S. Johnson, Synlett 2005, 1799. (e) A. M. Berman, J. S. Johnson, J. Am. Chem. Soc. 2004, 126, 5680.

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2016

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� Experimental procedure for Cu-catalyzed electrophilic amination of vinylaluminum 2a via

direct hydroalumination of diphenylacetylene (1a):

Ph Phhexanes, 60 oC Ph Ph

Al(i-Bu)2

used in situ

THF, 22 oC, 1 h

BzO-N(Bn)2 3a Ph Ph

N(Bn)2

12 h

75% conv

1 mol % CuCl

>98% conv, 53% yield

H Al(i-Bu)2

no CuCl: 45% conv, <2% yield

1a

H

2a 4aa

To a solution of diphenylacetylene (1a) (178 mg, 1.00 mmol) in hexanes (1.25 mL) was added

diisobutylaluminum hydride (178 μL, 1.00 mmol) slowly under N2 gas. The solution was allowed to

heat to 60 °C and stir for 12 h. After that time, the resulting vinylaluminum reagent 2a (~0.7 M, >98%

E-vinylAl) 3

was directly used for the amination without further filtration and purification.

O-Benzoyl-N,N-dibenzylhydroxylamine (3a) (47.6 mg, 0.150 mmol), CuCl (0.200 mg, 1.50x10-3

mmol)

and THF (0.5 mL) were added to a 8 mL vial under N2 gas and then vinylaluminum reagent 2a (~0.7 M

in hexanes, 0.320 mL, 0.225 mmol) was added slowly. The reaction mixture was allowed to stir at room

temperature for 1 h. After that time, reaction was quenched with an aqueous solution of 1 M NaOH (1

mL) and a saturated aqueous solution of Rochelle`s salt (1 mL). The resulting solution was allowed to

stir vigorously for 10 min and washed with EtOAc (3 x 2 mL). The combined organic layers were dried

over MgSO4, filtered and concentrated. The stereoselectivity of E-enamine was determined by analysis

of 1H NMR spectra of the unpurified reaction mixtures through comparison of the previously reported

data.4 (E)-N,N-Dibenzyl-1,2-diphenylethenamine (4aa) was dominatly observed (>98:<2 E:Z-enamine).

The crude enamine product was dissolved in CH2Cl2 (1.5 mL) and then NaB(OAc)3H (127 mg, 0.60

mmol) and AcOH (34.3 μL, 0.60 mmol) were added. The reaction mixture was allowed to stir at 22 °C

for 12 h. After that time, The resulting solution was quenched with an aqueous solution of 1 M NaOH (1

(2) (a) T. Torigoe, T. Ohmura, M. Suginome, Chem. Eur. J. 2016, 22, 10415. (b) K. Park, G. Bae, J. Moon, J.

Choe, K. H. Song, S. Lee, J. Org. Chem. 2010, 75, 6244.

(3) The vinylaluminum reagents reagent 2a was quenched with H2O and conversion and stereoselectivity were

determined by analysis of 1H NMR spectrum. The (Z)-1,2-diphenylethene was observed in >98:<2 Z:E selectivity.

The spectra data of the obtained (Z)-1,2-diphenylethene match those reported previously. For spectra data of (Z)-

1,2-diphenylethene, see: (a) Y. S. Wagh, N. Asao, J. Org. Chem. 2015, 80, 847. For spectra data of (E)-1,2-

diphenylethene, see: (b) F. Zhao, J. Luo, Q. Tan, Y. Liao, S. Peng, G.-J. Deng, Adv. Synth. Catal. 2012, 354, 1914.

(4) J. S. Bandar, M. T. Pirnot, S. L. Buchwald, J. Am. Chem. Soc. 2015, 137, 14812.

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mL) and washed with CH2Cl2 (3 x 1mL). The combined organic layers were dried over MgSO4, filtered

and concentrated. The desired product was quantified by analysis of 1H NMR spectra using 1,3,5-

trimethoxybenzene as an internal standard (53% NMR yield).

� Representative experimental procedures for Cu-catalyzed electrophilic amination of

vinylaluminum 2 via Ni-catalyzed hydroalumination of internal aryl acetylene 1:

General procedure A: 1,2-Bis(4-(trifluoromethyl)phenyl)ethyne (1b) (141 mg, 0.450 mmol),

Ni(PPh3)2Cl2 (2.90 mg, 0.00450 mmol) and THF (0.28 mL) were added to a 8 mL vial and then

diisobutylaluminum hydride (80.0 μL, 0.450 mmol) was added slowly under N2 gas. The solution was

allowed to stir at 22 °C for 3 h. After that time, to a solution of O-benzoyl-N,N-dibenzylhydroxylamine

(3a) (95.2 mg, 0.300 mmol) and CuCl (0.300 mg, 0.00300 mmol) in THF (1 mL) was added slowly the

resulting vinylaluminum reagent 2b. The reaction mixture was allowed to stir at room temperature for

0.5 h. And then the resulting solution was quenched with an aqueous solution of 1 M NaOH (1 mL) and

a saturated aqueous solution of Rochelle`s salt (1 mL). The solution was allowed to stir vigorously for

10 min and washed with EtOAc (3 x 2 mL). The combined organic layers were dried over MgSO4,

filtered and concentrated. The crude product was purified by neutral alumina (100% hexanes with 1% of

Et3N → EtOAc:hexanes=1:20) to afford the desired (E)-N,N-dibenzyl-1,2-bis(4-(trifluoromethyl)

phenyl)ethenamine (4ba) (132 mg, 0.258 mmol, 86%) as a yellow sticky oil.

General procedure B: Diphenylacetylene (1a) (80.2 mg, 0.450 mmol), Ni(PPh3)2Cl2 (2.90 mg, 0.00450

mmol) and THF (0.28 mL) were added to a 8 mL vial and then diisobutylaluminum hydride (80.0 μL,

0.450 mmol) was added slowly under N2 gas. The solution was allowed to stir at 22 °C for 3 h. After

that time, to a solution of O-benzoyl-N,N-dibenzylhydroxylamine (3a) (95.2 mg, 0.300 mmol) and CuCl

(0.300 mg, 0.00300 mmol) in THF (1 mL) was added slowly the resulting vinylaluminum reagent 2b.

The reaction mixture was allowed to stir at room temperature for 0.5 h. And then the resulting solution

was quenched with an aqueous solution of 1 M NaOH (1 mL) and a saturated aqueous solution of

Rochelle`s salt (1 mL). The solution was allowed to stir vigorously for 10 min and washed with EtOAc

(3 x 2 mL). The combined organic layers were dried over MgSO4, filtered and concentrated. The crude

enamine product was dissolved in CH2Cl2 (3 mL). And then NaB(OAc)3H (254 mg, 1.20 mmol) and

AcOH (68.7 μL, 1.20 mmol) were added to the mixture, which was allowed to stir at 22 °C for 12 h.

After that time, the resulting solution was quenched with an aqueous solution of 1 M NaOH (2 mL) and

washed with CH2Cl2 (3 x 2 mL). The combined organic layers were dried over MgSO4, filtered and

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concentrated. The crude product was purified by silica gel column chromatography (100% hexanes with

1% of Et3N → EtOAc:hexanes=1:20) to afford the desired N,N-dibenzyl-1,2-diphenylethanamine (4aa’)

(102 mg, 0.270 mmol, 90%) as a colorless oil.

(E)-N,N-Dibenzyl-1,2-bis(4-(trifluoromethyl)phenyl)ethenamine (4ba). Compound 4ba was

synthesized according to general procedure A using O-benzoyl-N,N-dibenzylhydroxylamine (3a, 0.300

mmol) to obtain as a yellow solid in 86% yield (132 mg, 0.258 mmol). The compound exists as a 98:2

mixture of E:Z isomers after alumina purification. 1H NMR (CDCl3, 400 MHz): δ 7.64 (d, J = 7.9 Hz,

2H), 7.60 (d, J = 7.9 Hz, 2H), 7.36 (dd, J = 7.2, 7.2 Hz, 4H), 7.30 (d, J = 6.8 Hz, 2H), 7.24 (d, J = 7 Hz,

6H), 6.74 (d, J = 8.1 Hz, 2H), 5.70 (s, 1H), 4.15 (s, 4H); 13

C NMR (CDCl3, 100 MHz): δ 149.8, 142.2,

140.6, 137.6, 131.0, 130.3 (q, J = 20 Hz), 129.9 (q, J = 20 Hz), 128.6, 128.0, 128.0, 127.4, 125.9 (q, J =

4.0 Hz), 124.7 (q, J = 4.0 Hz), 124.4 (q, J = 270 Hz), 124.0 (q, J = 271 Hz), 106.6, 52.8; HRMS (ESI)

m/z: [M+H]+ Calcd for C30H24F6N 512.1813, Found 512.1807.

(E)-N,N-Dibenzyl-1,2-bis(3-(trifluoromethyl)phenyl)ethenamine (4ca). Compound 4ca was


mmol) to obtain as slightly yellow sticky oil in 71% yield (108 mg, 0.220 mmol). The compound exists

as a 96:4 mixture of E:Z isomers after alumina purification. 1H NMR (CDCl3, 400 MHz): δ 7.71 (s, 1H),

7.65 (dd, J = 5.7, 5.7 Hz, 2H), 7.50 (dd, J = 7.6, 7.6 Hz, 1H), 7.40-7.37 (m, 4H), 7.32 (d, J = 6.8 Hz,

2H), 7.29-7.20 (m, 4H), 7.16 (d, J = 7.0 Hz, 1H), 7.10 (dd, J = 7.6, 7.6 Hz, 1H), 6.87 (s, 1H), 6.84 (d, J

= 7.4 Hz, 1H), 5.73 (s, 1H), 4.19 (s, 4H); 13

C NMR (CDCl3, 100 MHz): δ 149.5, 139.1, 137.7, 134.0,

131.5 (q, J = 33 Hz), 130.1 (q, J = 32 Hz), 129.5, 128.9, 128.7, 128.6, 128.1, 128.0, 127.4 (q, J = 4.0

Hz), 127.4, 125.5 (q, J = 4.0 Hz), 124.7 (q, J = 4.0 Hz), 124.1 (q, J = 272 Hz), 123.9 (q, J = 272 Hz),

120.7 (q, J = 4.0 Hz), 106.4, 52.9; HRMS (ESI) m/z: [M+H]+ Calcd for C30H24F6N 512.1813, Found

512.1810.

(E)-N,N-Dibenzyl-1,2-bis(3-methoxyphenyl)ethenamine (4da). Compound 4da was synthesized

according to general procedure A using O-benzoyl-N,N-dibenzylhydroxylamine (3a, 0.300 mmol) to

obtain as slightly yellow sticky oil in 91% yield (119 mg, 0.273 mmol). The compound exists as a 93:7

mixture of E:Z isomers after alumina purification. 1H NMR (CDCl3, 400 MHz): δ 7.36-7.31 (m, 5H),

7.30-7.26 (m, 6H), 7.13 (d, J = 7.8 Hz, 1H), 7.06 (s, 1H), 6.99-6.89 (m, 2H), 6.49 (dd, J = 8.2, 2.1 Hz,

1H), 6.41 (d, J = 7.6 Hz, 1H), 6.28 (s, 1H), 5.62 (s, 1H), 4.17 (s, 4H), 3.76 (s, 3H), 3.53 (s, 3H); 13C

NMR (CDCl3, 100 MHz): δ 160.1, 159.1, 149.5, 140.4, 138.9, 138.4, 129.8, 129.2, 128.5, 128.4, 128.1,

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127.3, 127.0, 123.2, 121.0, 116.0, 114.2, 112.5, 110.4, 106.4, 55.2, 54.7, 52.7; HRMS (ESI) m/z:

[M+H]+

Calcd for C30H30NO2 436.2277, Found 436.2265.

(E)-N,N-Dibenzyl-1,2-bis(4-chlorophenyl)ethenamine (4ea). Compound 4ea was synthesized


obtain as yellow-green sticky oil in 85% yield (114 mg, 0.256 mmol). The compound exists as a >98:<2

mixture of E:Z isomers after alumina purification. 1H NMR (CDCl3, 400 MHz): δ 7.40 (d, J = 8.3 Hz,

2H), 7.36-7.32 (m, 6H), 7.29-7.26 (m, 2H), 7.24-7.22 (m, 4H), 6.98 (d, J = 8.6 Hz, 2H), 6.64 (d, J = 8.5

Hz, 2H), 5.58 (s, 1H), 4.11 (s, 4H); 13C NMR (CDCl3, 100 MHz): δ 148.8, 138.0 137.2, 135.5, 134.5,

132.0, 129.6, 129.4, 129.2, 129.1, 129.0, 128.6, 128.6, 128.5, 128.1, 127.9, 127.2, 106.6, 52.7; HRMS

(ESI) m/z: [M+H]+

Calcd for C28H24Cl2N 444.1286, Found 444.1290.

N,N-Dibenzyl-1,2-bis(4-fluorophenyl)ethanamine (4fa’). Compound 4fa’ was synthesized according

to general procedure B using O-benzoyl-N,N-dibenzylhydroxylamine (3a, 0.300 mmol) to obtain as a

white solid in 95% yield (118 mg, 0.285 mmol). mp 107-108 °C; 1H NMR (CDCl3, 400 MHz): δ 7.30-

7.27 (m, 5H), 7.25-7.20 (m, 7H), 7.08 (dd, J = 8.6, 8.6 Hz, 2H), 7.02 (dd, J = 8.6, 5.4 Hz, 2H), 6.94 (dd,

J = 8.6, 8.6 Hz, 2H), 4.00 (t, J = 7.7 Hz, 1H), 3.87 (d, J = 13.9 Hz, 2H), 3.35 (dd, J = 13.9, 8.2 Hz, 1H),

3.18 (d, J = 13.9 Hz, 2H), 3.00 (dd, J = 13.9, 7.3 Hz, 1H); 13C NMR (CDCl3, 100 MHz): δ 162.0 (d, J

= 245 Hz), 161.5 (d, J = 243 Hz), 139.7, 135.3 (d, J = 3.0 Hz), 134.0 (d, J = 3.0 Hz), 130.8 (d, J = 8.0

Hz), 130.4 (d, J = 8.0 Hz), 128.6, 128.3, 126.9, 115.0 (d, J = 5.8 Hz), 114.7 (d, J = 5.8 Hz), 62.7, 53.5,

36.9; HRMS (ESI) m/z: [M+H]+ Calcd for C28H26F2N 414.2033, Found 414.2032.

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N,N-Dibenzyl-1,2-bis(4-methoxyphenyl)ethanamine (4ga’). Compound 4ga’ was synthesized

according to general procedure B using O-benzoyl-N,N-dibenzylhydroxylamine (3a, 0.300 mmol) to

obtain as a white solid in 87% yield (114 mg, 0.261 mmol). mp 75-76 °C; 1H NMR (CDCl3, 400 MHz):

δ 7.26-7.20 (m, 10H), 7.18 (d, J = 8.5 Hz, 2H), 6.98 (d, J = 8.6 Hz, 2H), 6.91 (d, J = 8.3 Hz, 2H), 6.78

(d, J = 8.5 Hz, 2H), 3.96 (t, J = 7.7 Hz, 1H), 3.86 (d, J = 14.4 Hz, 2H), 3.83 (s, 3H), 3.81 (s, 3H), 3.30

(dd, J = 13.9, 8.0 Hz, 1H), 3.19 (d, J = 14.1 Hz, 2H), 3.00 (dd, J = 14.0, 7.2 Hz, 1H); 13

C NMR (CDCl3,

100 MHz): δ 158.6, 157.9, 140.2, 132.9, 132.1, 130.4, 130.1, 128.6, 128.2, 126.7, 113.4, 113.2, 62.6,

55.2, 55.1, 53.4, 36.8; HRMS (ESI) m/z: [M+H]+

Calcd for C30H32NO2 438.2433, Found 438.2436.

N,N-Dibenzyl-1,2-di-p-tolylethanamine (4ha’). Compound 4ha’ was synthesized according to general

procedure B using O-benzoyl-N,N-dibenzylhydroxylamine (3a, 0.300 mmol) to obtain as colorless

sticky oil in 93% yield (113 mg, 0.279 mmol). mp 66-67 °C; 1H NMR (CDCl3, 400 MHz): δ 7.26-7.18

(m, 10H), 7.16 (dd, J = 7.1, 7.1 Hz, 4H), 7.04 (d, J = 7.8 Hz, 2H), 6.97 (d, J = 7.8 Hz, 2H), 4.00 (t, J =

7.6 Hz, 1H), 3.86 (d, J = 13.9 Hz, 2H), 3.33 (dd, J = 13.9, 8.0 Hz, 1H), 3.19 (d, J = 13.9 Hz, 2H), 3.05

(dd, J = 14.1, 7.2 Hz, 1H), 2.37 (s, 3H), 2.34 (s, 3H); 13

C NMR (CDCl3, 100 MHz): δ 140.2, 136.9,

136.6, 135.4, 135.2, 129.4, 129.0, 128.7, 128.7, 128.2, 126.7, 62.8, 53.5, 37.1, 21.0, 21.0; HRMS (ESI)

m/z: [M+H]+

Calcd for C30H32N 406.2535, Found 406.2534.

(E)-N,N-Dibenzyl-1,2-bis(2-fluorophenyl)ethenamine (4ia). Compound 4ia was synthesized


obtain as pale yellow sticky oil in 62% yield (76.1 mg, 0.185 mmol). 1H NMR (CDCl3, 400 MHz): δ

7.41-7.24 (m, 12H), 7.12-7.05 (m, 2H), 6.88 (dd, J = 6.0, 6.0 Hz, 2H), 6.66-6.62 (m, 1H), 6.46 (dd, J =

7.8, 7.8 Hz, 1H), 5.77 (s, 1H), 4.22 (s, 4H); 13

C NMR (CDCl3, 100 MHz): δ 160.9 (d, J = 248 Hz),

159.9 (d, J = 244 Hz), 144.5, 138.2, 132.6 (d, J = 4.0 Hz), 130.5 (d, J = 4.0 Hz), 128.8 (d, J = 3.0 Hz),

128.4, 128.0, 127.0, 126.7, 125.5 (d, J = 8.0 Hz), 124.9, 124.5 (d, J = 4.0 Hz), 123.1 (d, J = 4.0 Hz),

116.1 (d, J = 22.4 Hz), 114.7 (d, J = 22.4 Hz), 98.7, 52.8; HRMS (ESI) m/z: [M+H]+

Calcd for

C28H24F2N 412.1877, Found 412.1880.

(E)-N,N-Dibenzyl-1,2-di-o-tolylethenamine (4ja). Compound 4ja was synthesized according to

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general procedure A using O-benzoyl-N,N-dibenzylhydroxylamine (3a, 0.300 mmol) to obtain as

yellowish sticky oil in 30% yield (36.5 mg, 0.090 mmol). 1H NMR (CDCl3, 400 MHz): δ 7.36-7.29 (m,

10H), 7.20 (dd, J = 6.7, 6.7 Hz, 2H), 7.12 (dd, J = 6.3, 6.3 Hz, 2H), 7.01 (d, 7.4 Hz, 1H), 6.82 (dd, J =

7.3, 7.3 Hz, 1H), 6.66 (dd, J = 7.5, 7.5 Hz, 1H), 6.36 (d, J = 7.9 Hz, 1H), 5.67 (s, 1H), 4.30 (d, J = 15.4

Hz, 2H), 4.14 (d, J = 15.3 Hz, 2H), 2.21 (s, 6H); 13

C NMR (CDCl3, 100 MHz): δ 148.2, 139.6, 138.9,

137.8, 136.6, 135.2, 131.1, 130.3, 129.4, 129.1, 128.4, 128.0, 126.9, 126.6, 125.8, 125.0, 124.1, 103.5,

52.7, 20.3, 19.7; HRMS (ESI) m/z: [M+H]+ Calcd for C30H30N 404.2378, Found 404.2376.

(E)-N,N-Dibenzyl-1,2-di(thiophen-2-yl)ethenamine (4ka). Compound 4ka was synthesized according

to general procedure A using O-benzoyl-N,N-dibenzylhydroxylamine (3a, 0.300 mmol) to obtain as

yellow sticky oil in 76% yield (88.7 mg, 0.229 mmol). 1H NMR (CDCl3, 400 MHz): δ 7.54 (dd, J = 5.0,

1.0 Hz, 1H), 7.38-7.31 (m, 5H), 7.30-7.23 (m, 6H), 7.11 (dd, J = 5.1, 3.7 Hz, 1H), 6.84 (dd, 5.3, 0.9 Hz,

1H), 6.78 (dd, J = 5.1, 3.7 Hz, 1H), 6.54 (d, J = 3.7 Hz, 1H), 5.94 (s, 1H), 4.20 (s, 4H); 13

C NMR

(CDCl3, 100 MHz): δ 142.5, 140.5, 138.1, 137.7, 130.4, 128.5, 128.2, 127.9, 127.5, 127.1, 126.1, 124.0,

122.0, 102.6, 52.7; HRMS (ESI) m/z: [M+H]+ Calcd for C24H22NS2 388.1194, Found 388.1179.

N,N-Dibenzyl-1,4-diphenylbutan-2-amine (4la’).

Compound 4la’ was synthesized according to

general procedure B using O-benzoyl-N,N-dibenzylhydroxylamine (3a, 0.300 mmol) to obtain as

colorless oil in 72% yield (88.0 mg, 0.217 mmol). 1H NMR (CDCl3, 400 MHz): δ 7.36-7.10 (m, 16H),

7.02 (dd, J = 5.6, 5.6 Hz, 4H), 3.83 (d, J = 13.6 Hz, 2H), 3.59 (d, J = 13.9 Hz, 2H), 3.13 (dd, J = 13.2,

4.6 Hz, 1H), 2.96-2.82 (m, 2H), 2.49 (dd, J = 13.2, 8.8 Hz, 1H), 2.35-2.26 (m, 1H), 1.94-1.82 (m, 1H),

1.66-1.56 (m, 1H); 13

C NMR (CDCl3, 100 MHz): δ 140.7, 140.3, 139.7, 130.4, 130.0, 129.4, 128.9,

128.5, 128.4, 128.3, 126.9, 126.0, 57.9, 53.4, 35.2, 33.4, 32.3; HRMS (ESI) m/z: [M+H]+ Calcd for

C30H32N 406.2535, Found 406.2535.

N,N-Dibenzyl-1,2-diphenylethanamine (4aa’). Compound 4aa’ was synthesized according to general

procedure B using O-benzoyl-N,N-dibenzylhydroxylamine (3a, 0.300 mmol) to obtain as a white solid

in 90% yield (102 mg, 0.270 mmol). This compound has been previously reported and spectra data

8

match described.5 1H NMR (CDCl3, 400 MHz): δ 7.44-7.40 (m, 2H), 7.36-7.23 (m, 16H), 7.14-7.12 (m,

2H), 4.10 (dd, J = 7.4, 7.4 Hz, 1H), 3.93 (d, J = 14.2 Hz, 2H), 3.43 (dd, J = 14.0, 8.5 Hz, 1H), 3.24 (d, J

= 13.9 Hz, 2H), 3.12 (dd, J = 13.9, 7.1 Hz, 1H); 13

C NMR (CDCl3, 100 MHz): δ 140.0, 139.9, 138.5,

129.6, 129.1, 128.7, 128.2, 128.1, 128.0, 127.2, 126.7, 126.0, 63.1, 53.5, 37.6.

N-(1,2-Diphenylethyl)-N-isopropylpropan-2-amine (4ab). Compound 4ab was synthesized according

to general procedure B using O-benzoyl-N,N-diisopropylhydroxylamine (3b, 0.300 mmol). The

resulting reaction product was purified by acid/base workup. The crude product was diluted with Et2O

(1 mL) and acidified with 1 N HCl (3 x 1 mL). The aqueous layers were combined, basified with 1 N

NaOH (3 mL) and washed with Et2O (3 x 3 mL). Then the organic layers were combined, dried over

MgSO4 and concentrated to afford as a colorless oil in 66% yield (56.1 mg, 0.199 mmol). This

compound has been previously reported and spectra data match described.6 1H NMR (CDCl3, 400

MHz): δ 7.33 (d, J = 7.3 Hz, 2H), 7.24-7.13 (m, 5H), 7.13-7.07 (m, 3H), 4.22 (dd, J = 8.8, 5.9 Hz, 1H),

3.30 (sept, J = 6.7 Hz, 2H), 3.21-3.10 (m, 2H), 1.06 (d, J = 6.6 Hz, 6H), 0.91 (d, J = 6.8 Hz, 6H); 13C

NMR (CDCl3, 100 MHz): δ 144.1, 140.6, 129.3, 128.8, 128.0, 127.8, 126.2, 125.6, 60.5, 45.6, 41.0,

23.0, 22.4.

N-Allyl-N-(1,2-Diphenylethyl)prop-2-en-1-amine (4ac). Compound 4ac was synthesized according to

general procedure B using N,N-diallyl-O-benzoylhydroxylamine (3c, 0.300 mmol) to obtain as colorless

oil in 61% yield (51.1 mg, 0.184 mmol). 1H NMR (CDCl3, 400 MHz): δ 7.30-7.27 (m, 2H), 7.24-7.17

(m, 5H), 7.13 (d, J = 7.1 Hz, 1H), 7.05 (d, J = 7.1 Hz, 2H), 5.82-5.72 (m, 2H), 5.16-5.09 (m, 4H), 4.03

(t, J = 7.5 Hz, 1H), 3.36-3.27 (m, 3H), 2.97 (dd, J = 13.5, 8.3 Hz, 1H), 2.86 (dd, J = 14.4, 7.3 Hz, 2H);

13C NMR (CDCl3, 100 MHz): δ 140.1, 139.9, 136.9, 129.4, 128.9, 127.9, 127.9, 127.0, 125.8, 116.8,

65.1, 52.7, 38.5; HRMS (ESI) m/z: [M+H]+ Calcd for C20H24N 278.1909, Found 278.1897.

N-Benzyl-N-methyl-1,2-diphenylethanamine (4ad). Compound 4ad was synthesized according to

general procedure B using O-benzoyl-N-benzyl-N-methylhydroxylamine (3d, 0.300 mmol) to obtain as

colorless oil in 75% yield (68.0 mg, 0.226 mmol). 1H NMR (CDCl3, 400 MHz): δ 7.44-7.26 (m, 13H),

7.16 (d, J = 7.3 Hz, 2H), 3.95 (t, J = 7.5 Hz, 1H), 3.76 (d, J = 13.2 Hz, 1H), 3.49 (dd, J = 13.7, 6.6 Hz,

1H), 3.43 (d, J = 13.4 Hz, 1H), 3.14 (dd, J = 13.6, 8.4 Hz, 1H), 2.31 (s, 3H); 13

C NMR (CDCl3, 100

MHz): δ 140.0, 140.0, 139.5, 129.5, 128.9, 128.7, 128.2, 128.0, 127.9, 127.0, 126.8, 125.8, 69.5, 58.8,

38.8, 38.0; HRMS (ESI) m/z: [M+H]+ Calcd for C22H24N 302.1909, Found 302.1910.

(5) S. Zhu, N. Niljianskul, S. L. Buchwald, J. Am. Chem. Soc. 2013, 135, 15746

(6) H. Takahashi, T. Tsubuki, K. Higashiyama, Synthesis 1988, 3, 238.

9

1-(1,2-Diphenylethyl)piperidine (4ae). Compound 4ae was synthesized according to general procedure

B using piperidin-1-yl benzoate (3e, 0.300 mmol) to obtain as colorless oil in 80% yield (63.5 mg, 0.239

mmol). This compound has been previously reported and spectra data match described.7 1H NMR

(CDCl3, 400 MHz): δ 7.33-7.25 (m, 3H), 7.22-7.14 (m, 5H), 7.08 (d, J = 7.0 Hz, 2H), 3.67 (dd, J = 9.2,

5.1 Hz, 1H), 3.39 (dd, J = 13.3, 5.0 Hz, 1H), 3.07 (dd, J = 13.0, 9.6 Hz, 1H), 2.56-2.51 (m, 4H), 1.71-

1.58 (m, 4H), 1.45 (q, J = 5.6 Hz, 2H); 13

C NMR (CDCl3, 100 MHz): δ 140.0, 139.5, 129.4, 129.0,

127.9, 127.7, 126.7, 125.7, 72.3, 51.3, 39.1, 26.3, 24.6.

4-(1,2-Diphenylethyl)thiomorpholine (4af). Compound 4af was synthesized according to general

procedure B using thiomorpholino benzoate (3f, 0.300 mmol) to obtain as a white solid in 85% yield

(72.6 mg, 0.256 mmol). This compound has been previously reported and spectra data match described.7

1H NMR (CDCl3, 400 MHz): δ 7.30-7.21 (m, 3H), 7.20-7.09 (m, 5H), 7.06 (d, J = 7.1 Hz, 2H), 3.73 (t,

J = 7.3 Hz, 1H), 3.27 (dd, J = 13.7, 6.3 Hz, 1H), 3.02 (dd, J = 13.7, 8.5 Hz, 1H), 2.87-2.82 (m, 2H),

2.74-2.67 (m, 2H), 2.65-2.59 (m, 4H); 13C NMR (CDCl3, 100 MHz): δ 139.8, 139.0, 129.3, 128.7,

128.1, 128.0, 127.2, 125.9, 72.0, 52.2, 29.6, 28.2.

4-(1,2-Diphenylethyl)morpholine (4ag). Compound 4ag was synthesized according to general

procedure B using morpholino benzoate (3g, 0.300 mmol) to obtain as colorless oil in 79% yield (63.3

mg, 0.237 mmol). This compound has been previously reported and spectra data match described.7

1H

NMR (CDCl3, 400 MHz): δ 7.25-7.19 (m, 3H), 7.17-7.08 (m, 5H), 6.94 (d, J = 6.9 Hz, 2H), 3.71 (t, J =

4.7 Hz, 4H), 3.49 (dd, J = 9.4, 5.3 Hz, 1H), 3.34 (dd, J = 13.2, 5.2 Hz, 1H), 2.89 (dd, J = 12.9, 9.5 Hz,

1H), 2.56-2.45 (m, 4H); 13C NMR (CDCl3, 100 MHz): δ 139.8, 139.3, 129.4, 128.8, 127.9, 127.1, 125.8,

72.5, 67.2, 51.2, 39.2.

tert-Butyl 4-(1,2-diphenylethyl)piperazine-1-carboxylate (4ah). Compound 4ah was synthesized

according to general procedure B using tert-butyl 4-(benzoyloxy)piperazine-1-carboxylate (3h, 0.300

mmol) to obtain as colorless oil in 83% yield (91.3 mg, 0.249 mmol). This compound has been

previously reported and spectra data match described.7

1H NMR (CDCl3, 400 MHz): δ 7.25-7.20 (m,

3H), 7.17-7.10 (m, 5H), 6.98 (d, J = 6.8 Hz, 2H), 3.59 (dd, J = 9.1, 5.7 Hz, 1H), 3.40 (brs, 4H), 3.32 (dd,

J = 13.3, 5.7 Hz, 1H), 2.96 (dd J = 13.3, 9.2 Hz, 1H), 2.44 (brs, 4H), 1.43 (s, 9H); 13

C NMR (CDCl3,

100 MHz): δ 154.7, 139.4, 139.4, 129.4, 128.7, 128.0, 127.2, 125.8, 79.4, 71.8, 50.1, 44.2, 39.1, 28.3.

(7) K. D. Hesp, M. Stradiotto, M. J. Am. Chem. Soc. 2010, 132, 18026.

10

tert-Butyl 4-(1,2-diphenylethyl)-1,4-diazepane-1-carboxylate (4ai). Compound 4ai was synthesized

according to general procedure B using tert-butyl 4-(benzoyloxy)-1,4-diazepane-1-carboxylate (3i,

0.300 mmol) to obtain as colorless sticky oil in 69% yield (78.4 mg, 0.206 mmol). The compound exists

as a 1:1 mixture of ratamers. 1H NMR (CDCl3, 400 MHz): δ 7.26-7.09 (m, 8H), 7.05 (dd, J = 7.5, 7.5

Hz, 2H), 3.90 (dd, J = 12.7, 5.9 Hz, 1H), 3.52-3.30 (m, 4H), 3.30-3.20 (m, 1H), 3.04-2.92 (m, 1H),

2.86-2.70 (m, 2H), 2.70-2.62 (m, 1H), 2.62-2.52 (m, 1H), 1.79-1.72 (m, 1H), 1.72-1.65 (m, 1H), 1.44 (d,

J = 3.9 Hz, 9H); 13

C NMR (CDCl3, 100 MHz): δ 155.6, 140.6, 139.9, 129.3, 128.4, 128.0, 127.9, 127.0,

125.8, 79.1, 70.4, 52.9, 51.9, 47.6, 45.9, 39.2, 28.4; HRMS (ESI) m/z: [M+H]+ Calcd for C24H33N2O2

381.2542, Found 381.2549.

N-(1,2-Diphenylethyl)-2-methylpropan-2-amine (4aj). Compound 4aj was synthesized according to

general procedure B using O-benzoyl-N-(tert-butyl)hydroxylamine (3j, 0.300 mmol). The resulting

reaction product was purified by acid/base workup. The crude product was diluted with Et2O (1 mL)

and acidified with 1 N HCl (3 x 1 mL). The aqueous layers were combined, basified with 1 N NaOH (3

mL) and washed with Et2O (3 x 3 mL). Then the organic layers were combined, dried over MgSO4 and

concentrated to afford as colorless oil in 36% yield (27.0 mg, 0.107 mmol). This compound has been

previously reported and spectra data match described.8 1H NMR (CDCl3, 400 MHz): δ 7.38 (d, J = 7.5

Hz, 2H), 7.26 (dd, J = 13.7, 7.1 Hz, 3H), 7.18 (dd, J = 7.1, 7.1 Hz, 3H), 7.13 (d, J = 7.6 Hz, 2H), 3.98

(dd, J = 8.8, 5.7 Hz, 1H), 2.91 (dd, J = 13.5, 5.4 Hz, 1H), 2.70 (dd, J = 13.5, 9.1 Hz, 1H), 0.82 (s, 9H);

13C NMR (CDCl3, 100 MHz): δ 147.6, 139.3, 129.4, 128.3, 128.1, 127.2, 126.5, 126.4, 59.2, 51.1, 47.1,

29.8.

� Ni-catalyzed hydroalumination of internal aryl acetylene 5a:

OMe

5a

1 mol % Ni(PPh3)2Cl2

DIBAL-H, THF, 22 °C, 3 h

OMe

Al(i-Bu)2

OMe

(i-Bu)2Al

+

7a6a

OMe

D

OMe

D

+

D2O

6a' 7a'

(8) M. Esteruelas, A. M. López, A. C. Mateo, E. Oñate, Organometallics 2005, 24, 5084.

11

1-Methoxy-2-(phenylethynyl)benzene (5a) (41.7 mg, 0.200 mmol), Ni(PPh3)2Cl2 (1.30 mg, 0.00200

mmol) and THF (0.2 mL) were added to a 8 mL vial and then diisobutylaluminum hydride (35.6 μL,

0.200 mmol) was added slowly under N2 gas. The solution was allowed to stir at 22 °C for 3 h. After

that time, the solution was quenched with D2O (or H2O) and the stereo- and site selectivity were

determined by analysis of 1H NMR spectra. The (Z)-1-methoxy-2-styrylbenzene was observed in

>98:<2 Z:E selectivity. The (Z)-1-methoxy-2-styrylbenzene has been previously reported and spectra

data match described.9 (Z)-1-methoxy-2-styrylbenzene:

1H NMR (CDCl3, 400 MHz): δ 7.27-7.16 (m,

6H), 6.90 (d, J = 8.3 Hz , 1H), 6.76 (t, J = 7.4 Hz, 1H), 6.70 (d, J = 12.2 Hz, 1H), 6.64 (d, J = 12.2 Hz,

1H), 3.86 (s, 3H); (Z)-1-(1-deutrio-2-phenylvinyl)-2-methoxybenzene (6a’): 1H NMR (CDCl3, 400

MHz): δ 7.27-7.16 (m, 6H), 6.90 (d, J = 8.3 Hz , 1H), 6.76 (t, J = 7.4 Hz, 1H), 6.64 (s, 1H), 3.86 (s, 3H).

Site selectivity (91:9) was determined by analysis of 1H NMR spectra of the unpurified reaction

mixtures through comparison of the protonated sample (below left) with deuterated sample (below

right).

(E)-N,N-Dibenzyl-1-(2-methoxyphenyl)-2-phenylethenamine (8aa). Compound 8aa was synthesized


obtain as slightly yellow oil in 89% yield (108 mg, 0.267 mmol). 1H NMR (CDCl3, 400 MHz): δ 7.38-

7.32 (m, 10H), 7.29-7.22 (m, 2H), 6.99-6.94 (m, 4H), 6.85 (dd, J = 7.2, 7.2 Hz, 1H), 6.65 (d, J = 7.6 Hz,

2H), 5.64 (s, 1H), 4.32 (d, J = 15.9 Hz, 2H), 4.23 (d, J = 15.9 Hz, 2H), 3.78 (s, 3H); 13

C NMR (CDCl3,

100 MHz): δ 158.1, 145.7, 139.5, 138.9, 132.0, 129.9, 128.3, 127.8, 127.6, 127.1, 128.7, 126.3, 123.3,

121.3, 111.3, 103.6, 55.4, 52.4; HRMS (ESI) m/z: [M+H]+ Calcd for C29H28NO 406.2171, Found

406.2148.

(9) J. Li, R. Hua, T. Liu, J. Org. Chem. 2010, 75, 2966.

12

(E)-N,N-Dibenzyl-2-(3-chlorophenyl)-1-(2-methoxyphenyl)ethenamine (8ba). Compound 8ba was


mmol) to obtain as slightly yellow sticky oil in 84% yield (111 mg, 0.252 mmol). 1H NMR (CDCl3, 400

MHz): δ 7.40-7.24 (m, 12H), 6.98 (dd, J = 7.3, 7.3 Hz, 2H), 6.85 (dd, 7.7, 7.7 Hz, 1H), 6.80 (d, J = 7.8

Hz, 1H), 6.58 (s, 1H), 6.46 (d, J = 7.8 Hz, 1H), 5.53 (s, 1H), 4.35 (d, J = 15.8 Hz, 2H), 4.25 (d, J = 15.8

Hz, 2H), 3.80 (s, 3H); 13

C NMR (CDCl3, 100 MHz): δ 157.9, 147.0, 141.6, 138.6, 133.4, 131.7, 130.3,

128.6, 128.4, 127.6, 126.8, 126.8, 125.7, 124.9, 122.9, 121.5, 111.3, 101.3, 55.4, 52.4; HRMS (ESI)

m/z: [M+H]+ Calcd for C29H27ClNO 440.1781, Found 440.1787.

(E)-N,N-Dibenzyl-1-(2-methoxyphenyl)-2-(3-(trifluoromethyl)phenyl)ethenamine (8ca). Compound

8ca was synthesized according to general procedure A using O-benzoyl-N,N-dibenzylhydroxylamine

(3a, 0.300 mmol) to obtain as yellow sticky oil in 80% yield (114 mg, 0.241 mmol). 1H NMR (CDCl3,

400 MHz): δ 7.39-7.24 (m, 12H), 7.03-7.01 (m, 2H), 6.96 (dd, J =7.3, 4.4 Hz, 2H), 6.80 (s, 1H), 6.75 (d,

J = 6.8 Hz, 1H), 5.58 (s, 1H), 4.34 (d, J = 15.8 Hz, 2H), 4.24 (d, J = 15.8 Hz, 2H), 3.76 (s, 3H); 13C

NMR (CDCl3, 100 MHz): δ 157.9, 147.4, 140.4, 138.5, 131.7, 130.4, 129.8 (q, J = 32 Hz), 128.4, 128.4

(q, J = 17 Hz), 127.6, 127.7 (q, J = 16 Hz), 126.9, 125.5, 124.4 (q, J = 272 Hz), 123.5 (q, J = 4 Hz),

121.5, 111.2, 101.2, 55.5, 52.4; HRMS (ESI) m/z: [M+H]+ Calcd for C30H27F3NO 474.2045, Found

474.2048.

(E)-N,N-Dibenzyl-2-(4-fluorophenyl)-1-(2-methoxyphenyl)ethenamine (8da). Compound 8da was


mmol) to obtain as colorless sticky oil in 87% yield (111 mg, 0.262 mmol). 1H NMR (CDCl3, 400

MHz): δ 7.58-7.50 (m, 1H), 7.38-7.23 (m, 10H), 6.98-6.93 (m, 3H), 6.66 (dd, J = 12.2, 8.8 Hz, 2H),

6.59 (dt, J = 6.0, 2.7 Hz, 2H), 5.58 (s, 1H), 4.28 (d, J = 15.6 Hz, 2H), 4.21 (d, J = 15.6 Hz, 2H), 3.77 (s,

3H); 13

C NMR (CDCl3, 100 MHz): δ 159.7 (d, J = 242 Hz), 158.0, 145.5, 138.9, 135.6 (d, J = 3.0 Hz),

133.6 (d, J = 3.0 Hz), 132.1, 130.0, 129.9, 128.3 (d, J = 6.0 Hz), 127.8, 126.8, 126.1, 121.2, 120.6,

114.2 (d, J = 12 Hz), 111.2, 102.5, 55.3, 52.5; HRMS (ESI) m/z: [M+H]+ Calcd for C29H27FNO

424.2077, Found 424.2063.

13

�� Cu-catalyzed electrophilic amination of 1-phenyl-1-propyne:10

�� Cu-catalyzed electrophilic amination of phenylacetylene:11

1 mol % Ni(dppp)Cl2

Al(i-Bu)2(i-Bu)2Al

+

>98:<2, S8:S9

S8 S9

5 mol % CuCl

THF, 22 C, 1 h

N

S10 (55% yield)

BzO N 3e

S7

>98% conv+

H Al(i-Bu)2

THF, 22 C, 3 h

(10) (a) Reaction was performed according to general procedure A. Yields were determined by 1H NMR

spectrum analysis using 1,3,5-trimethoxybenzene as an internal standard. (b) The hydroalumination of 1-phenyl-

1-propyne (S1) in the presence of 1 mol % of Ni(dppp)Cl2 was also not regioselective, delivering a 55:45 mixture

of S2 and S3 vinylaluminums.

(11) Reactions were performed according to general procedure A. Yields were determined by 1H NMR spectrum

analysis using 1,3,5-trimethoxybenzene as an internal standard. Hydroalumination of phenylacetylene (S7) with 1

mol % Ni(dppp)Cl2 provided the internal vinylaluminum S8 in >98% yield. Cu-catalyzed electrophilic amination

of S8 with 3e was less efficient than that of 1,2-diaryl-substituted vinylaluminums, affording the desired enamine

product S10 in 55% yield with unidentified byproducts. In the presence of 1 mol % Ni(PPh3)2Cl2,

hydroalumination of S7 resulted in a 23:77 mixture of S8 and S9 vinylaluminums (a 12:88 mixture of S8 and S9

under the conditions developed by the Hoveyda group (F. Gao, A. H. Hoveyda, J. Am. Chem. Soc. 2010, 132,

10961.)). When the following amination with a mixture of regioisomers was carried out, vinylaluminum S8 was

aminated in 18% yield of the desired enamine S10. However, amination of terminal vinylaluminum S9 did not

proceed efficiently to give the enamine product S11 (<5% yield) under the optimized conditions for internal aryl

acetylenes.

14

�� 2D-NOSEY proton NMR specta of enamines 4ca and 8ba and 1H NOESY correlations

6.0 5.5 5.0 4.5 4.0

F2 Chemical Shift (ppm)

4.5

5.0

5.5

6.0

F1

Ch

em

ica

l S

hift

(pp

m)

5.5 5.0 4.5 4.0

F2 Chemical Shift (ppm)

4.5

5.0

5.5 F1

Ch

em

ica

l S

hift

(pp

m)

15

■ 1H NMR and

13C NMR spectra for all products:

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5

Chemical Shift (ppm)

0

0.5

1.0

No

rma

lize

d I

nte

nsity

0.144.161.000.022.146.632.034.724.46

4.1

5

5.7

0

6.7

36.7

57.2

37.2

57.2

97.3

17.3

47.3

67.3

87.6

17.6

3

NPh

Ph

CF3F3C

E

Z

Figure S1.

1H NMR spectrum of the compound 4ba (98:2 mixture of E:Z isomers)

170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0


0.5

1.0

Norm

aliz

ed Inte

nsity

52

.83

76

.68

77

.00

77

.32

10

6.5

9

12

5.2

01

25

.92

12

7.3

71

27

.97

12

8.0

31

28

.59

12

9.0

31

29

.06

12

9.6

11

31

.01

13

7.6

0

14

2.1

9

14

9.8

5

Figure S2. 13

C NMR spectrum of the compound 4ba

16

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5


0

0.5

1.0

No

rma

lize

d I

nte

nsity

0.214.301.000.042.121.121.174.862.424.631.312.241.09

1.5

7

4.1

9

5.7

3

6.8

56

.87

7.1

07

.15

7.2

67

.27

7.3

17

.33

7.3

77

.38

7.4

07

.64

7.6

57

.72

NPh

Ph

CF3F3C

E

Z

Figure S3. 1H NMR spectrum of the compound 4ca (96:4 mixture of E:Z isomers)

160 140 120 100 80 60 40 20 0


0.5

1.0

No

rma

lize

d I

nte

nsity

14

9.4

71

39

.15

13

7.6

71

33

.99

13

1.2

31

29

.47

12

8.9

61

28

.73

12

8.5

91

28

.11

12

8.0

01

27

.35

12

5.4

81

24

.80

12

0.7

3

10

6.3

7

77

.31

77

.00

76

.68

52

.89

Figure S4. 13

C NMR spectrum of the compound 4ca

17

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0


0

0.5

1.0

1.5

2.0

No

rma

lize

d I

nte

nsity

3.333.174.311.000.071.011.151.142.311.181.366.735.823

.53

3.7

5

4.1

7

5.6

2

6.2

86

.40

6.4

26

.48

6.4

86

.89

6.9

36

.95

7.0

67

.11

7.1

37

.27

7.2

97

.32

7.3

47

.36

7.3

7

E

Z

N

Ph

Ph

OMeMeO

Figure S5. 1H NMR spectrum of the compound 4da (93:7 mixture of E:Z isomers)

170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10


0.5

1.0

No

rma

lize

d I

nte

nsity

16

0.0

71

59

.08

14

9.4

9

14

0.3

71

38

.91

13

8.4

41

29

.80

12

9.2

01

28

.52

12

8.3

91

28

.05

12

7.3

31

27

.00

12

3.1

71

20

.95

11

5.9

71

14

.15

11

2.5

21

10

.44

10

6.4

1

77

.31

77

.00

76

.68

55

.24

54

.70

52

.65

Figure S6. 13

C NMR spectrum of the compound 4da

18

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0


0

0.5

1.0

1.5

2.0

No

rma

lize

d I

nte

nsity

4.461.000.012.072.074.641.586.842.34

4.1

1

5.5

8

6.6

36

.65

6.9

76

.99

7.2

27

.24

7.2

47

.27

7.2

97

.33

7.3

57

.39

7.4

1N

Ph

Ph

ClCl

Figure S7. 1H NMR spectrum of the compound 4ea (>98:<2 mixture of E:Z isomers)

160 140 120 100 80 60 40 20


0

0.5

1.0

1.5

2.0

No

rma

lize

d I

nte

nsity

14

8.8

1

13

7.9

81

35

.49

13

2.0

21

29

.39

12

9.1

51

28

.64

12

8.6

31

28

.47

12

8.0

81

27

.90

12

7.1

9

10

6.5

8

77

.31

77

.00

76

.68

52

.72

Figure S8. 13

C NMR spectrum of the compound 4ea

19

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0


0

0.5

1.0

1.5

2.0

No

rma

lize

d I

nte

nsity

1.092.091.012.061.012.302.302.257.335.29

2.9

72

.99

3.0

13

.03

3.1

63

.19

3.3

23

.34

3.3

63

.38

3.8

63

.89

3.9

84

.00

4.0

2

6.9

46

.97

7.0

17

.08

7.2

07

.22

7.2

37

.25

7.2

77

.28

7.3

0

N

Ph

Ph

FF

Figure S9. 1H NMR spectrum of the compound 4fa’

180 160 140 120 100 80 60 40 20 0


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

No

rma

lize

d I

nte

nsity

16

3.2

71

62

.70

16

0.8

21

60

.27

13

9.7

11

35

.26

13

4.0

21

30

.76

13

0.4

51

30

.37

12

8.6

41

28

.59

12

8.3

11

26

.93

11

4.9

81

14

.93

11

4.7

7

77

.32

77

.00

76

.68

62

.68

53

.50

36

.90

Figure S10. 13

C NMR spectrum of the compound 4fa’

20

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

No

rma

lize

d I

nte

nsity

1.052.031.023.125.881.000.881.982.431.972.229.64

2.9

93

.01

3.0

33

.17

3.2

03

.27

3.2

93

.31

3.3

33

.81

3.8

33

.87

3.9

43

.96

3.9

84

.12

4.1

4

6.7

96

.90

6.9

26

.97

7.1

67

.19

7.2

17

.23

7.2

47

.26

7.2

7N

Ph

Ph

OMeMeO

Figure S11. 1H NMR spectrum of the compound 4ga’

160 140 120 100 80 60 40 20


0

0.5

1.0

1.5

No

rma

lize

d I

nte

nsity

15

8.6

11

57

.87

14

0.1

71

32

.91

13

2.0

81

30

.61

13

0.3

91

30

.08

12

8.6

41

28

.17

12

6.6

9

11

3.9

71

13

.40

11

3.2

3

77

.31

77

.00

76

.68

62

.57

55

.20

55

.11

53

.44

36

.77

Figure S12. 13

C NMR spectrum of the compound 4ga’

21

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0


0

0.5

1.0

No

rma

lize

d I

nte

nsity

5.971.002.031.011.941.002.192.234.0511.24

7.2

57

.25

7.2

37

.22

7.2

17

.20

7.1

77

.15

7.0

36

.98

4.0

24

.00

3.9

83

.88

3.8

4

3.3

53

.33

3.3

23

.30

3.2

13

.17

3.0

73

.05

3.0

4

2.3

72

.34

N

Ph

Ph

MeMe

Figure S13. 1H NMR spectrum of the compound 4ha’

160 140 120 100 80 60 40 20 0


0

0.5

1.0

1.5

2.0

No

rma

lize

d I

nte

nsity

14

0.2

01

36

.88

13

6.6

01

35

.43

13

5.2

21

29

.42

12

9.0

11

28

.77

12

8.6

81

28

.15

12

6.6

7

77

.32

77

.00

76

.68

62

.79

53

.49

37

.10

20

.97

Figure S14. 13

C NMR spectrum of the compound 4ha’

22

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5


0

0.5

1.0

1.5

No

rma

lize

d I

nte

nsity

4.111.001.051.082.262.611.9410.14

4.2

2

5.7

7

6.4

46

.46

6.4

86

.64

6.8

76

.89

6.9

07

.10

7.2

67

.27

7.2

97

.32

7.3

37

.34

7.3

57

.36

N

Ph

Ph

FF

Figure S15. 1H NMR spectrum of the compound 4ia

160 140 120 100 80 60 40 20 0


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

No

rma

lize

d I

nte

nsity

16

2.1

11

61

.09

15

9.6

31

58

.65

14

4.4

91

38

.17

13

2.5

31

30

.42

12

8.7

61

28

.73

12

8.4

21

27

.95

12

7.0

41

25

.54

12

5.4

61

24

.47

12

3.0

91

16

.18

11

5.9

61

14

.77

11

4.5

5

98

.71

77

.32

77

.00

76

.68

52

.82

Figure S16. 13

C NMR spectrum of the compound 4ia

23

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5


0

0.5

1.0

1.5

2.0

No

rma

lize

d In

ten

sity

6.632.272.211.011.051.021.511.3312.898.64

2.2

02.2

1

4.1

14.1

5

4.2

74.3

1

5.6

7

6.3

56.3

7

6.6

56.6

76.8

16.9

97.1

27.1

77.1

97.1

97.2

47.2

67.3

07.3

27.3

37.3

4

N

Ph

Ph

MeMe

Figure S17. 1H NMR spectrum of the compound 4ja

160 140 120 100 80 60 40 20 0


0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

No

rma

lize

d In

ten

sity

148.2

0139.6

4138.8

7137.6

5131.1

3130.3

3129.3

5129.1

2128.3

6128.0

3127.9

8126.9

1125.8

2124.9

8

103.5

3

77.3

177.0

076.6

8

52.7

0

20.3

319.6

9

Figure S18. 13

C NMR spectrum of the compound 4ja

24

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0


0

0.5

1.0

1.5

2.0

No

rma

lize

d I

nte

nsity

4.141.000.991.021.031.106.794.981.07

4.2

0

5.9

4

6.5

36

.54

6.7

76

.78

6.8

37

.10

7.2

47

.25

7.2

57

.26

7.2

77

.28

7.3

27

.34

7.5

27

.54

N

Ph

Ph

SS

Figure S19. 1H NMR spectrum of the compound 4ka

170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10


0.5

1.0

1.5

No

rma

lize

d I

nte

nsity

14

2.4

71

40

.47

13

8.1

1

13

0.3

71

29

.32

12

8.4

91

28

.40

12

8.2

01

27

.87

12

7.5

11

27

.10

12

6.0

71

23

.96

12

1.9

8

10

2.5

9

77

.32

77

.00

76

.68

52

.71

Figure S20. 13

C NMR spectrum of the compound 4ka

25

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

No

rma

lize

d I

nte

nsity

0.950.991.020.991.891.202.421.983.828.668.78

1.5

91

.60

1.6

11

.62

1.6

4

1.8

92

.30

2.3

22

.46

2.4

82

.49

2.5

22

.85

2.8

62

.87

2.8

92

.92

3.1

03

.12

3.1

43

.15

3.5

73

.60

3.8

13

.85

7.0

27

.03

7.2

07

.21

7.2

37

.25

7.3

07

.32

7.3

37

.35

N

Ph

Ph

Figure S21. 1H NMR spectrum of the compound 4la’

160 140 120 100 80 60 40 20


0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

No

rma

lize

d I

nte

nsity

14

0.7

21

40

.30

12

9.3

81

28

.90

12

8.7

81

28

.54

12

8.4

01

28

.39

12

8.2

61

26

.84

12

6.0

3

77

.32

77

.00

76

.68

57

.88

53

.43

35

.24

33

.36

32

.30

Figure S22. 13

C NMR spectrum of the compound 4la’

26

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0


0

0.5

1.0

1.5

2.0

No

rma

lize

d I

nte

nsity

1.001.911.021.871.001.8615.511.97

3.1

13

.13

3.1

53

.22

3.2

53

.40

3.4

33

.44

3.4

6

3.9

13

.94

4.0

84

.10

4.1

2

7.1

47

.23

7.2

47

.25

7.2

77

.29

7.3

07

.31

7.3

17

.42

N Ph

Ph

Figure S23. 1H NMR spectrum of the compound 4aa’

160 140 120 100 80 60 40 20 0


0.5

1.0

No

rma

lize

d I

nte

nsity

14

0.0

4

13

8.5

01

29

.61

12

9.0

91

28

.68

12

8.2

01

28

.05

12

7.1

71

26

.74

12

5.9

6

77

.32

77

.00

76

.69

63

.14

53

.51

37

.55

Figure S24. 13

C NMR spectrum of the compound 4aa’

27

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

No

rma

lize

d I

nte

nsity

6.416.382.112.131.003.145.122.11

0.9

20

.94

1.0

81

.10

3.1

83

.19

3.2

03

.30

3.3

13

.33

3.3

5

4.2

04

.22

4.2

4

7.0

87

.10

7.1

17

.15

7.1

67

.18

7.2

07

.22

7.3

57

.36

N

Figure S25. 1H NMR spectrum of the compound 4ab

170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10


0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

No

rma

lize

d I

nte

nsity

14

4.0

5

14

0.5

8

12

9.3

01

28

.83

12

7.9

71

27

.75

12

6.1

91

25

.62

77

.31

77

.00

76

.68

60

.47

45

.63

40

.98

22

.95

22

.35

Figure S26. 13

C NMR spectrum of the compound 4ab

28

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

No

rma

lize

d I

nte

nsity

2.101.043.121.004.162.001.970.925.202.42

1.5

8

2.8

32

.85

2.8

72

.89

2.9

83

.01

3.2

83

.30

3.3

23

.32

3.3

53

.36

4.0

14

.03

4.0

5

5.0

95

.12

5.1

6

5.7

45

.74

5.7

55

.76

5.7

85

.79

5.7

95

.80

7.0

57

.06

7.1

77

.18

7.1

97

.20

7.2

17

.24

7.2

77

.28

N

Figure S27. 1H NMR spectrum of the compound 4ac

170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10


0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

No

rma

lize

d I

nte

nsity

14

0.0

71

39

.90

13

6.9

4

12

9.4

31

28

.85

12

7.9

41

26

.95

12

5.7

6

11

6.8

2

77

.32

77

.00

76

.69

65

.09

52

.72

38

.52

Figure S28. 13

C NMR spectrum of the compound 4ac

29

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0


0

0.5

1.0

1.5

2.0

No

rma

lize

d I

nte

nsity

3.141.021.070.971.231.002.0313.70

2.3

1

3.1

23

.14

3.1

53

.17

3.4

13

.45

3.4

73

.48

3.5

23

.74

3.7

73

.93

3.9

53

.97

7.1

77

.19

7.2

97

.31

7.3

37

.35

7.3

67

.38

7.4

07

.42

N Ph

CH3

Figure S29. 1H NMR spectrum of the compound 4ad

160 140 120 100 80 60 40 20 0


0

0.5

1.0

1.5

2.0

No

rma

lize

d I

nte

nsity

13

9.9

91

39

.50

12

9.4

51

28

.89

12

8.7

41

28

.18

12

7.9

91

27

.04

12

5.8

2

77

.32

77

.21

77

.00

76

.68

69

.54

58

.80

38

.83

37

.97

Figure S30. 13

C NMR spectrum of the compound 4ad

30

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0


0

0.5

1.0

No

rma

lize

d I

nte

nsity

2.214.224.041.041.041.042.005.043.04

1.4

31

.44

1.4

61

.47

1.6

11

.62

1.6

41

.65

1.6

61

.68

2.5

12

.52

2.5

43

.05

3.0

73

.08

3.1

13

.37

3.3

83

.40

3.4

13

.65

3.6

63

.67

3.6

9

7.0

97

.19

7.2

07

.20

7.2

17

.21

7.2

27

.22

7.3

07

.33

N

Figure S31. 1H NMR spectrum of the compound 4ae

180 160 140 120 100 80 60 40 20 0


0

0.5

1.0

1.5

No

rma

lize

d I

nte

nsity

14

0.0

31

39

.44

12

9.4

11

28

.97

12

7.8

91

27

.70

12

6.8

61

25

.66

77

.32

77

.00

76

.69

72

.28

51

.35

39

.11

26

.27

24

.56

Figure S32. 13

C NMR spectrum of the compound 4ae

31

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

No

rma

lize

d I

nte

nsity

3.882.202.031.011.001.001.975.083.33

1.5

7

2.6

22

.63

2.6

42

.64

2.6

52

.71

2.7

22

.84

2.8

53

.02

3.0

43

.26

3.2

93

.73

3.7

33

.75

3.7

8

7.0

57

.07

7.1

57

.17

7.1

87

.26

7.2

67

.27

7.2

77

.29

N

S

Figure S33. 1H NMR spectrum of the compound 4af

160 140 120 100 80 60 40 20 0


0

0.5

1.0

1.5

No

rma

lize

d I

nte

nsity

13

9.8

01

38

.96

12

9.3

31

28

.70

12

8.0

41

27

.97

12

7.1

81

25

.88

77

.31

77

.00

76

.68

72

.01

52

.15

29

.63

28

.22

Figure S34. 13

C NMR spectrum of the compound 4af

32

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

No

rma

lize

d I

nte

nsity

3.910.950.981.003.921.984.982.97

2.4

62

.48

2.4

92

.50

2.5

3

2.8

82

.89

2.9

23

.32

3.3

33

.37

3.4

63

.48

3.4

93

.70

3.7

13

.72

6.9

36

.95

7.1

17

.12

7.1

37

.14

7.1

97

.21

7.2

27

.25

N

O

Figure S35. 1H NMR spectrum of the compound 4ag

160 140 120 100 80 60 40 20


0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

No

rma

lize

d I

nte

nsity

13

9.7

61

39

.26

12

9.4

11

28

.76

12

7.9

11

27

.11

12

5.7

9

77

.31

77

.00

76

.68

72

.45

67

.18

51

.21

39

.19

Figure S36. 13

C NMR spectrum of the compound 4ag

33

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

No

rma

lize

d I

nte

nsity

9.133.920.951.053.971.001.925.042.88

1.4

3

2.4

42

.93

2.9

52

.96

2.9

83

.29

3.3

13

.33

3.3

43

.40

3.5

73

.58

3.5

93

.61

6.9

76

.99

7.1

07

.11

7.1

37

.15

7.1

77

.22

7.2

37

.25

N

NBoc

Figure S37. 1H NMR spectrum of the compound 4ah

160 140 120 100 80 60 40 20 0


0.5

1.0

No

rma

lize

d I

nte

nsity

15

4.7

4

13

9.4

31

39

.35

12

9.3

71

28

.74

12

7.9

61

27

.17

12

5.8

4

79

.41

77

.32

77

.00

76

.69

71

.77

50

.12

44

.23

39

.13

28

.32

Figure S38. 13

C NMR spectrum of the compound 4ah

34

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

No

rma

lize

d I

nte

nsity

9.622.342.112.111.031.174.161.022.018.67

1.4

4

1.6

91

.75

2.5

82

.64

2.7

82

.96

2.9

93

.01

3.2

43

.27

3.2

73

.36

3.4

1

3.9

0

7.0

47

.11

7.1

27

.13

7.1

57

.18

7.2

07

.24

7.2

6N

NBoc

Figure S39. 1H NMR spectrum of the compound 4ai

160 140 120 100 80 60 40 20 0


0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

No

rma

lize

d I

nte

nsity

15

5.6

21

55

.51

14

0.5

61

39

.90

13

9.8

2

12

9.2

91

28

.44

12

7.9

81

27

.92

12

6.9

81

26

.96

79

.09

79

.04

77

.31

77

.00

76

.68

70

.43

70

.29

52

.89

52

.53

51

.92

51

.56

47

.63

47

.23

45

.86

45

.05

39

.18

28

.41

Figure S40. 13

C NMR spectrum of the compound 4ai

35

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0


0

0.5

1.0

No

rma

lize

d I

nte

nsity

10.011.011.011.002.152.704.732.21

0.8

2

2.6

72

.69

2.7

02

.72

2.8

82

.90

2.9

22

.93

3.9

53

.97

3.9

73

.99

7.1

17

.13

7.1

87

.20

7.2

37

.25

7.2

77

.29

7.3

77

.38

NH

Figure S41. 1H NMR spectrum of the compound 4ai

160 140 120 100 80 60 40 20 0


0.5

1.0

No

rma

lize

d I

nte

nsity

14

7.6

2

13

9.3

4

12

9.3

51

28

.34

12

8.1

21

27

.15

12

6.4

81

26

.35

77

.31

77

.00

76

.68

59

.19

51

.07

47

.13

29

.80

Figure S42. 13

C NMR spectrum of the compound 4ai

36

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0


0

0.5

1.0

1.5

2.0

No

rma

lize

d I

nte

nsity

3.322.202.161.002.061.084.102.4610.38

3.7

7

4.2

04

.24

4.3

04

.34

5.6

4

6.6

46

.66

6.9

46

.95

6.9

66

.97

6.9

86

.99

7.2

67

.27

7.3

27

.33

7.3

6

N Ph

Ph

OMe

Figure S43. 1H NMR spectrum of the compound 8aa

160 140 120 100 80 60 40 20 0


0.5

1.0

No

rma

lize

d I

nte

nsity

15

8.0

6

14

5.7

21

39

.50

13

8.9

21

32

.02

12

9.8

81

28

.26

12

7.7

71

27

.60

12

7.0

81

26

.72

12

6.3

41

23

.27

12

1.2

9

11

1.2

7

10

3.5

6

77

.32

77

.00

76

.69

55

.38

52

.44

Figure S44. 13

C NMR spectrum of the compound 8aa

37

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0


0

0.5

1.0

1.5

2.0

No

rma

lize

d I

nte

nsity

3.642.322.141.061.041.121.091.132.3715.37

3.8

0

4.2

34

.27

4.3

34

.37

5.5

3

6.4

56

.47

6.5

86

.81

6.8

56

.97

6.9

87

.26

7.2

67

.29

7.3

17

.32

7.3

47

.36

7.4

0N Ph

Ph

OMe

Cl

Figure S45. 1H NMR spectrum of the compound 8ba

170 160 150 140 130 120 110 100 90 80 70 60 50 40 30


0

0.5

1.0

No

rma

lize

d I

nte

nsity

15

7.8

5

14

6.9

8

14

1.5

9

13

8.5

81

33

.36

13

1.7

41

30

.26

12

8.6

41

28

.36

12

7.6

11

26

.84

12

6.7

9

12

4.9

41

22

.89

12

1.4

5

11

1.2

5

10

1.3

1

77

.32

77

.00

76

.68

55

.39

52

.40

Figure S46. 13

C NMR spectrum of the compound 8ba

38

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0


0

0.5

1.0

1.5

2.0

No

rma

lize

d I

nte

nsity

3.262.121.951.001.161.022.192.0213.47

3.7

7

4.2

24

.26

4.3

24

.36

5.5

8

6.7

46

.80

6.9

46

.95

6.9

67

.03

7.2

47

.26

7.2

77

.29

7.3

07

.32

7.3

4N Ph

Ph

OMe

F3C

Figure S47. 1H NMR spectrum of the compound 8ca

170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10


0

0.5

1.0

1.5

No

rma

lize

d I

nte

nsity

15

7.8

7

14

7.3

7

14

0.4

21

38

.54

13

1.6

71

30

.35

12

9.9

41

28

.53

12

8.3

91

27

.79

12

7.7

11

27

.62

12

6.8

81

25

.51

12

1.4

11

19

.45

11

1.1

8

10

1.2

1

77

.32

77

.00

76

.68

55

.45

52

.41

Figure S48. 13

C NMR spectrum of the compound 8ca

39

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

No

rma

lize

d I

nte

nsity

3.534.501.022.152.243.0613.491.00

7.5

77

.56

7.3

57

.33

7.3

17

.29

7.2

97

.27

7.2

67

.25

6.9

66

.95

6.6

66

.64

6.5

96

.58

5.5

8

4.3

04

.26

4.2

34

.19

3.7

7

1.5

6

N Ph

Ph

OMeF

Figure S49. 1H NMR spectrum of the compound 8da

180 160 140 120 100 80 60 40 20


0.5

1.0

No

rma

lize

d I

nte

nsity

16

0.9

51

58

.53

15

8.0

4

14

5.4

91

38

.89

13

5.6

01

33

.62

13

2.0

51

29

.96

12

9.8

81

28

.29

12

7.7

81

26

.76

12

6.1

11

21

.27

12

0.5

61

15

.65

11

5.4

41

14

.36

11

4.1

51

11

.24

10

2.5

4

77

.32

77

.00

76

.68

55

.33

52

.52

Figure S50. 13

C NMR spectrum of the compound 8da

Cu-Catalyzed Electrophilic Amination of Internal Alkynes ... · PDF file1 Cu-Catalyzed...

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