Supplementary Information

Pd-catalyzed decarboxylative allylic coupling of acetates of Baylis-Hillman alcohols with propiolic acids: A highly regio- and stereoselective synthesis of 1,5-diarylpent-1-en-4-yne derivatives.Satyanarayana Tummanapalli*,a Parthasarathy Muthuraman,a Dhanunjaya Naidu Vangapandu,a Gnanakalai Shanmugavel,a

Sanjeeva Kambampatia and Kee Wei Leea

a Albany Molecular Research Singapore Research Center, 61 Science Park Road, #03-13 The Galen, Singapore Science Park II, Singapore 117525.

1) Typical procedure for the synthesis of methyl 2-(acetoxy(4-methoxyphenyl)methyl)acrylate (2a):

OCO2Me

O

2a

OHCO2Me

Pydrine (1.5 equiv)CH2Cl2, rt, 30 min.

MeO

Cl

MeOMeOI

To a stirred solution of methyl 2-(hydroxy(4-methoxyphenyl)methyl)acrylate I (0.45

mmol), pyridine (0.90 mmol) in dichloromethane (5 mL), acetyl chloride (0.54 mmol) was

added at 0 °C and allowed to stir at room temperature for 30 min. Upon reaction completion

as judged by TLC, the resulting mixture was diluted with dichloromethane (10 mL), washed

with 2N HCl solution (5 mL), satd. NaHCO3 solution (5 mL) and dried over Na2SO4. The

organic layer was concentrated under reduced and purified by column chromatograph on

silica (0-5% EtOAc/hexanes) to afford methyl 2-(acetoxy(4-methoxyphenyl)methyl)acrylate

2a (0.42 mmol, 95%). 1H NMR (400 MHz, CDCl3): δ 2.07 (s, 3H), 3.68 (s, 3H), 3.77 (s, 3H),

5.86-5.87 (m, 1H), 6.37 (s, 1H), 6.63 (s, 1H), 6.86-6.86 (d, J = 8.79 Hz, 2H), 7.28-7.31 (d, J =

8.67 Hz, 2H; 13C NMR (100 MHz, CDCl3): δ 21.0, 51.94, 55.22, 72.85, 113.8, 125.11, 129.1,

129.8, 139.7, 159.6, 165.4, 169.4; ESI-MS calc. for C14H17O5 [M+H]+ = 265; Found: m/z

265.

Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2015

2) Typical procedure for the synthesis of (E)-methyl 2-(4-methoxybenzylidene)-5-phenylpent-4-ynoate (4b):

CO2Me

4aE-isomer

(isolated yield = 88%)

OCO2Me

O

2a

Me

Pd(OAc)2 (5 mol%)

Cs2CO3 (2 equiv.)THF, 70 oC, 30 min

S-Phos (10 mol%) MeOMeO

CO2H

3a

To a stirred solution of methyl 2-(acetoxy(4-methoxyphenyl)methyl)acrylate 2a (0.42 mmol)

) in dry THF (15 mL), was added Pd(OAc)2 (0.021 mmol), 2-dicyclohexylphosphino-2',6'-

dimethoxybiphenyl (0.042 mmol) was added followed by 3-phenylpropiolic acid (0.50 mmol)

and Cs2CO3 (0.84 mmol) was added and the mixture was heated to 70 °C for 30 min. Upon

reaction completion as judged by TLC, the resulting mixture was diluted with ethyl acetate

(10 mL), washed with water (5 mL), brine (5 mL) and dried over Na2SO4. The organic layer

was concentrated under reduced pressure and purified by column chromatography on silica

(0-5% EtOAc/hexanes) to afford (E)-methyl 2-(4-methoxybenzylidene)-5-phenylpent-4-

ynoate 4a (0.036 mmol, 85%).

1H NMR (400 MHz, CDCl3):

2D NOESY (400 MHz, CDCl3):

13C NMR (100 MHz, CDCl3):

ESI-MS calc. for C20H19O3[M+H]+ : 307; Found: m/z 307:

3) Typical procedure for the synthesis of 2-cyano-1-(4-methoxyphenyl)allyl acetate (7a):

OCN

O

OHCN

Pydrine (1.5 equiv)CH2Cl2, rt, 30 min.

MeO

Cl

MeOMeOII 7a

To a stirred solution of 2-(hydroxy(4-methoxyphenyl)methyl)acrylonitrile II (0.52 mmol),

pyridine (1.04 mmol) in dichloromethane (5 mL), acetyl chloride (0.63 mmol) was added at 0

°C and allowed to stir at room temperature for 30 min. Upon the reaction completion as

judged by TLC, the resulting mixture was diluted with dichloromethane (10 mL), washed

with 2N HCl solution (5 mL), satd. NaHCO3 solution (5 mL) and dried over Na2SO4. The

organic layer was concentrated under reduced and purified by column chromatograph on

silica (0-5% EtOAc/hexanes) to afford 2-cyano-1-(4-methoxyphenyl)allyl acetate 7a (0.69

mmol, 91%). 1H NMR (400 MHz, CDCl3): δ 2.15 (s, 3H), 3.81 (s, 3H), 5.97-5.98 (d, J = 1.39

Hz, 1H), 6.05-6.06 (d, J = 1.07 Hz, 1H), 6.28 (s, 1H), 6.90-6.93 (d, J = 8.78 Hz, 2H), 7.31-

7.33 (d, J = 8.53 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 20.9, 55.3, 74.0, 114.3, 116.3,

123.3, 127.7, 128.5, 131.5, 160.2, 169.2; ESI-MS calc. for C13H14NO3 [M+H]+ = 232; Found:

m/z 232.

4) Typical procedure for the synthesis of (Z)-2-(4-methoxybenzylidene)-5-phenylpent-4-

ynenitrile (8a):

Pd(OAc)2 (5 mol%)

Cs2CO3 (2 equiv.)THF, 70 oC, 30 min

CNMeO

8a(Z-isomers)

(isolated yield =89%)

S-Phos (10 mol%)

OCN

O

Me

MeO

7a

CO2H

3a

To a stirred solution of 2-cyano-1-(4-methoxyphenyl)allyl acetate 7a (0.43 mmol) in dry THF

(15 mL), was added Pd(OAc)2 (0.021 mmol), 2-dicyclohexylphosphino-2',6'-

dimethoxybiphenyl (0.042 mmol) was added and followed by 3-phenylpropiolic acid (0.51

mmol) and Cs2CO3 (0.86 mmol) was added and the mixture was heated to 70 °C for 30 min.

Upon reaction completion as judged by TLC, the resulting mixture was diluted with ethyl

acetate (10 mL), washed with water (5 mL), brine (5 mL) and dried over Na2SO4. The

organic layer was concentrated under reduced pressure and purified by column

chromatography on silica (0-5% EtOAc/hexanes) to afford (Z)-2-(4-methoxybenzylidene)-5-

phenylpent-4-ynenitrile (8a) (0.38 mmol, 89%).

1H NMR (300 MHz, CDCl3):

2D NOESY (400 MHz, CDCl3):

13C NMR (75 MHz, CDCl3):

ESI-MS calc. for C19H16NO [M+H]+ : 274; Found: m/z 274:

3) Analytical data of aryl propiolates (physical description, melting point, 1H NMR, 13C NMR and MS data):

Products Analytical Data

References for known compounds

CO2Me

4a

MeO

(E)-methyl 2-(4-methoxybenzylidene)-5-phenylpent-4-ynoate (4a): Physical description: Yellowish gum; 1H NMR (400 MHz, CDCl3): δ 3.62 (s, 2H), 3.85 (s, 3H), 3.86 (s, 3H), 6.97 (d, J = 8.83 Hz, 2H), 7.26-7.28 (m, 3H), 7.39-7.42 (m, 2H), 7.58 (d, J = 8.71 Hz, 2H), 7.76 (s, 1H); 13C NMR (100 MHz, CDCl3): δ 18.7, 52.2, 55.3, 80.8, 87.2, 114.1, 123.6, 125.4, 127.5, 127.7, 128.1, 131.7, 131.7, 140.5, 160.3, 168.0; ESI-MS calc. for C19H19O3[M+H]+ : 307; Found: m/z 307.

1

CO2Me

4b

(E)-methyl 2-benzylidene-5-phenylpent-4-ynoate (4b): Physical description: Brown gum; 1H NMR (400 MHz, CDCl3): δ 3.61 (s, 2H), 3.88 (s, 3H), 7.25-7.28 (m, 3H), 7.37-7.46 (m, 5H), 7.57-7.59 (m, 2H), 7.81 (s, 1H); 13C NMR (100 MHz, CDCl3): δ 18.7, 52.3, 80.9, 87.1, 123.6, 127.7, 127.8, 128.1, 128.6, 129.0, 129.7, 131.7, 134.9, 140.7, 167.7; ESI-MS calc. for C19H17O2[M+H]+ : 277; Found: m/z 277.

1, 2

CO2Me

4c

Me

MeMe

(E)-methyl 2-(4-(tert-butyl)benzylidene-5-(m-tolyl)pent-4-ynoate (4c): Physical description: Yellowish gum; 1H NMR (400 MHz, CDCl3): δ 1.34 (s, 9H), 3.62 (s, 2H), 3.87 (s, 3H), 7.26-7.28 (m, 3H), 7.39-7.41 (m, 2H), 7.46 (d, J= 8.49 Hz, 2H), 7.55 (d, J= 8.49 Hz, 2H), 7.79 (s, 1H); 13C NMR (100 MHz,

---

CDCl3): δ 18.8. 31.2, 34.8, 52.2, 80.8, 87.2, 123.6, 125.6, 126.8, 127.7, 128.1, 129.7, 131.7, 132.1, 140.7, 152.4, 167.9; ESI-MS calc. for C23H25O2[M+H]+ : 333; Found: m/z 333.

CO2Me

4d

Me

(E)-methyl 2-(4-methylbenzylidene)-5-phenylpent-4-ynoate (4d): Physical description: Brown gum; 1H NMR (400 MHz, CDCl3): δ 2.38 (s, 3H), 3.61 (s, 2H), 3.86 (s, 3H), 7.23-7.27 (m, 5H), 7.38-7.39 (m, 1H), 7.40-7.41 (m, 1H), 7.49-51 (m, 2H), 7.78 (s, 1H); 13C NMR (100 MHz, CDCl3): δ 18.8, 21.4, 52.2, 80.8, 87.2, 123.6, 126.7, 127.7, 128.1, 129.3, 129.8, 131.7, 132.1, 139.3, 140.8, 167.9; ESI-MS calc. for C20H17O2 [M-H]- : 289; Found: m/z 289.

---

CO2Me

4e

Me

(E)-methyl 2-benzylidene-5-(m-tolyl)pent-4-ynoate (4e): Physical description: Light Brown gum; 1H NMR (400 MHz, CDCl3): δ 2.31 (s, 3H), 3.60 (s, 2H), 3.88 (s, 3H), 7.08 (d, J = 7.21 Hz, 1H), 7.16 (t, J = 7.20 Hz, 1H), 7.23 (t, J = 6.40 Hz, 2H), 7.35-7.39 (m, 1H), 7.42-7.46 (m, 2H), 7.58 (s, 2H), 7.80 (s, 1H); 13C NMR (100 MHz, CDCl3): δ 18.7, 21.1, 52.3, 81.1, 86.7, 123.4, 127.8, 128.0, 128.6, 128.6, 128.7, 129.0, 129.7, 132.3, 134.9, 137.8, 140.6, 167.7; ESI-MS calc. for C20H19O2[M+H]+ : 291; Found: m/z 291.

3

CO2Me

4f

Me

Me

(E)-methyl 2-(4-methylbenzylidene)-5-(m-tolyl)phenylpent-4-ynoate (4f): Physical description: colourless gum; 1H NMR (400 MHz, CDCl3): δ 2.30 (s, 3H), 2.39 (s, 3H), 3.60 (s, 2H), 3.86 (s, 3H), 7.07-7.09 (m, 1H), 7.14-7.18 (m, 1H), 7.20-7.26 (m, 4H), 7.49-7.51 (m, 2H), 7.78 (s, 1H); 13C NMR (100 MHz, CDCl3): δ 21.2, 21.4, 26.2, 82.6, 85.8, 105.0, 118.5, 122.5, 128.2, 128.8, 128.8, 129.3, 129.5, 130.5, 1325.3, 138.0, 140.7, 144.2; ESI-MS calc. for C21H21O2[M+H]+ : 305; Found: m/z 305.

---

CO2Me

4gMe

Me

MeMe

(E)-methyl 2-(4-(tert-butyl)benzylidene)-5-(p-tolyl)pent-4-ynoate (4g): Physical description: Light Brown gum; 1H NMR (400 MHz, CDCl3): δ 1.34 (s, 9H), 2.33 (s, 3H), 3.61 (s, 2H), 3.87 (s, 3H), 7.07 (d, J = 7.82 Hz , 2H), 7.29 (d, J = 7.64 Hz, 2H), 7.45 (d, J = 8.18 Hz, 2H), 7.55 (d, J = 7.82 Hz, 2H), 7.78 (s, 1H); 13C NMR (100 MHz, CDCl3): δ 18.8, 21.4, 31.2, 34.8, 52.2, 80.9, 86.4, 120.6, 125.6, 127.0, 128.8, 129.7, 131.6, 132.1, 137.7, 140.6, 152.4, 167.9; ESI-MS calc. for C24H27O2[M+H]+ : 347; Found: m/z 347.

---

CNMeO

8a

(Z)-2-(4-methoxybenzylidene)-5-(phenylpent-4-ynenitrile) (8a): Physical description: Brown gum; 1H NMR (300 MHz, CDCl3): δ 3.56 ( d, J = 3.0Hz, 2H ), 3.85 (s, 3H), 6.92-6.95 (m, 2H), 7.31-7.34 (m, 3H), 7.45-7.49 (m, 2H), 7.74-7.77 (m, 2H); 13C NMR (75 MHz, CDCl3): δ 26.2, 55.4, 83.2, 85.5, 103.1, 114.2, 118.7, 122.8, 126.0, 128.3, 128.4, 130.6, 131.7, 143.8, 161.2; ESI-MS calc. for C19H16NO [M+H]+ : 274; Found: m/z 274.

---

CO2Me

4hOMe

(E)-methyl 2-(3-methoxybenzylidene)-5-phenylpent-4-ynoate (4h): Physical description: Colorless oil; 1H NMR (400 MHz, CDCl3): δ 3.61 (s, 2H), 3.83 (s, 3H), 3.88 (s, 3H), 6.91-6.94 (m, 1H), 7.13-7.15 (m, 1H), 7.20 (t, J = 2.00 Hz, 1H), 7.26-7.27 (m, 3H), 7.34 (t, J = 8.00 Hz, 1H), 7.39-7.41 (m, 2H), 7.78 (s, 1H); 13C NMR (100 MHz, CDCl3): δ 18.9, 52.3, 55.3, 81.0, 87.1, 114.4, 115.3, 122.2, 123.6, 127.8, 127.9, 128.1, 129.6, 131.6, 136.2, 140.7, 159.6, 167.6; ESI-MS calc. for C20H19O3[M+H]+ : 307; Found: m/z 307.

---

CO2Me

4iOMe

Me

(E)-methyl 2-(3-methoxybenzylidene)-5-(p-tolyl)pent-4-ynoate (4i): Physical description: Colorless oil ; 1H NMR (400 MHz, CDCl3): δ 2.32 (s, 3H), 3.60 (s, 2H), 3.82 (s, 3H), 3.87 (s, 3H), 6.90-6.93 (m, 1H), 7.07 (d, J = 7.6 Hz, 2H), 7.14 (dd, J1-3 = 7.6 Hz, J1-2 = 0.4 Hz, 1H), 7.21 (t, J = 2.00 Hz, 1H), 7.28 (d, J = 8.0 Hz, 2H), 7.35 (t, J = 7.97 Hz, 1H), 7.77 (s, 1H); 13C NMR (100 MHz, CDCl3): δ 18.9, 21.4, 52.3, 55.3, 81.1, 86.3, 114.3, 115.4, 120.5, 122.2, 128.0, 128.9, 129.6, 131.5, 136.3, 137.8, 140.6, 159.6, 167.7; ESI-MS calc. for C21H21O3[M+H]+ : 321; Found: m/z 321.

---

CN

8b

(Z)-2-benzylidene-5-phenylpent-4-ynenitrile (8a): Physical description: colourless gum; 1H NMR (CDCl3): δ 3.58 (d, J = 1.69 Hz, 2H), 7.32-7.35 (m, 4H), 7.42-7.43 (m, 3H), 7.46-7.49 (m, 2H), 7.77-7.78 (m, 2H) ; 13C NMR (100 MHz, CDCl3): δ 26.3, 82.8, 85.8, 106.3, 118.2, 122.7, 128.3, 128.4, 128.8, 128.8, 130.3, 131.7, 133.2, 144.3; ESI-MS calc. for C18H12N [M-H]-: 242; Found: m/z 242.

1

CN

8cMe

MeMe

(Z)-2-(4-(tert-butyl)benzylidene)-5-phenylpent-4-ynenitrile (8c): Physical description: Yellowish gum; 1H NMR (400 MHz, CDCl3): δ 1.33 (s, 9H), 3.56 (d, J = 1.70, 2H), 7.31-7.33 (m, 4H), 7.43-7.48 (m, 4H), 7.71 (d, J = 8.35 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 26.2, 31.1, 34.9, 83.1, 85.6, 105.1, 118.4, 122.7, 125.8. 128.3, 128.4, 128.6, 130.5, 131.7, 144.2, 153.9; ESI-MS calc. for C22H20N [M-H]- : 298; Found: m/z 298.

---

CNMe

8d

(Z)-2-(4-methylbenzylidene)-5-phenylpent-4-ynenitrile (8d): 1H NMR (400 MHz, CDCl3): δ 2.37 (s, 3H), 3.55 ( d, J = 1.50 Hz, 2H), 7.21 ( d, J = 8.10 Hz, 2H), 7.29 (s, 1H), 7.31-7.32 (m, 3H), 7.46-7.48 (m, 2H), 7.65-7.67 ( d, J = 8.24 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 21.5, 26.2, 83.1, 85.7, 105.0, 118.4, 122.7, 128.3, 128.4, 128.8, 129.5, 130.5, 131.7, 140.8, 144.3; ESI-MS calc. for C19H14N [M-H]- : 256; Found: m/z 256.

1

CN

8e

Me

(Z)-2-benzylidene-5-(m-tolyl)pent-4-ynenitrile (8e): Physical description: colourless gum; 1H NMR (300 MHz, CDCl3): δ 2.34 (s, 3H), 3.57 (d, J = 1.60 Hz, 2H), 7.13-7.24 (m, 2H), 7.25-7.30 (m, 2H), 7.35 (s, 1H), 7.41-7.43 (m, 3H), 7.75-7.78 (m, 2H); 13C NMR (100 MHz, CDCl3): δ 21.2, 26.3, 82.4, 86.0, 106.4, 118.2, 122.4, 128.2, 128.8, 128.8, 129.3, 130.3, 132.3, 133.3, 138.0, 144.3; ESI-MS calc. for C19H16N [M+H]+ : 258; Found: m/z 258.

3

CNMe

8f

Me

(Z)-2-(4-methylbenzylidene)-5-(m-tolyl)pent-4-ynenitrile (8f): Physical description: Brown gum; 1H NMR (300 MHz, CDCl3): δ 2.33 (s, 3H), 2.38 (s, 3H), 3.55 (d, J = 1.50 Hz, 2H), 7.13-7.25 (m, 1H), 7.19-7.23 (m, 3H), 7.24-7.30 (m, 3H), 7.66-7.68 (m, 2H); 13C NMR (100 MHz, CDCl3): δ 18.7, 21.1, 21.4, 52.2, 81.0, 86.8, 123.4, 126.8, 128.0, 128.6, 128.7, 129.3, 129.8, 132.1, 132.3, 137.7, 139.3, 140.7; ESI-MS calc. for C20H18N[M+H]+ : 272; Found: m/z 272.

---

CN

8gMe

MeMe

Me

(Z)-2-(4-(tert-butyl)benzylidene)-5-(p-tolyl)pent-4-ynenitrile (8g): Physical description: colourless gum; 1H NMR (400 MHz, CDCl3): δ 1.33 (s, 9H), 2.35 (s, 3H), 3.55 (d, J = 1.48 Hz, 2H), 7.13 ( d, J = 7.92 Hz, 2H ), 7.31 (s, 1H), 7.36 ( d, J = 8.14 Hz, 2H), 7.44 ( d, J = 8.47 Hz, 2H), 7.71 ( d, J = 8.40 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 21.4, 26.2, 31.1, 34.9, 82.3, 85.8, 105.3, 118.5, 119.6, 125.8, 128.6, 129.1, 130.5, 131.6, 138.5, 144.1, 153.8; ESI-MS calc. for C23H22N [M-H]- : 312; Found: m/z 312.

---

CN

8hMe

(Z)-2-(3-methylbenzylidene)-5-phenylpent-4-ynenitrile (8h): Physical description: Light yellow oil; 1H NMR (400 MHz, CDCl3): δ 2.38 (s, 3H), 3.56 (d, J = 1.6 Hz, 2H), 7.21 (d, J = 7.55 Hz, 1H), 7.30-7.33 (m, 5H), 7.46-7.48 (m, 2H), 7.54 (s, 1H), 7.58 (d, J = 7.77 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ 21.3, 26.3, 83.0, 85.8, 106.0, 118.3, 122.7, 125.8, 128.3, 128.4, 128.7, 129.5, 131.1, 131.7, 133.2, 138.5, 144.5; ESI-MS calc. for C19H14N[M-H]- : 256; Found: m/z 256.

---

CN8iMe Me

(Z)-2-(3-methylbenzylidene)-5-(p-tolyl)pent-4-ynenitrile (8i): Physical description: Light yellow oil ; 1H NMR (400 MHz, CDCl3): δ 2.33 (s, 3H), 2.38 (s, 3H), 3.55 (d, J = 1.50 Hz, 2H), 7.13-7.25 (m, 1H), 7.19-7.23 (m, 3H), 7.24-7.30 (m, 3H), 7.66-7.68 (m, 2H); 13C NMR (100 MHz, CDCl3): δ 18.7, 21.1, 21.4, 52.2, 81.0, 86.8, 123.4, 126.8, 128.0, 128.6, 128.7, 129.3, 129.8, 132.1, 132.3, 137.7, 139.3, 140.7; ESI-MS calc. for C20H18N[M+H]+ : 272; Found: m/z 272.

---

CN

8jOMe

(Z)-2-(3-methoxybenzylidene)-5-phenylpent-4-ynenitrile (8j): Physical description: Light yellow oil ; 1H NMR (400 MHz, CDCl3): δ 3.57 (d, J = 1.64 Hz, 2H), 3.84 (s, 3H), 6.94-6.97 (m, 1H), 7.30-7.33 (m, 6H), 7.36 (s, 1H), 7.46-7.48 (m, 2H); 13C NMR (100 MHz, CDCl3): δ 26.3, 55.3, 82.8, 85.8, 106.5, 113.2, 116.7, 118.2, 121.6, 122.6, 128.3, 128.4, 129.8, 131.7, 134.5, 144.2, 159.8; ESI-MS calc. for C19H14NO[M-H]- : 272; Found: m/z 272.

---

CN

8kOMe Me

(Z)-2-(3-methoxybenzylidene)-5-(p-tolyl)pent-4-ynenitrile (8k): Physical description: Light yellow oil; 1H NMR (400 MHz, CDCl3): δ 2.35 (s, 3H), 3.55 (d, J = 1.62 Hz, 2H), 3.83 (s, 3H), 6.93-6.96 (m, 1H), 7.12 (d, J = 7.60 Hz, 2H), 7.27-7.32 (m, 3H), 7.35-7.37 (m, 3H); 13C NMR (100 MHz, CDCl3): δ 21.4, 26.3, 55.3, 82.1, 86.0, 106.6, 113.1, 116.7, 118.2, 119.6, 121.6, 129.1, 129.8, 131.6, 134.5, 138.6, 144.2, 159.8; ESI-MS calc. for C20H18NO[M+H]+ : 288; Found: m/z 288.

---

14

OMe

(E)-4-benzylidene-7-phenylhept-6-yn-3-one (14): Physical description: Light yellow oil; 1H NMR (400 MHz, CDCl3): δ 1.21 ( t, J = 7.23 Hz, 3H ), 2.90 ( q, J = 7.27 Hz, 2H ), 3.60 (s, 2H), 7.24-7.27 (m, 3H), 7.36-7.40 (m, 3H), 7.43-7.47 (m, 2H), 7.61 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 8.6, 17.7, 31.0, 80.8, 87.4, 123.6, 127.7, 128.1, 128.6, 129.1, 131.7, 135.1, 136.3, 139.5, 201.0; ESI-MS calc. for C20H19O[M+H]+ : 275; Found: m/z 275.

---

15Me

OMe

(E)-4-benzylidene-7-(p-tolyl)hept-6-yn-3-one (15): Physical description: Light yellow oil; 1H NMR (400 MHz, CDCl3): δ 1.20 ( t, J = 7.13 Hz, 3H ), 2.31 (s, 3H), 2.89 ( q, J = 7.13 Hz, 2H ), 3.59 (s, 2H), 7.06 ( d, J = 7.87 Hz, 2H), 7.27 ( d, J = 8.04 Hz, 2H), 7.35-7.39 (m, 1H), 7.42-7.46 (m, 2H), 7.60-7.62 (m, 3H); 13C NMR (100 MHz, CDCl3): δ 8.6, 17.7, 21.4, 31.0, 80.8, 86.6, 120.5, 128.6, 128.8, 129.0, 129.7, 131.5, 136.4, 137.7, 139.4, 201.1; ESI-MS calc. for C21H21O[M+H]+ : 289; Found: m/z 289.

---

References:

1. J. S. Yadav, B. V. S. Reddy, N. N. Yadav, A. P. Singh, M. Choudhary, and A. C. Kunwar, Tetrahedron Lett. 2008, 49, 6090–6094.

2. S. Gowrisankar, K.Y. Lee, C. G. Lee, and J. N. Kim, Tetrahedron Lett. 2004, 45, 6141–6146.3. T. Satyanarayana, V. Dhanunjaya Naidu, M. Parthasarathy and N. Shashidhar, DOI:

10.1016/j.tetlet.2015.02.125.

16

O

O Me

OMe

(E)-ethyl 2-(3-methoxybenzylidene)-5-phenylpent-4-ynoate (16): Physical description: Light yellow oil; 1H NMR (400 MHz, CDCl3): δ 1.38 (t, J = 7.13 Hz, 3H), 3.61 (s, 2H), 3.83 (s, 3H), 4.34 (q, J = 7.13 Hz, 2H), 6.91-6.94 (m, 1H), 7.13-7.15 (m, 1H), 7.19-7.20 (m, 1H), 7.25-7.28 (m, 3H), 7.32-7.38 (m, 1H), 7.39-7.41 (m, 2H), 7.78 (s, 1H); 13C NMR (100 MHz, CDCl3): δ 14.3, 18.8, 55.3, 61.2, 80.9, 87.3, 114.4, 115.2, 122.1, 123.6, 127.7, 128.1, 128.2, 129.6, 131.6, 136.3, 140.4, 159.6, 167.1; ESI-MS calc. for C21H21O3[M+H]+ : 321; Found: m/z 321.

GKS

83%

O

O Me

OMe

Me17

(E)-ethyl 2-(3-methoxybenzylidene)-5-(p-tolyl)pent-4-ynoate (17): Physical description: Light yellow oil; 1H NMR (400 MHz, CDCl3): δ 1.37 (t, J = 7.30 Hz, 3H), 3.59 (s, 2H), 3.80 (s, 3H), 4.32 (q, J = 7.14 Hz, 2H), 6.90-6.92 (m, 1H), 7.07 (d, J = 7.74 Hz, 2H), 7.12-7.15 (m, 1H), 7.19-7.20 (m, 1H), 7.24-7.30 (m, 3H), 7.33 (d, J = 7.89 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 14.3, 18.9, 21.4, 55.3, 61.2, 81.0, 86.5, 114.3, 115.3, 120.6, 122.2, 128.4, 128.9, 129.6, 131.5, 136.4, 137.7, 140.3, 159.6, 167.2; ESI-MS calc. for C22H23O3[M+H]+ : 335; Found: m/z 335.

GKS

85%

18

SO

O

MeO

Me

(E)-1-methoxy-4-(2-(phenylsulfonyl)-5-(p-tolyl)pent-1-en-4-yn-1-yl)benzene (18): Physical description: Light yellow oil; 1H NMR (400 MHz, CDCl3): δ 2.30 (s, 3H), 3.68 (s, 2H), 3.84 (s, 3H), 6.93-6.98 (m, 4H), 7.01 (d, J = 7.88 Hz, 2H), 7.48-7.53 (m, 3H), 7.62 (d, J = 8.84 Hz, 2H), 7.89 (s, 1H), 7.98-8.01 (m, 2H); 13C NMR (100 MHz, CDCl3): δ 18.4, 21.4, 55.4, 81.9, 83.8, 114.4, 119.7, 125.6, 128.4, 128.7, 129.0, 131.4, 132.0, 133.1, 133.7, 138.0, 139.4, 140.3, 161.1; ESI-MS calc. for C25H23O3S[M+H]+ : 403; Found: m/z 403.

MPS

78%

19

SO

O

Me

Me

(E)-4,4'-(2-(phenylsulfonyl)pent-1-en-4-yne-1,5-diyl)bis(methylbenzene) (19): Physical description: Light yellow oil; 1H NMR (400 MHz, CDCl3): δ 2.31 (s, 3H), 2.39 (S, 3h), 3.68 (s, 2H), 6.95 (d, J = 7.6 Hz, 2H), 7.01 (d, J = 8.00 Hz, 2H), 7.25 (s, 1H), 7.27 (s, 1H), 7.49-7.55 (m, 5H), 7.93 (s, 1H), 8.01 (d, J = 7.60 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 18.4, 21.4, 21.4, 82.0, 83.8, 119.7, 128.1, 128.5, 128.7, 129.0, 129.6, 130.1, 130.2, 131.4, 133.2, 135.4, 139.8, 140.2, 140.5; ESI-MS calc. for C25H23O2S[M+H]+ : 387; Found: m/z 387.

MPS

80%,

(E)-methyl 2-benzylidene-5-phenylpent-4-ynoate (4b):

i) 1H NMR (400 MHz, CDCl3):

ii) 13C NMR (100 MHz, CDCl3):

iii) ESI-MS calc. for C19H17O2[M+H]- : 277; Found: m/z 277:

(E)-methyl 2-(4-(tert-butyl)benzylidene)-5-phenylpent-4-ynoate (4c):

i) 1H NMR (400 MHz, CDCl3):

ii) 13C NMR (100 MHz, CDCl3):

iii) ESI-MS calc. for C23H25O2 [M+H]+: 333; Found: m/z 333:

(E)-methyl 2-(4-methylbenzylidene)-5-phenylpent-4-ynoate (4d):

i) 1H NMR (400 MHz, CD3Cl3):

ii) 13C NMR (100 MHz, CDCl3):

iii) ESI-MS calc. for C20H17O2 [M-H]- : 289; Found: m/z 289:

(E)-methyl 2-benzylidene-5-(m-tolyl)pent-4-ynoate (4e):i) 1H NMR (400 MHz, CDCl3):

ii) 13C NMR (100 MHz, CDCl3):

iii) ESI-MS calc. for C20H19O2 [M+H]+ : 291; Found: m/z 291:

(E)-methyl 2-(4-methylbenzylidene)-5-(m-tolyl)pent-4-ynoate (4f):

i) 1H NMR (400 MHz, CDCl3):

ii) 13C NMR (100 MHz, CDCl3):

iii) ESI-MS calc. for C21H21O2 [M+H]+ : 305; Found: m/z 305:

(E)-methyl 2-(4-(tert-butyl)benzylidene)-5-(p-tolyl)pent-4-ynoate (4g):

i) 1H NMR (400 MHz, CDCl3):

ii) 13C NMR (100 MHz, CDCl3):

iii) ESI-MS calc. for C24H27O2 [M+H]+ : 347; Found: m/z 347:

(E)-methyl 2-(3-methoxybenzylidene)-5-phenylpent-4-ynoate (4h):

i) 1H NMR (400 MHz, CDCl3):

ii) 13C NMR (100 MHz, CDCl3):

iii) ESI-MS calc. for C20H19O3[M+H]+ : 307; Found: m/z 307:

(E)-methyl 2-(3-methoxybenzylidene)-5-(p-tolyl)pent-4-ynoate (4i):

i) 1H NMR (400 MHz, CDCl3):

ii) 13C NMR (100 MHz, CDCl3):

iii) ESI-MS calc. for C21H21O3[M+H]+ : 321; Found: m/z 321:

(Z)-2-benzylidene-5-phenylpent-4-ynenitrile (8b):

i) 1H NMR (400 MHz, CDCl3):

ii) 13C NMR (100 MHz, CDCl3):

iii) ESI-MS calc. for C18H12N [M-H]- : 242; Found: m/z 242:

(Z)-2-(4-(tert-butyl)benzylidene)-5-phenylpent-4-ynenitrile (8c):

i) 1H NMR (400 MHz, CDCl3):

ii) 13C NMR (100 MHz, CDCl3 ):

iii) ESI-MS calc. for C22H20NO [M-H]- : 298; Found: m/z 298:

(Z)-2-(4-methylbenzylidene)-5-phenylpent-4-ynenitrile (8d):

i) 1H NMR (400 MHz, CDCl3):

ii) 13C NMR (100 MHz, CDCl3):

iii) ESI-MS calc. for C19H14N [M-H]- : 256; Found: m/z 256:

(Z)-2-benzylidene-5-(m-tolyl)pent-4-ynenitrile (8e):

i) 1H NMR (300 MHz, CDCl3):

ii) 13C NMR (100 MHz, CDCl3 ):

iii) ESI-MS calc. for C19H16N [M+H]+ : 258; Found: m/z 258:

(Z)-2-(4-methylbenzylidene)-5-(m-tolyl)pent-4-ynenitrile (8f):

i) 1H NMR (300 MHz, CDCl3):

ii) 13C NMR (100 MHz, CDCl3):

iii) ESI-MS calc. for C20H18N [M+H]+ : 272; Found: m/z 272:

(Z)-2-(4-(tert-butyl)benzylidene)-5-(p-tolyl)pent-4-ynenitrile (8g):

i) 1H NMR (400 MHz, CDCl3):

ii) 13C NMR (100 MHz, CDCl3):

iii) ESI-MS calc. for C23H14N [M+H]+ : 312; Found: m/z 312:

(Z)-2-(3-methylbenzylidene)-5-phenylpent-4-ynenitrile (8h):

i) 1H NMR (400 MHz, CDCl3):

ii) 13C NMR (100 MHz, CDCl3):

iii) ESI-MS calc. for C19H14N [M-H]- : 256; Found: m/z 256:

(Z)-2-(4-methylbenzylidene)-5-(m-tolyl)pent-4-ynenitrile (8i):

i) 1H NMR (400 MHz, CDCl3):

ii) 13C NMR (100 MHz, CDCl3):

iii) ESI-MS calc. for C20H18N [M+H]+: 272; Found: m/z 272:

(Z)-2-(3-methoxybenzylidene)-5-phenylpent-4-ynenitrile (8j):

i) 1H NMR (400 MHz, CDCl3):

ii) 13C NMR (100 MHz, CDCl3):

iii) ESI-MS calc. for C19H14NO [M-H]-: 272; Found: m/z 272:

(Z)-2-(3-methoxybenzylidene)-5-(p-tolyl)pent-4-ynenitrile (8k):

i) 1H NMR (400 MHz, CDCl3):

ii) 13C NMR (100 MHz, CDCl3):

iii) ESI-MS calc. for C20H18NO [M+H]+: 288; Found: m/z 288:

(E)-4-benzylidene-7-phenylhept-6-yn-3-one (14):

i) 1H NMR (400 MHz, CDCl3):

ii) 13C NMR (100 MHz, CDCl3):

iii) ESI-MS calc. for C20H19O [M+H]+: 275; Found: m/z 275:

(E)-4-benzylidene-7-(p-tolyl)hept-6-yn-3-one (15):

i) 1H NMR (400 MHz, CDCl3):

ii) 13C NMR (100 MHz, CDCl3):

iii) ESI-MS calc. for C21H21O [M+H]+: 289; Found: m/z 289:

(E)-ethyl 2-(3-methoxybenzylidene)-5-phenylpent-4-ynoate (16):

i) 1H NMR (400 MHz, CDCl3):

ii) 13C NMR (100 MHz, CDCl3):

iii) ESI-MS calc. for C21H21O3 [M+H]+: 321; Found: m/z 321:

(E)-ethyl 2-(3-methoxybenzylidene)-5-(p-tolyl)pent-4-ynoate (17):

i) 1H NMR (400 MHz, CDCl3):

ii) 13C NMR (100 MHz, CDCl3):

iii) ESI-MS calc. for C22H23O3 [M+H]+: 335; Found: m/z 335:

(E)-1-methoxy-4-(2-(phenylsulfonyl)-5-(p-tolyl)pent-1-en-4-yn-1-yl)benzene (18):

i) 1H NMR (400 MHz, CDCl3):

ii) 13C NMR (100 MHz, CDCl3):

iii) ESI-MS calc. for C25H23O3S [M+H]+: 403; Found: m/z 403:

(E)-4,4'-(2-(phenylsulfonyl)pent-1-en-4-yne-1,5-diyl)bis(methylbenzene) (19):

i) 1H NMR (400 MHz, CDCl3):

ii) 13C NMR (100 MHz, CDCl3):

iii) ESI-MS calc. for C25H23O2S [M+H]+: 387; Found: m/z 387: