Highly stereoselective synthesis of (Z)-1,2-dihaloalkenes by a ...1 Supporting Materials to Highly...

1

Supporting Materials to

Highly stereoselective synthesis of (Z)-1,2-dihaloalkenes by a

Pd-catalyzed hydrohalogenation of alkynyl halides

Gangguo Zhu,* Dongxu Chen, Yuyi Wang, and Renwei Zheng

Department of Chemistry, Zhejiang Normal University, 688 Yingbin Road, Jinhua

321004, China

General………….………………………………………………………..………….S2

General Procedures for Experiments and Analytical Data……………..…..S2-S15

References………………………………………………………………………….S15

NMR Spectra……………………...…………………………..…..………… S16-S59

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012

2

General: Unless otherwise noted, all reactions and manipulations were conducted

under air atmosphere. Column chromatography was performed using silica gel

(300–400 mesh). 1H NMR and 13C NMR spectra were recorded on a 400 MHz NMR

spectrometers. Chemical shifts were reported in ppm downfield from

tetramethylsilane with the solvent resonance as the internal standard. MS and

microanalysis were performed in the state authorized analytical center of Zhejiang

Normal University. HOAc were distilled from KMnO4 and acetic anhydride prior to

use.

General Procedure for the Pd-Catalyzed Synthesis of (Z)-1,2-Dihaloalkenes:

Compound 5.1 To a solution of LiCl (42.5 mg, 1.0 mmol) and [(allyl)PdCl]2 (4.6 mg,

0.0125 mmol) in 1 mL of HOAc was added cis,cis-1,5-cyclooctadiene (5.4 mg, 0.05

mmol) and phenylethynyl chloride (1a) (68 mg, 0.5 mmol). After stirring for 6 h at 80 oC, the reaction mixture was quenched with 5 mL of water, extracted with ethyl

acetate, washed with brine, dried over anhydrous Na2SO4 and concentrated. Column

chromatography on silica gel (petroleum ether) gave 74 mg (yield: 85%) of

(Z)-1,2-dichloro-l-phenylethene (5) as a colorless oil. 1H NMR (CDCl3, 400 MHz): δ

6.70 (s, 1 H), 7.36–7.42 (m, 3 H), 7.51–7.58 (m, 2 H); 13C NMR (CDCl3, 100 MHz):

δ 116.0, 126.6 (2 C), 128.6 (2 C), 129.4, 135.6, 135.7; MS (EI, m/z): 176 (8), 174 (60),

172 (M+, 90), 139 (28), 137 (M+–35Cl, 100).

6

ClCl

H

F

Compound 6. The title compound was prepared from 1b in 72% yield as a colorless

oil. 1H NMR (CDCl3, 400 MHz): δ 6.65 (s, 1 H), 7.08 (t, J = 8.4 Hz, 2 H), 7.48–7.56


3

(m, 2 H); 13C NMR (CDCl3, 100 MHz): δ 115.7 (d, J = 21.9 Hz, 2 C), 115.9 (d, J =

1.6 Hz, 1 C), 128.5 (d, J = 8.4 Hz, 2 C), 132.0 (d, J = 3.3 Hz, 1 C), 134.6, 162.8 (d, J

= 248.6 Hz, 1 C); MS (EI, m/z): 194 (6), 192 (38), 190 (M+, 58), 157 (32), 155

(M+–35Cl, 100); Anal. Calcd. for C8H5Cl2F, HRMS (EI): Cacl. 189.9752, Found:

189.9756.

7

ClCl

H

Cl

Compound 7.2 The title compound was prepared from 1c in 88% yield as a colorless

oil. 1H NMR (CDCl3, 400 MHz): δ 6.70 (s, 1 H), 7.36 (d, J = 8.4 Hz, 2 H), 7.47 (d, J

= 8.4 Hz, 2 H); 13C NMR (CDCl3, 100 MHz): δ 116.6, 127.8 (2 C), 128.8 (2 C), 134.2,

134.6, 135.5; MS (EI, m/z): 210 (20), 208 (70), 206 (M+, 75), 175 (10), 173 (60), 171

(M+–35Cl, 100); Anal. Calcd. for C8H5Cl3, HRMS (EI): Cacl. 205.9457, Found:

205.9455.

8

ClCl

HCl

Cl

Compound 8. The title compound was prepared from 1d in 90% yield as a colorless

oil. 1H NMR (CDCl3, 400 MHz): δ 6.52 (s, 1 H), 7.27–7.34 (m, 2 H), 7.46 (d, J = 2.0

Hz, 1 H); 13C NMR (CDCl3, 100 MHz): δ 120.6, 127.3, 130.0, 130.9, 131.9, 133.8,

134.1, 136.2; MS (EI, m/z): 244 (38), 242 (80), 240 (M+, 65), 209 (28), 207 (90), 205

(M+–35Cl, 100); Anal. Calcd. for C8H4Cl4, HRMS (EI): Cacl. 239.9067, Found:

239.9062.


4

9

ClCl

H

Br

Compound 9. The title compound was prepared from 1e in 76% yield as a colorless


= 8.6 Hz, 2 H); 13C NMR (CDCl3, 100 MHz): δ 116.7, 123.7, 128.0 (2 C), 131.8 (2 C),

134.7; MS (EI, m/z): 254 (44), 252 (100), 250 (M+, 65), 138 (22), 136 (M+–79Br–35Cl,

72); Anal. Calcd. for C8H5BrCl2, HRMS (EI): Cacl. 249.8952, Found: 249.8955.

10

ClCl

H

Compound 10. The title compound was prepared from 1f in 84% yield as a colorless

oil. 1H NMR (CDCl3, 400 MHz): δ 2.38 (s, 3 H), 6.66 (s, 1 H), 7.19 (d, J = 8.0 Hz, 2

H), 7.43 (d, J = 8.0 Hz, 2 H); 13C NMR (CDCl3, 100 MHz): δ 21.2, 115.2, 126.5 (2 C),

129.3 (2 C), 133.0, 135.7, 139.6; MS (EI, m/z): 190 (7), 188 (50), 186 (M+, 79), 153

(27), 151 (M+–35Cl, 80). Anal. Calcd. for C9H8Cl2, HRMS (EI): Cacl. 186.0003,

Found: 186.0002.

11

ClCl

H

Compound 11. The title compound was prepared from 1g in 90% yield as a colorless

oil. 1H NMR (CDCl3, 400 MHz): δ 1.27 (d, J = 7.2 Hz, 6 H), 2.88–2.99 (m, 1 H), 6.66

(s, 1 H), 7.24 (d, J = 8.0 Hz, 2 H), 7.46 (d, J = 8.0 Hz, 2 H); 13C NMR (CDCl3, 100

MHz): δ 23.8 (2 C), 33.9, 115.1, 126.6 (2 C), 126.7 (2 C), 133.3, 135.7, 150.5; MS (EI,

m/z): 216 (25), 214 (M+, 40), 201 (60), 199 (M+–Me, 80), 165 (5), 163 (M+–Me–35Cl,

80); Anal. Calcd. for C11H12Cl2, HRMS (EI): Cacl. 214.0316, Found: 214.0317.


5

12

ClCl

H

MeO

Compound 12. The title compound was prepared from 1h in 80% yield as a colorless


H), 7.47 (d, J = 8.4 Hz, 2 H); 13C NMR (CDCl3, 100 MHz): δ 55.4, 114.0 (2 C), 114.2,

128.0 (2 C), 128.3, 135.4, 160.5; MS (EI, m/z): 206 (3), 204 (24), 202 (M+, 39), 169

(29), 167 (M+–35Cl, 100); Anal. Calcd. for C9H8Cl2O, HRMS (EI): Cacl. 201.9952,

Found: 201.9952.

13

ClCl

HMeO

MeO

Compound 13. The title compound was prepared from 1i in 78% yield as a colorless

oil. 1H NMR (CDCl3, 400 MHz): δ 3.90 (s, 3 H), 3.91 (s, 3 H), 6.60 (s, 1 H), 6.84 (d,

J = 8.4 Hz, 1 H), 7.02 (d, J = 2.0 Hz, 1 H), 7.09 (dd, J = 8.4, 2.0 Hz, 1 H); 13C NMR

(CDCl3, 100 MHz): δ 55.9 (2 C), 109.6, 110.7, 114.4, 119.4, 128.5, 135.3, 148.7,

150.0; MS (EI, m/z): 236 (10), 234 (62), 232 (M+, 100), 199 (6), 197 (M+–35Cl, 18);

Anal. Calcd. for C10H10Cl2O2, HRMS (EI): Cacl. 232.0058, Found: 232.0051.

14

ClCl

HS

Compound 14.2 The title compound was prepared from 1j in 75% yield as a colorless

oil. 1H NMR (CDCl3, 400 MHz): δ 6.74 (s, 1 H), 7.01–7.04 (m, 1 H), 7.28–7.31 (m, 2

H); 13C NMR (CDCl3, 100 MHz): δ 114.6, 126.5, 126.7, 127.5, 129.3, 138.7; MS (EI,

m/z): 182 (7), 180 (35), 178 (M+, 53), 145 (35), 143 (M+–35Cl).


6

15

ClCl

H

Compound 15. The title compound was prepared from 1k in 83% yield as a colorless


H), 7.83–7.88 (m, 3 H), 8.04 (s, 1 H); 13C NMR (CDCl3, 100 MHz): δ 116.3, 123.5,

126.4, 126.8, 127.0, 127.6, 128.3, 128.4, 132.8, 133.0, 133.4, 135.7; MS (EI, m/z):

226 (2), 224 (12), 222 (M+, 20), 189 (35), 187 (M+–35Cl, 100); Anal. Calcd. for

C12H8Cl2, HRMS (EI): Cacl. 222.0003, Found: 221.9997.

Compound 16. The title compound was prepared from 1l in 80% yield as a colorless


H), 7.92 (t, J = 7.2 Hz, 2 H), 8.11 (d, J = 8.4 Hz, 1 H); 13C NMR (CDCl3, 100 MHz):

δ 118.8, 125.0, 125.0, 126.4, 126.9, 127.6, 128.4, 130.3, 130.9, 133.6, 133.7, 139.9;

MS (EI, m/z): 226 (5), 224 (31), 222 (M+, 49), 189 (33), 187 (M+–35Cl, 100); Anal.

Calcd. for C12H8Cl2, HRMS (EI): Cacl. 222.0003, Found: 222.0001.

17

ClCl

HBnO

Compound 17. The title compound was prepared from 1m in 73% yield as a

colorless oil. 1H NMR (CDCl3, 400 MHz): δ 4.16 (s, 2 H), 4.56 (s, 2 H), 6.50 (s, 1 H),

7.32–7.40 (m, 5 H); 13C NMR (CDCl3, 100 MHz): δ 71.4, 72.2, 117.3, 127.8 (2 C),

128.0, 128.5 (2 C), 133.2, 137.0; Anal. Calcd. for C10H10Cl2O, HRMS (ESI): Cacl.

216.0109, Found: 216.0105.


7

18n-C8H17

ClCl

H

Compound 18.3 The title compound was prepared from 1n in 80% yield as a

colorless oil, Z/E = 11/1. 1H NMR (CDCl3, 400 MHz): δ 0.89 (t, J = 6.4 Hz, 3 H),

1.19–1.32 (m, 10 H), 1.51–1.61 (m, 2 H), 2.38 (t, J = 7.2 Hz, 2 H), 6.14 (s, 1 H); 13C

NMR (CDCl3, 100 MHz): δ 14.1, 22.6, 27.1, 28.5, 29.1, 29.2, 31.8, 37.6, 113.2, 137.7;

MS (EI, m/z): 212 (1), 210 (5), 208 (M+, 7), 137 (40), 109 (100).

19

Cl Cl

Compound 19. The title compound was prepared from 1o in 60% yield as a colorless

oil. 1H NMR (CDCl3, 400 MHz): δ 6.51 (s, 1 H), 6.79 (t, J = 15.2 Hz, 1 H), 7.05 (d, J

= 15.2 Hz, 1 H), 7.28–7.41 (m, 3 H), 7.42–7.48 (m, 2 H); 13C NMR (CDCl3, 100

MHz): δ 118.8, 122.9, 127.0 (2 C), 128.6, 128.9 (2 C), 132.9, 135.2, 135.8; Anal.

Calcd. for C10H8Cl2, HRMS (ESI): Cacl. 198.0003, Found: 198.0006.

Compound 20. The title compound was prepared from 1p in 68% yield as a colorless

oil. 1H NMR (CDCl3, 400 MHz): δ 1.57–1.60 (m, 2 H), 1.67–1.71 (m, 2 H),

2.18–2.20 (m, 4 H), 6.36 (s, 2 H); 13C NMR (CDCl3, 100 MHz): δ 21.7, 22.4, 25.7,

25.9, 113.7, 130.2, 131.6, 137.5; MS (EI, m/z): 180 (6), 178 (35), 176 (M+, 50), 143

(38), 141 (M+–35Cl, 100); Anal. Calcd. for C8H10Cl2, HRMS (EI): Cacl. 176.0160,

Found: 176.0165.


8

Compound 21. The title compound was prepared from 2a in 72% yield as a colorless

oil. 1H NMR (CDCl3, 400 MHz): δ 1.56–1.62 (m, 2 H), 1.66–1.73 (m, 2 H), 2.12–2.17

(m, 2 H), 2.20–2.24 (m, 2 H), 6.40 (t, J = 4.0 Hz, 1 H), 6.53 (s, 1 H); 13C NMR

(CDCl3, 100 MHz): δ 21.7, 22.4, 25.8, 26.1, 103.1, 130.6, 132.5, 140.2; MS (EI, m/z):

224 (8), 222 (44), 220 (M+, 34), 187 (23), 185 (M+–35Cl, 16); Anal. Calcd. for

C8H10BrCl, HRMS (EI): Cacl. 219.9654, Found: 219.9652.

22

Cl Br

Ph

Compound 22. The title compound was prepared from 2b in 75% yield as a colorless

oil. 1H NMR (CDCl3, 400 MHz): δ 3.33 (dt, J = 7.0, 1.2 Hz, 2 H), 6.20 (dt, J = 16.0,

7.0 Hz, 1 H), 6.43 (t, J = 1.2 Hz, 1 H), 6.54 (d, J = 16.0 Hz, 1 H), 7.28–7.44 (m, 5 H); 13C NMR (CDCl3, 100 MHz): δ 42.4, 103.8, 123.6, 126.4 (2 C), 127.8, 128.7 (2 C),

133.9, 136.7, 138.6; MS (EI, m/z): 258 (3), 256 (M+, 3), 179 (9), 177 (M+–79Br, 30),

115 (100); Anal. Calcd. for C11H10BrCl, HRMS (EI): Cacl. 255.9654, Found:

255.9650.

23

BrCl

H

Compound 23.4 The title compound was prepared from 2c in 87% yield as a colorless


H); 13C NMR (CDCl3, 100 MHz): δ 105.3, 126.7 (2 C), 128.7 (2 C), 129.5, 136.5,

138.5; MS (EI, m/z): 220 (25), 218 (100), 216 (M+, 84), 183 (38), 181 (M+–35Cl, 36).


9

24

BrCl

H

F

Compound 24. The title compound was prepared from 2d in 76% yield as a colorless


H); 13C NMR (CDCl3, 100 MHz): δ 105.1 (d, J = 1.6 Hz, 2 C), 115.7 (d, J = 21.8 Hz,

1 C), 128.6 (d, J = 8.4 Hz, 2 C), 132.7, 134.6, 163.6 (d, J = 248.6 Hz, 1 C); MS (EI,

m/z): 238 (22), 236 (88), 234 (M+, 70), 201 (39), 199 (M+–35Cl, 41); Anal. Calcd. for

C8H5BrClF, HRMS (EI): Cacl. 233.9247, Found: 233.9252.

Compound 25. The title compound was prepared from 2e in 92% yield as a colorless


= 6.8 Hz, 2 H); 13C NMR (CDCl3, 100 MHz): δ 105.8, 127.9 (2 C), 128.8 (2 C), 135.0,

135.5, 137.4; MS (EI, m/z): 254 (30), 252 (70), 250 (M+, 44), 219 (9), 217 (38), 215

(M+–35Cl, 30); Anal. Calcd. for C8H5BrCl2, HRMS (EI): Cacl. 249.8952, Found:

249.8951.

26

BrCl

H

Compound 26. The title compound was prepared from 2f in 81% yield as a colorless


H), 7.44 (d, J = 8.0 Hz, 2 H); 13C NMR (CDCl3, 100 MHz): δ 21.2, 104.2, 126.5 (2 C),

129.2 (2 C), 133.7, 138.5, 139.6; MS (EI, m/z): 234 (22), 232 (100), 230 (M+, 79), 197

(39), 195 (M+–35Cl, 35); Anal. Calcd. for C9H8BrCl, HRMS (EI): Cacl. 229.9498,

Found: 229.9501.


10

Compound 27. The title compound was prepared from 2g in 77% yield as a colorless

oil. 1H NMR (CDCl3, 400 MHz): δ 3.89 (s, 3 H), 3.90 (s, 3 H), 6.76 (s, 1 H), 6.83 (d, J

= 8.4 Hz, 1 H), 7.03 (d, J = 1.6 Hz, 1 H), 7.10 (dd, J = 8.4, 1.6 Hz, 1 H); 13C NMR

(CDCl3, 100 MHz): δ 59.9 (2 C), 103.6, 109.8, 110.8, 119.7, 129.4, 138.2, 148.8,

150.1; MS (EI, m/z): 280 (25), 278 (100), 276 (M+, 80), 263 (34), 261 (M+–35Cl, 28);

Anal. Calcd. for C10H10BrClO2, HRMS (EI): Cacl. 275.9553, Found: 275.9550.

BrCl

H

OHC28

Compound 28. The title compound was prepared from 2h in 86% yield as a colorless


= 8.4 Hz, 2 H), 10.0 (s, 1 H); 13C NMR (CDCl3, 100 MHz): δ 108.3, 127.2 (2 C),

129.2 (2 C), 136.6, 137.4, 141.7, 191.3; MS (EI, m/z): 248 (14), 246 (63), 244 (M+,

73), 138 (32), 136 (M+–79Br, 100); Anal. Calcd. for C9H6BrClO, HRMS (EI): Cacl.

243.9291, Found: 243.9292.

Compound 29. The title compound was prepared from 2i in 83% yield as a colorless

solid. 1H NMR (CDCl3, 400 MHz): δ 1.39 (t, J = 7.2 Hz, 3 H), 4.38 (q, J = 7.2 Hz, 2

H ), 7.00 (s, 1 H), 7.59 (d, J = 8.4 Hz, 2 H), 8.02 (d, J = 8.4 Hz, 2 H); 13C NMR

(CDCl3, 100 MHz): δ 14.3, 61.3, 107.4, 126.5 (2 C), 129.8 (2 C), 131.2, 137.6, 140.2,

165.8; MS (EI, m/z): 292 (5), 290 (23), 288 (M+, 24), 247 (17), 245 (76), 243

(M+–OEt, 76); Anal. Calcd. for C11H10BrClO2, HRMS (EI): Cacl. 287.9553, Found:


11

287.9553.

BrCl

HAcHN 30

Compound 30. The title compound was prepared from 2j in 82% yield as a colorless

solid. 1H NMR (CDCl3, 400 MHz): δ 2.17 (s, 3 H), 6.82 (s, 1 H), 7.20–7.31 (m, 2 H),

7.50–7.55 (m, 1 H), 7.73 (s, 1 H), 8.41 (s, 1 H); 13C NMR (CDCl3, 100 MHz): δ 24.5,

105.8, 118.4, 121.1, 122.5, 129.2, 137.1, 137.9, 138.3, 169.4; MS (EI, m/z): 275 (7),

273 (M+, 6), 154 (15), 152 (47); Anal. Calcd. for C10H9BrClNO, HRMS (EI): Cacl.

272.9556, Found: 272.9553.

Compound 31. The title compound was prepared from 2k in 85% yield as a colorless


H), 7.09–7.12 (m, 1 H), 7.12–7.27 (m, 1 H); 13C NMR (CDCl3, 100 MHz): δ 105.6,

113.8, 116.6, 119.2, 129.9, 137.9, 138.0, 155.6; MS (EI, m/z): 236 (6), 234 (26), 232

(M+, 25), 155 (17), 153 (M+–79Br, 50); Anal. Calcd. for C8H6BrClO, HRMS (EI):

Cacl. 231.9291, Found: 231.9286.

Compound 32. The title compound was prepared from 2l in 95% yield as a colorless

oil. 1H NMR (CDCl3, 400 MHz): δ 1.09 (s, 9 H), 2.65 (t, J = 6.0 Hz, 2 H), 3.88 (t, J =

6.0 Hz, 2 H), 6.41 (s, 1 H), 7.40–7.48 (m, 6 H), 7.68–7.72 (m, 4 H); 13C NMR (CDCl3,

100 MHz): δ 19.2, 26.8 (3 C), 42.2, 60.4, 104.1 (2 C), 127.8 (4 C), 129.8 (2 C), 133.5,

135.6 (4 C), 137.3; MS (EI, m/z): 369 (4), 368 (5), 367 (14), 366 (8), 365 (M+−tBu, 9);

Anal. Calcd. for C20H24BrClOSi, HRMS (ESI): Cacl. 422.0468, Found: 422.0472.


12

33

BrCl

HBnO

Compound 33. The title compound was prepared from 2m in 84% yield as a

colorless oil. 1H NMR (CDCl3, 400 MHz): δ 4.16 (s, 2 H), 4.58 (s, 2 H), 6.69 (s, 1 H),

7.31–7.45 (m, 5 H); 13C NMR (CDCl3, 100 MHz): δ 72.3, 72.4, 106.1, 127.9 (2 C),

128.1, 128.6 (2 C), 136.3, 137.2; MS (EI, m/z): 227 (0.5), 225 (M+–35Cl, 0.6), 183

(13), 181 (M+–79Br, 45); Anal. Calcd. for C10H10BrClO, HRMS (ESI): Cacl. 259.9604,

Found: 259.9604.

34

ClBr

H

Compound 34. The title compound was prepared from 1a using of 1 equiv of 4h in

62% yield as a colorless oil. 1H NMR (CDCl3, 400 MHz): δ 6.82 (s, 1 H), 7.35–7.41

(m, 3 H), 7.48–7.54 (m, 2 H); 13C NMR (CDCl3, 100 MHz): δ 119.3, 127.7 (2 C),

127.9, 128.6 (2 C), 129.4, 137.5; MS (EI, m/z): 220 (12), 218 (54), 216 (M+, 43), 139

(32), 137 (M+–79Br, 100); Anal. Calcd. for C8H6BrCl, HRMS (EI): Cacl. 215.9341,

Found: 215.9341.

35

ClBr

H

Compound 35. The title compound was prepared using of 1 equiv of 4h from 1g in

72% yield as a colorless oil. 1H NMR (CDCl3, 400 MHz): δ 1.28 (d, J = 6.8 Hz, 6 H),

2.86–2.98 (m, 1 H), 6.79 (s, 1 H), 7.24 (d, J = 8.4 Hz, 2 H), 7.44 (d, J = 8.4 Hz, 2 H); 13C NMR (CDCl3, 100 MHz): δ 23.9 (2 C), 33.9, 118.5, 126.7 (2 C), 127.7 (2 C),

128.0, 135.0, 150.5; MS (EI, m/z): 262 (16), 260 (65), 258 (M+, 51), 181 (8), 179

(M+–79Br, 25); Anal. Calcd. for C11H12BrCl, HRMS (EI): Cacl. 257.9811, Found:


13

257.9807.

Compound 36.5 The title compound was prepared using of 1 equiv of 4h from 2c in

53% yield as a colorless oil. 1H NMR (CDCl3, 400 MHz): δ 7.07 (s, 1 H), 7.34–7.40

(m, 3 H), 7.48–7.50 (m, 2 H); 13C NMR (CDCl3, 100 MHz): δ 108.8, 127.7 (2 C),

128.5 (2 C), 129.4, 131.1, 138.4; MS (EI, m/z): 264 (14), 262 (29), 260 (M+, 15), 183

(62), 181 (M+–79Br, 64).

Compound 37. The titled compound was prepared using of 1 equiv of 4h from 2e in

a 45% yield as a colorless oil. 1H NMR (CDCl3, 400 MHz): δ 7.07 (s, 1 H), 7.33 (d, J

= 8.4 Hz, 2 H), 7.44 (d, J = 8.4 Hz, 2 H); 13C NMR (CDCl3, 100 MHz): δ 109.5,

128.8 (2 C), 128.9 (2 C), 129.9, 135.5, 136.9; MS (EI, m/z): 298 (8), 296 (13), 294

(M+, 6), 217 (38), 215 (M+–79Br, 31); Anal. Calcd. for C8H5Br2Cl, HRMS (EI): Cacl.

293.8447, Found: 293.8445.

23Ph

BrCl

H+ Ph

Pd(PPh3)2Cl2CuI, Et3N

Ph

Cl

H

Ph

38

toluene, 80 oC

Compound 38.6 To a mixture of Pd(PPh3)2Cl2 (16.6 mg, 0.05 mmol), CuI (14.5 mg,

0.075 mmol) and Et3N (0.17 mL, 1.5 mmol) was added a solution of 23 (109 mg, 0.5

mmol) and phenylacetylene (0.16 mL, 1.0 mmol) in 1 mL of dry toluene. After

stirring overnight at 80 oC under nitrogen, the reaction mixture was quenched with

water, extracted with ethyl acetate, washed with brine, dried over anhydrous Na2SO4


14

and concentrated. Column chromatography on silica gel (petroleum ether) gave 97 mg

(yield: 81%) of 38. 1H NMR (CDCl3, 400 MHz): δ 6.48 (s, 1 H), 7.36–7.38 (m, 3 H),

7.40–7.42 (m, 3 H), 7.55–7.57 (m, 2 H), 7.67–7.69 (m, 2 H); 13C NMR (CDCl3, 100

MHz): δ 86.1, 97.9, 107.1, 123.0, 126.3 (2 C), 128.4 (2 C), 128.5 (2 C), 128.6, 129.6,

131.7 (2 C), 136.6, 143.9; MS (EI, m/z): 240 (25), 238 (M+, 71), 203 (M+–35Cl, 55),

101 (28).

Ph

Cl

H

Ph

38

+

Pd(OAc)2Cs2CO3, PPh3B(OH)2

Ph H

Ph

39

1,4-dioxane, 90 oC

Compound 39. To a mixture of Pd(OAc)2 (11.2 mg, 0.05 mmol), PPh3 (52.4 mg, 0.2

mmol), Cs2CO3 (448 mg, 1.5 mmol) and p-tolylboronic acid (136 mg, 1.0 mmol) was

added a solution of 38 (120 mg, 0.5 mmol) in 1 mL of dry 1,4-dioxane. After stirring

overnight at 90 oC under nitrogen, the reaction mixture was quenched with water,

extracted with ethyl acetate, washed with brine, dried over anhydrous Na2SO4 and

concentrated. Column chromatography on silica gel (petroleum ether) gave 103.0 mg

(yield: 70%) of compound 39. 1H NMR (CDCl3, 400 MHz): δ 2.43 (s, 3 H), 6.19 (s, 1

H), 7.23 (d, J = 8.0 Hz, 2 H), 7.28–7.30 (m, 3 H), 7.31–7.34 (m, 7 H), 7.47 (d, J = 8.0

Hz, 2 H); 13C NMR (CDCl3, 100 MHz): δ 21.4, 89.3, 93.5, 106.6, 123.7, 127.9, 128.1

(2 C), 128.2 (5 C), 128.4 (2 C), 130.1 (2 C), 131.4 (2 C), 136.2, 138.1, 141.8, 152.6;

MS (EI, m/z): 294 (M+, 100), 279 (M+–Me, 42), 202 (13); Anal. Calcd. for C23H18,

HRMS (EI): Cacl. 294.1409, Found: 294.1412.

Compound 40. To a solution of 20 (84 mg, 0.5 mmol) in 1 mL of xylene was added

diethyl acetylenedicarboxylate (93.5 mg, 0.55 mmol). After stirring overnight at 120


15

oC, the reaction mixture was concentrated and purified by column chromatography on

silica gel (EtOAc/hexanes = 1/10) to give 102.5 mg (yield: 66%) of 40. Compound 40

could also be prepared from 21 in 61% yield using the procedure mentioned above. 1H

NMR (CDCl3, 400 MHz): δ 1.33–1.38 (m, 6 H), 1.75–1.81 (m, 4 H), 2.72–2.75 (m, 2

H), 2.78–2.81 (m, 2 H), 4.31 (q, J = 7.2 Hz, 2 H), 4.39 (q, J = 7.2 Hz, 2 H), 7.83 (s, 1

H); 13C NMR (CDCl3, 100 MHz): δ 14.1, 14.2, 21.9, 22.0, 26.7, 28.0, 61.5, 61.6,

125.9, 127.7, 134.3, 135.5, 136.6, 140.7, 164.7, 168.8; MS (EI, m/z): 310 (1), 275 (3),

264 (93), 236 (100); Anal. Calcd. for C16H19ClO4, HRMS: Cacl. 310.0972, Found:

310.0970.

References:

1. K. Yates and T. A. Go, J. Org. Chem., 1980, 45, 2377.

2. A. Minato, K. Suzuki and K. Tamao, J. Am. Chem. Soc., 1987, 109, 1257.

3. M. Ochiai, K. Oshima and Y. Masaki, Chem. Lett., 1994, 871.

4. A. V. Martynov, S. V. Amosova and N. A. Makhaeva, Russ. J. Gen. Chem., 2005,

75, 1840.

5. M. G. Organ, H. Ghasemi and C. Valente, Tetrahedron, 2004, 60, 9453.

6. I. L. Reich, C. L. Haile and H. J. Reich, J. Org. Chem., 1978, 43, 2402.


16

ClCl

H

5

ClCl

H

5


17

HMBC

ClCl

H

5


18

6

ClCl

H

F

6

ClCl

H

F


19

NOE

6

ClCl

H

F


20

7

ClCl

H

Cl

7

ClCl

H

Cl


21

8

ClCl

HCl

Cl

8

ClCl

HCl

Cl


22

9

ClCl

H

Br

9

ClCl

H

Br


23

9

ClCl

H

Br


24

10

ClCl

H

10

ClCl

H


25

11

ClCl

H

11

ClCl

H


26

12

ClCl

H

MeO

12

ClCl

H

MeO


27

13

ClCl

HMeO

MeO

13

ClCl

HMeO

MeO


28

14

ClCl

HS

14

ClCl

HS


29

15

ClCl

H

15

ClCl

H


30

16

ClCl

H

16

ClCl

H


31

17

ClCl

HBnO

17

ClCl

HBnO


32

18n-C8H17

ClCl

H

18n-C8H17

ClCl

H


33

19

Cl Cl

19

Cl Cl


34

20

ClCl

H

20

ClCl

H


35

21

BrCl

H

21

BrCl

H


36

22

Cl Br

Ph

22

Cl Br

Ph


37

23

BrCl

H

23

BrCl

H


38

HMBC

23

BrCl

H


39

24

BrCl

H

F

24

BrCl

H

F


40

25

BrCl

H

Cl

25

BrCl

H

Cl


41

26

BrCl

H

26

BrCl

H


42

27

BrCl

H

MeO

MeO

27

BrCl

H

MeO

MeO


43

BrCl

H

OHC28

BrCl

H

OHC28


44

NOE

HMBC of 28

BrCl

H

OHC28


45

BrCl

H

EtO2C29

BrCl

H

EtO2C29


46

NOE BrCl

H

EtO2C29


47

BrCl

HAcHN 30

BrCl

HAcHN 30


48

BrCl

HHO 31

BrCl

HHO 31


49

32

BrCl

HTBDPSO

32

BrCl

HTBDPSO


50

NOE

HMBC of 32

32

BrCl

HTBDPSO


51

33

BrCl

HBnO

33

BrCl

HBnO


52

NOE

HMBC of 33

33

BrCl

HBnO


53

34

ClBr

H

34

ClBr

H


54

35

ClBr

H

35

ClBr

H


55

36

BrBr

H

36

BrBr

H


56

37

BrBr

H

Cl

37

BrBr

H

Cl


57

Ph

Cl

H

Ph

38

Ph

Cl

H

Ph

38


58

Ph H

Ph

39

Ph H

Ph

39


59

Cl

CO2EtCO2Et40

Cl

CO2EtCO2Et40


Highly stereoselective synthesis of (Z)-1,2-dihaloalkenes by a ...1 Supporting Materials to Highly...

Documents

Transcript of Highly stereoselective synthesis of (Z)-1,2-dihaloalkenes by a ...1 Supporting Materials to Highly...