Highly stereoselective synthesis of (Z)-1,2-dihaloalkenes by a ...1 Supporting Materials to Highly...
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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
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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
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(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.
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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.
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9
ClCl
H
Br
Compound 9. The title compound was prepared from 1e in 76% yield as a colorless
oil. 1H NMR (CDCl3, 400 MHz): δ 6.71 (s, 1 H), 7.40 (d, J = 8.6 Hz, 2 H), 7.51 (d, J
= 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.
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12
ClCl
H
MeO
Compound 12. The title compound was prepared from 1h in 80% yield as a colorless
oil. 1H NMR (CDCl3, 400 MHz): δ 3.84 (s, 3 H), 6.59 (s, 1 H), 6.90 (d, J = 8.4 Hz, 2
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).
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15
ClCl
H
Compound 15. The title compound was prepared from 1k in 83% yield as a colorless
oil. 1H NMR (CDCl3, 400 MHz): δ 6.84 (s, 1 H), 7.54–7.56 (m, 2 H), 7.59–7.62 (m, 1
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
oil. 1H NMR (CDCl3, 400 MHz): δ 6.59 (s, 1 H), 7.46–7.61 (m, 2 H), 7.57–7.61 (m, 2
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.
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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.
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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
oil. 1H NMR (CDCl3, 400 MHz): δ 6.89 (s, 1 H), 7.36–7.43 (m, 3 H), 7.52–7.59 (m, 2
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).
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24
BrCl
H
F
Compound 24. The title compound was prepared from 2d in 76% yield as a colorless
oil. 1H NMR (CDCl3, 400 MHz): δ 6.83 (s, 1 H), 7.03–7.11 (m, 2 H), 7.49–7.57 (m, 2
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
oil. 1H NMR (CDCl3, 400 MHz): δ 6.89 (s, 1 H), 7.35 (d, J = 6.8 Hz, 2 H), 7.48 (d, J
= 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
oil. 1H NMR (CDCl3, 400 MHz): δ 2.38 (s, 3 H), 6.83 (s, 1 H), 7.19 (d, J = 8.0 Hz, 2
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.
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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
oil. 1H NMR (CDCl3, 400 MHz): δ 7.08 (s, 1 H), 7.72 (d, J = 8.4 Hz, 2 H), 7.89 (d, J
= 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:
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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
oil. 1H NMR (CDCl3, 400 MHz): δ 5.52 (s, 1 H), 6.85–6.88 (m, 2 H), 7.02–7.04 (m, 1
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.
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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:
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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
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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
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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.
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16
ClCl
H
5
ClCl
H
5
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17
HMBC
ClCl
H
5
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18
6
ClCl
H
F
6
ClCl
H
F
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19
NOE
6
ClCl
H
F
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20
7
ClCl
H
Cl
7
ClCl
H
Cl
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21
8
ClCl
HCl
Cl
8
ClCl
HCl
Cl
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22
9
ClCl
H
Br
9
ClCl
H
Br
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23
9
ClCl
H
Br
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24
10
ClCl
H
10
ClCl
H
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25
11
ClCl
H
11
ClCl
H
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26
12
ClCl
H
MeO
12
ClCl
H
MeO
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27
13
ClCl
HMeO
MeO
13
ClCl
HMeO
MeO
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28
14
ClCl
HS
14
ClCl
HS
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29
15
ClCl
H
15
ClCl
H
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30
16
ClCl
H
16
ClCl
H
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31
17
ClCl
HBnO
17
ClCl
HBnO
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32
18n-C8H17
ClCl
H
18n-C8H17
ClCl
H
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33
19
Cl Cl
19
Cl Cl
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34
20
ClCl
H
20
ClCl
H
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35
21
BrCl
H
21
BrCl
H
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36
22
Cl Br
Ph
22
Cl Br
Ph
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37
23
BrCl
H
23
BrCl
H
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38
HMBC
23
BrCl
H
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39
24
BrCl
H
F
24
BrCl
H
F
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40
25
BrCl
H
Cl
25
BrCl
H
Cl
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41
26
BrCl
H
26
BrCl
H
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42
27
BrCl
H
MeO
MeO
27
BrCl
H
MeO
MeO
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43
BrCl
H
OHC28
BrCl
H
OHC28
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44
NOE
HMBC of 28
BrCl
H
OHC28
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45
BrCl
H
EtO2C29
BrCl
H
EtO2C29
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46
NOE BrCl
H
EtO2C29
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47
BrCl
HAcHN 30
BrCl
HAcHN 30
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
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48
BrCl
HHO 31
BrCl
HHO 31
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49
32
BrCl
HTBDPSO
32
BrCl
HTBDPSO
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50
NOE
HMBC of 32
32
BrCl
HTBDPSO
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51
33
BrCl
HBnO
33
BrCl
HBnO
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52
NOE
HMBC of 33
33
BrCl
HBnO
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53
34
ClBr
H
34
ClBr
H
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54
35
ClBr
H
35
ClBr
H
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55
36
BrBr
H
36
BrBr
H
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56
37
BrBr
H
Cl
37
BrBr
H
Cl
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57
Ph
Cl
H
Ph
38
Ph
Cl
H
Ph
38
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58
Ph H
Ph
39
Ph H
Ph
39
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59
Cl
CO2EtCO2Et40
Cl
CO2EtCO2Et40
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012