LETTER
Solvent-Free Synthesis of Homoallylic Alcohols
141
(13) (a) Wang, Z. Y.; Yuan, S. Z.; Zha, Z. G.; Zhang, Z. D. Chin.
J. Chem. 2003, 21, 1231. (b) Andrews, P. C.; Peatt, A. C.;
Raston, C. L. Tetrahedron Lett. 2004, 45, 243. (c) Wang, Z.
Y.; Yuan, S. Z.; Li, C. J. Tetrahedron Lett. 2002, 43, 5097.
(14) Chan, T. H.; Yang, Y. Tetrahedron Lett. 1999, 40, 3863.
(15) Loh, T. P.; Xu, J. Tetrahedron Lett. 1999, 40, 2431.
(16) (a) Tanaka, K. Solvent-Free Organic Synthesis; Wiley-
VCH: Weinheim, 2003. (b) Astruc, D.; Heuzé, K.; Gatard,
S.; Méry, D.; Nlate, S.; Plault, L. Adv. Synth. Catal. 2005,
347, 329. (c) Cave, G. W. V.; Raston, C. L.; Scott, J. L.
Chem. Commun. 2001, 2159. (d) Mestres, R. Green Chem.
2004, 6, 853. (e) Cole-Hamilton, D. J. Science 2003, 299,
1072.
poured into the mixture, the mixture was extracted with Et2O
(3 × 10 mL) and the organic layer was separated, dried over
anhyd MgSO4, filtered, and evaporated. The pure products
were obtained by flash chromatography over silica gel, and
characterized by IR, 1H NMR, 13C NMR and MS.
(21) Representative Spectroscopic Data for Compounds 3.
Compound 3i: IR: 3475, 2976, 1670, 1456, 1269, 1101, 920,
771, 738 cm–1. 1H NMR (400 MHz, CDCl3): d = 7.24–7.84
(m, 7 H), 5.60–5.70 (m, 1 H), 5.09–5.19 (m, 2 H), 3.88 (q,
J = 6.4 Hz, 2 H), 2.65–2.76 (m, 1 H), 2.52–2.63 (m, 1 H),
2.14 (s, 1 H), 1.61 (s, 3 H). 13C NMR (100 MHz, CDCl3): d
= 146.4, 143.3, 143.3, 141.4, 140.2, 133.7, 126.7, 126.5,
125.0, 123.4, 121.5, 119.8, 119.4, 73.8, 48.6, 37.0, 30.1,
26.8. EI–MS: m/z (%) = 250 (2.4) [M+], 209 (64.9), 193
(16.8), 165 (37.7), 43 (100), 39 (17.2). Anal. Calcd for
C18H18O: C, 86.36; H, 7.25. Found: C, 86.36; H, 7.36.
Compound 3p: IR: 3406, 3077, 2977, 1644, 1439, 1372,
1114, 923, 796 cm–1. 1H NMR (400 MHz, CDCl3): d = 6.88
(d, J = 3.6 Hz, 1 H), 6.63 (d, J = 3.6 Hz, 1 H), 5.67–5.78 (m,
1 H), 5.12–5.19 (m, 2 H), 2.57–2.67 (m, 1 H), 2.48–2.54 (m,
1 H), 2.34 (s, 1 H), 1.57 (s, 3 H). 13C NMR (100 MHz,
CDCl3): d = 154.6, 132.8, 129.5, 122.5, 120.2, 110.5, 73.0,
48.7, 30.1. EI–MS: m/z (%) = 248 (0.3) [M+ + 2], 246 (0.2)
[M+], 231 (0.3) [M+ – Me], 229 (0.3) [M+ – OH], 207 (33.7),
43 (100), 39 (21.7). Anal. Calcd for C9H11BrOS: C, 43.74;
H, 4.49. Found: C, 43.29; H, 3.93. Compound 3q: IR: 3439,
3072, 2922, 1662, 1445, 1369, 1142, 917, 829 cm–1. 1H
NMR (400 MHz, CDCl3): d = 6.54 (s, 1 H), 5.67–5.78 (m, 1
H), 5.12–5.17 (m, 2 H), 2.15–2.50 (m, 8 H), 2.04 (s, 1 H),
1.51 (s, 3 H). 13C NMR (100 MHz, CDCl3): d = 142.1, 134.2,
133.9, 131.3, 125.3, 119.2, 73.6, 47.7, 30.9, 29.3, 15.0. EI–
MS: m/z (%) = 196 (2.37) [M+], 181 (0.04) [M+ – OH], 155
(24.9), 139 (10.5), 113 (5.7), 59 (9.3), 43 (100), 41 (16.2), 39
(16.9). Anal. Calcd for C11H16OS: C, 67.30; H, 8.22. Found:
C, 66.92; H, 8.07. Compound 3r: IR: 3411, 3077, 2981,
1684, 1373, 1097, 921, 786 cm–1. 1H NMR (400 MHz,
CDCl3): d = 6.05 (s, 1 H), 5.87 (s, 1 H), 5.68–5.72 (m, 1 H),
5.11–5.15 (m, 2 H), 2.64–2.69 (m, 1 H), 2.51–2.56 (m, 1 H),
2.28 (s, 3 H), 2.14 (s, 1 H), 1.51 (s, 3 H). 13C NMR (100
MHz, CDCl3): d = 157.3, 151.2, 133.5, 119.0, 105.8, 105.3,
70.5, 46.0, 26.3, 13.5. EI–MS: m/z (%) = 166 (0.7) [M+], 149
(1.7) [M+ – OH], 135 (0.7), 125 (91.5), 109 (10.3), 95 (2.1),
43 (100), 39 (20.6). Anal. Calcd for C10H14O2: C, 72.26; H,
8.49. Found: C, 72.28; H, 8.64.
(17) Hamasaki, R.; Chounan, Y.; Horino, H.; Yamamoto, Y.
Tetrahedron Lett. 2000, 41, 9883.
(18) (a) Wang, J.-X.; Fu, Y.; Hu, Y. L. Angew. Chem. Int. Ed.
2002, 41, 2757. (b) Wang, J.-X.; Fu, Y.; Hu, Y. L.; Wang, K.
H. Synthesis 2003, 1506. (c) Hu, Y. L.; Wang, J.-X.; Li, W.
B. Chem. Lett. 2001, 30, 174. (d) Wang, J.-X.; Wang, K. H.;
Zhao, L. B.; Li, H. X.; Fu, Y.; Hu, Y. L. Adv. Synth. Catal.
2006, 348, 1262. (e) Huang, D. F.; Wang, J.-X. Synlett 2007,
2272.
(19) (a) Hennion, G. F.; Sheehan, J. J. J. Am. Chem. Soc. 1949,
71, 1964. (b) Shank, R. S.; Shechter, H. J. Org. Chem. 1959,
24, 1825. (c) LeGoff, E. J. Org. Chem. 1964, 29, 2048.
(d) Suarez, R. M.; Sestelo, J. P.; Sarandeses, L. A. Synlett
2002, 1435. (e) Shimizu, M.; Iwata, A.; Makino, H. Synlett
2002, 1538. (f) Estevam, I. H. S.; Bieber, L. W. Tetrahedron
Lett. 2003, 44, 667.
(20) Preparation of the Zinc–Copper Couple: Zinc powder
(11.6 g) and distilled H2O (80 mL) were placed into a 100-
mL round-bottom flask equipped with a stir bar. With
stirring, HCl acid (37%, 2 × 1 mL) was added over 10 min.
Then the CuSO4 solution (20%, 20 mL) was added dropwise
with stirring and the stirring was continued for about 15 min.
Finally, the mixture was filtered and the solid was washed
with H2O (3 × 30 mL), acetone (3 × 10 mL), and Et2O (2 ×
10 mL). Then the solid was transferred into a flask equipped
with vacuum take-off and dried under vacuum for 3 h at 100
°C. Other M–Cu couples were also prepared in this way.
Preparation of the Homoallylic Alcohols: Zinc–copper
couple (0.24 g), allyl bromide (2.5 mmol) and ketones (2
mmol) were placed in a dried round-bottom flask, and the
mixture was stirred at r.t. and the reaction was monitored by
TLC. After reaction completed, sat. brine (10 mL) was
Synlett 2008, No. 1, 137–141 © Thieme Stuttgart · New York