Reductive Rearrangement of R-Hydroxy Epoxides
J . Org. Chem., Vol. 64, No. 2, 1999 633
temperature, 8 h), the epoxide 6a (1.0 g, 4.6 mmol) gave a
mixture of two isomers of 6b (0.85 g, 85%) in a ratio of 80:20.
Major isomer: 1H NMR δ 0.70 (d, J ) 6.4 Hz, 3H), 1.25-2.16
(m, 8H), 4.08 (q, J ) 6.4 Hz, 1H), 4.66 (s, 1H), 7.18-7.38 (m,
5H); 13C NMR δ 17.7, 19.1, 19.6, 21.0, 29.6, 48.4, 74.7, 76.3,
126.0-128.3, 141.8; GC-MS m/z (%) 202 (M+ - 18, 5), 158
(100), 143 (30), 130 (33), 129 (33); HRMS 202.1345, calcd for
C14H18O 202.1353. Minor isomer: 1H NMR δ 0.87 (d, J ) 6.4
Hz, 3H), 1.25-2.16 (m, 8H), 3.90 (q, J ) 6.4 Hz, 1H), 4.81 (s,
1H), 7.18-7.38 (m, 5H); 13C NMR δ 17.7, 19.6, 21.4, 27.0, 29.2,
49.1, 69.5, 73.9, 126.0-128.3, 141.0; GC-MS m/z (%) 202 (M+
- 18, 6), 158 (100), 143 (28), 130 (30), 129 (28).
1.94 (m, 8H), 3.23 (s, OH), 3.64, 3.84 (ABq, J ) 11 Hz, 2 ×
1H), 4.18 (dd, J ) 6, 3 Hz, 1H), 6.13 (d, J ) 3 Hz, 1H), 6.26
(dd, J ) 3, 1.8 Hz, 1H), 7.28 (d, J ) 1.8 Hz, 1H); 13C NMR δ
21.2, 21.5, 28.3, 29.9, 45.6, 66.8, 71.9, 106.4, 110.0, 141.0, 157.8;
GC-MS m/z (%) 196 (M+, 1), 178 (M+ - 18, 46), 135 (92), 134
(49), 108 (100); HRMS 178.0988, calcd for C11H14O2 178.0990.
No NMR data for the minor isomer could be collected due to
the low intensity and its poor resolution with background.
11c: 1H NMR δ 1.10 (d, J ) 6 Hz, 6H), 0.96-1.84 (m, 8H),
2.97 (s, OH), 3.46 (dd, J ) 7.5, 4 Hz, 1H), 3.68 (hept, J ) 6
Hz, 1H), 4.74 (s, 1H), 6.26 (m, 2H), 7.30 (dd, J ) 2, 1.8 Hz,
1H); 13C NMR δ 21.2, 21.6, 21.9, 23.3, 27.5, 32.2, 70.0, 70.6,
74.0, 80.8, 108.2, 110.0, 141.7, 153.8; GC-MS m/z (%) 221 (M+
- 15 - 18, 23), 178 (72), 148 (41), 135 (96), 108 (100); HRMS
221.1168, calcd for C13H17O3 221.1173.
2-Eth yl-2-(1-h ydr oxy-1-ph en ylm eth yl)cycloh exan ol (7b).
Following the typical procedure (above, 2 equiv of AIP,
refluxing temperature, 8 h), the epoxide 7a (0.2 g, 0.86 mmol)
gave a mixture of two isomers of 7b (0.19 g, 95%) in a ratio of
72:28. Major isomer: 1H NMR δ 0.68-0.82 (m, 3H), 0.77-2.18
(m, 10H), 3.66 (dd, J ) 8.8, 1.7 Hz, 1H), 4.17(s, OH), 4.56 (s,
1H), 7.09-7.29 (m, 5H); 13C NMR δ 11.0, 10.9, 20.5, 21.0, 23.9,
29.6, 48.5, 74.7, 82.1, 125.8-129.8, 141.8; GC-MS m/z (%) 216
(M+ - 18, 3), 158 (100), 143 (24), 130 (28), 129 (24); HRMS
216.1500, calcd for C15H20O 216.1509. Minor isomer: 1H NMR
δ 0.68-0.82 (m, 3 H), 0.77-2.18 (m, 10 H), 3.43 (dd, J ) 9.0,
1,7-Dih yd r oxysp ir o[5.5]u n d eca n e (12b). Following the
typical procedure (above, 2 equiv of AIP, refluxing tempera-
ture, 4 h), the epoxide 12a (0.5 g, 2.7 mmol) gave as the only
product 12b (0.49 g, 98%): 1H NMR δ 0.66-2.10 (m, 16H),
3.56 (dd, J ) 11, 4.4 Hz, 1H), 3.59 (s, 1H), 4.31 (s, OH); 13C
NMR δ 18.7, 19.6, 19.9, 20.2, 24.8, 29.0, 29.7, 30.3, 40.4, 78.5,
78.6; MS m/z (%) 166 (M+ - 18, 11), 148 (100), 122 (63), 111
(33), 81 (93); HRMS 166.1344, calcd for C11H18O 166.1353.
1,7-Dih yd r oxy-1-d eu ter iosp ir o[5.5]u n d eca n e (13b). To
the solution of 1.1 mL of 2-propanol-d8 (ca. 14 mmol) in dry
THF (20 mL) was added 1.7 mL of a 2.6 M solution of AlEt3 in
THF. The mixture was refluxed under Ar for 1 h to give the
deuterium AIP solution (ca. 4.4 mmol) which was used directly
in the reaction for 12a (0.4 g, 2.2 mmol) according to the typical
procedure (above, refluxing temperature, 4 h) to give the
product 13b (0.36 g, 88%): 1H NMR δ 1.11-2.06 (m, 16H), 3.54
(s, 1H), 4.55 (s, OH), 4.86 (s, OH); 13C NMR δ 18.6, 19.5, 19.8,
20.0, 24.7, 28.8, 29.4, 30.2, 40.1, 77.9 (t, CD), 78.4; GC-MS m/z
(%) 167 (M+ - 18, 12), 149 (100), 122 (47), 95 (38), 81 (95);
FAB-HRMS 186.1583, calcd for [C11H19DO2 + H] 186.1599.
2-Ben zyl-2-(1-h yd r oxyeth yl)cyclop en ta n ol (14b). Fol-
lowing the typical procedure (above, 2 equiv of AIP, refluxing
temperature, 8 h), the epoxide 14a (0.5 g, 2.3 mmol) gave a
mixture of two isomers of 14b (0.28 g, 55%) in ae ratio of 71:
29. Major isomer: 1H NMR δ 1.18 (d, J ) 6.5 Hz, 3H), 1.26-
2.83 (m, 8H), 3.95 (q, J ) 6.5 Hz, 1H), 4.17 (t, J ) 6.7 Hz,
1H), 7.04-7.87 (m, 5H); 13C NMR δ 18.5 (CH3), 21.1, 30.5, 36.3,
43.4, 51.2, 70.1, 79.8, 124.7-138.6 (Ph); GC-MS m/z (%) 202
(M+ - 18, 10), 158 (76), 143 (23), 129 (54), 91 (100); HRMS
202.1345 calcd for C14H18O 202.1353. Minor isomer: 1H NMR
δ 1.17-2.83 (m, 11H), 3.92 (q, J ) 6.4 Hz, 1H), 4.04 (t, J )
1.5 Hz, 1 H), 4.17 (s, OH), 4.72 (s, 1H), 7.09-7.29 (m, 5H); 13
C
NMR δ 11.2,19.9, 21.4, 24.2, 27.0, 29.1, 49.0, 69.6, 80.3, 125.8-
129.8, 141.4; GC-MS m/z (%) 216 (M+ - 18, 3), 158 (100), 143
(26), 131 (10), 130 (28).
2-Eth yl-2-(1-h yd r oxy-1-(6-m eth oxy-2-n a p h th yl)m eth yl-
)cycloh exa n ol (8b). Following the typical procedure (above,
2 of equiv AIP, refluxing temperature, 8 h), the epoxide 8a
(0.4 g, 1.28 mmol) gave a mixture of two isomers of 8b (0.29
g, 73%) in a ratio of 65:35. Major isomer: 1H NMR δ 0.68 (t,
J ) 7.3 Hz, 3H), 0.76-2.17 (m, 10H), 3.76 (dd, J ) 10, 2 Hz,
1H), 3.84 (s, 3H), 4.70 (s, 1H), 7.03-7.65 (m, 6H); 13C NMR δ
11.2, 19.3, 21.0, 21.4, 24.3, 29.8, 48.7, 55.4, 74.9, 83.0, 105.3-
137.2, 157.7; GC-MS m/z (%) (mixture of 2 isomers) 296 (M+
- 18, 3), 249 (3), 239 (19), 238 (100); HRMS 296.1780, calcd
for C20H24O2 296.1770. Minor isomer: 1H NMR δ 0.76-2.16
(m, 1H), 3.55 (dd, J ) 10, 2 Hz, 1H), 3.83 (s, 3H), 4.75 (s, 1H),
7.03-7.65 (m, 6H); 13C NMR δ 11.5, 20.2, 21.7, 24.5, 27.3, 29.4,
49.2, 55.4, 70.0, 80.5, 118.7-136.8, 157.7.
2-(1-H yd r oxy-1-p h en ylm et h yl)-2-isop r op ylcycloh ex-
a n ol (9b). Following the typical procedure (above, 2 equiv of
AIP, refluxing temperature, 8 h), the epoxide 9a (0.4 g, 1.6
mmol) gave a mixture of two isomers of 9b (0.38 g, 95%) in a
ratio of 73:27. Major isomer: 1H NMR δ 0.72, 0.73 (2 d, J )
6.5 Hz, 2 × 3H), 1.24-2.26 (m, 9H), 3.51 (s, OH), 3.84 (d, J )
1 Hz, 1H), 4.63 (s, 1H), 7.21-7.40 (m, 5H); 13C NMR δ 16.0,
18.8, 21.1, 21.2, 23.2, 28.7, 29.5, 49.4, 76.0, 84.4, 126.0-129.5,
141.9; GC-MS m/z (%) 230 (M+ - 18, 4), 158 (100), 145 (14),
143 (26), 130 (28); HRMS 230.1651, calcd for C16H22O 230.1665.
Minor isomer: 1H NMR δ 0.38, 0.82 (2 d, J ) 6.5 Hz, 2 × 3H),
1.24-2.26 (m, 9H), 3.51 (s, OH), 3.56 (d, J ) 1 Hz, 1H), 4.87
(s, 1H), 7.21-7.40 (m, 5H); 13C NMR δ 15.8, 19.8, 21.4, 23.8,
27.3, 27.8, 29.0, 49.2, 70.0, 82.9, 126.0-129.5, 141.2; GC-MS
m/z (%) 230 (M+ - 18, 3), 158 (100), 143 (25), 130 (26), 91 (22).
2-(1-H y d r o x y -1-p h e n y lm e t h y l)-2-p h e n y lc y c lo h e x -
a n ol (10b). Following the typical procedure (above, 2 equiv
of AIP, refluxing temperature, 8 h), the epoxide 10a (0.5 g,
1.8 mmol) gave a mixture of two isomers of 10b (0.46 g, 91%)
in a ratio of 80:20. 1H NMR δ (2 isomers) 1.19-2.42 (m, 16H),
4.17, 4.74, 4.75, 4.94 (4 s, 4 H), 6.65-7.37 (m, 20 H). Major
isomer: 13C NMR δ 18.9, 19.9, 20.7, 29.4, 49.3, 74.0, 82.9,
6.4 Hz, 1H), 7.04-7.87 (m, 5H); GC-MS m/z (%) 202 (M+
18, 9), 158 (100), 129 (55), 117 (29), 91 (94).
-
2-(1-Hyd r oxy-3-m eth ybu tyl)-2-(2-m eth ylp r op yl)cyclo-
p en ta n ol (15b). Following the typical procedure (above, 2
equiv of AIP, refluxing temperature, 8 h), the epoxide 14a (0.45
g, 2.0 mmol) gave the product 15a (0.39 g, 85%): 1H NMR δ
0.95 (m, 12H), 1.10-2.10 (m, 12H), 4.05 (m, 2H); 13C NMR δ
21.2, 21.3, 2 × 24.2, 24.4, 24.6, 25.4, 32.6, 37.5, 40.7, 47.6, 50.5,
71.6, 81.3; GC-MS m/z (%) 210 (M+ - 18, 1), 153 (10), 124 (100),
123 (13), 97 (31); HRMS 192.1877, calcd for C14H24 192.1872.
2-(1-Hyd r oxyeth yl)-2-p h en ylcyclop en ta n ol (16b). Fol-
lowing the typical procedure (above, 2 equiv of AIP, refluxing
temperature, 8 h), the epoxide 16a (0.57 g, 2.8 mmol) gave
the product 16b (0.24 g, 42%): 1H NMR δ 0.84 (d, J ) 6.6 Hz,
3H), 1.48-2.28 (m, 6H), 4.17 (q, J ) 6.6 Hz, 1H), 4.60 (t, J )
5.4 Hz, 1H), 7.16-7.42 (m, 5H); 13C NMR δ 19.5, 20.7, 31.8,
32.9, 58.5, 71.6, 80.6, 126.5, 4 × 128.0, 141.4S; MS m/z (%)
206 (M+, 23), 188 (69), 144 (100), 129 (89) 105 (95); HRMS
206.1308, calcd for C13H18O2 206.1302.
125.9-128.5 (10CH), 140.0, 140.5; GC-MS m/z (%) 264 (M+
-
18, 3), 158 (100), 143 (19), 130 (21), 129 (16); HRMS 264.1518,
calcd for C19H20O 264.1509. Minor isomer: 13C NMR δ 19.6,
21.2, 26.7, 28.9, 49.5, 67.0, 81.4, 125.9-128.5, 139.8, 140.4;
GC-MS m/z (%) 247 (M+ - 18 - 17, 3), 158 (100), 143 (19),
130 (21), 129 (16).
Ack n ow led gm en t. We are grateful for the financial
support of the Education Ministry of China and the
National Science Foundation of China. We also greatly
thank Ms. Wang Kai Qiu, Ms. Hui Ling Liang, Prof. Li
Yang, Dr. Yu Xin Cui, and Mr. Qi Xiu Zhu for their
helpful measurements of spectroscopic data.
2-(r-F u r yl)-2-(h yd r oxym eth yl)cycloh exa n ol (11b) a n d
1-((r-F u r yl)h yd r oxym et h yl)-2-isop op oxycycloh exa n ol
(11c). Following the typical procedure (above, 2 equiv of AIP,
refluxing temperature, 8 h), the epoxide 11a (0.9 g, 4.6 mmol)
gave a mixture of 11b (0.49 g, yielding 54%) in a ratio of 91:9
and 11c (0.36 g, 31%). Major isomer of 11b: 1H NMR δ 0.77-
J O981097Z