PAPER
Conversion of Alkyl Halides into Alcohols
3359
2
-(4-Methyl-5-oxocyclohex-3-enyl)allyl Formate (2)
15.2, 6.2 Hz, 1 H), 2.00–1.40 (m, 5 H), 1.39 (s, 3 H), 1.35–1.20 (m,
2 H), 0.99 (s, 3 H), 0.97 (s, 3 H).
[
a] –100 (c 0.3, CHCl ).
D
3
–
1
13
IR (film): 2924, 1724, 1671, 1434, 1367, 1160 cm .
C NMR (CDCl ): d = 211.9 (C), 206.5 (C), 205.8 (C), 160.4 (CH),
3
1
66.1 (CH ), 59.4 (CH), 55.2 (C), 50.2 (C), 49.1 (C), 46.9 (CH), 46.2
2
H NMR (CDCl ): d = 8.09 (s, 1 H), 6.73 (m, 1 H), 5.19 (s, 1 H),
3
(
(
CH), 43.1 (CH), 37.9 (C), 36.2 (CH ), 34.3 (CH ), 21.5 (CH ), 19.2
2 2 2
CH ), 18.5 (CH ), 17.7 (CH ), 13.0 (CH ), 12.7 (CH ).
5
2
1
.08 (s, 1 H), 4.67 (AB system, J = 13.2 Hz, 2 H), 2.85 (m, 1 H),
.63 (ddd, J = 16, 3.7, 1.6 Hz, 1 H), 2.54 (dddd, J = 18.2, 5.8, 5.8,
.6 Hz, 1 H), 2.40 (dd, J = 16, 13 Hz, 1 H), 2.33 (m, 1 H), 1.78 (s, 3
2
2
3
3
3
+
MS-FAB: m/z (%) = 359 (MH , 18), 313 (100), 295 (60), 285 (20),
H).
267 (10), 253 (8).
1
3
+
C NMR (CDCl ): d = 198.9 (C), 160.5 (CH), 144.4 (C), 144.0
HRMS-FAB: m/z calcd for C H O [M + H]: 359.1853; found:
359.1859.
3
21 27
5
(
CH), 135.7 (C), 114.3 (CH ), 65.1 (CH ), 42.9 (CH ), 38.3 (CH),
2
2
2
3
1.3 (CH ), 15.7 (CH ).
2 3
+
+
18-Hydroxytrachylobane-3,14,15-trione (16)
MS (EI): m/z (%) = 195 (M + 1, 1), 194 (M , 0.2), 149 (10), 148
(
Mp 189–191 °C (hexane–CH Cl ); [a] –15 (c 0.3, CHCl ).
2
2
D
3
87), 135 (7), 119 (8), 106 (65), 105 (37), 82 (100).
–
1
+
IR (KBr): 3410, 2918, 2847, 1754, 1689, 1465, 1372, 1039, cm .
HRMS (EI): m/z calcd for C H O [M ]: 194.0943; found:
1
1
14
3
1
1
94.0939.
H NMR (CDCl ): d = 3.68 and 3.35 (AB system, J = 11 Hz, 2 H),
.62 (d, J = 8 Hz, 1 H), 2.58 (ddd, J = 15, 13, 5 Hz, 1 H), 2.51 (ddd,
3
2
1
8-Bromotrachylobane-3,14,15-trione (13)
J = 7.8, 2.3, 2.3 Hz, 1 H), 2.29–2.13 (m, 2 H), 2.06 (dd, J = 12.3, 6.2
Hz, 1 H), 1.97 (ddd, J = 12.9, 6.3, 1.9 Hz, 1 H), 1.92–1.40 (m, 6 H),
Mp 250–253 °C (dec., MeOH); [a] +0.5 (c 0.1, CHCl ).
D
3
1
.29 (ddd, J = 13.7, 13.7, 4.5 Hz, 1 H), 1.42 (s, 3 H), 1.05 (s, 3 H),
IR (KBr): 2945, 2925, 2850, 1754, 1716, 1700, 1443, 1430, 1071,
1
–1
0.98 (s, 3 H).
010, 970, 651 cm .
13C NMR (CDCl
): d = 217.2 (C), 206.8 (C), 205.7 (C), 66.3 (CH ),
1
3
2
H NMR (CDCl ): d = 3.82 and 3.18 (AB system, J = 10 Hz, 2 H),
3
5
9.5 (CH), 55.4 (C), 52.5 (C), 49.2 (C), 47.1 (CH), 46.9 (CH), 43.1
2
.65 (d, J = 8 Hz, 1 H), 2.54 (ddd, J = 8, 3, 3 Hz, 1 H), 2.50–2.28
(
CH), 38.0 (C), 37.5 (CH ), 34.7 (CH ), 21.4 (CH ), 19.3 (CH ),
2
2
2
2
(m, 3 H), 2.22 (ddd, J = 17.7, 5.6, 2.4 Hz, 1 H), 2.14 (dd, J = 10.4,
1
8.5 (CH ), 16.9 (CH ), 13.4 (CH ), 12.8 (CH ).
2 3 3 3
2
.8 Hz, 1 H), 2.04–1.96 (m, 2 H), 1.93–1.77 (m, 3 H), 1.69 (ddd,
+
J = 13.3, 6.3, 2.3 Hz, 1 H), 1.44 (s, 3 H), 1.36 (ddd, J = 13.4, 13.4,
MS-FAB: m/z (%) = 331 (M + H, 75), 313 (100), 301 (20), 295
4
.7 Hz, 1 H), 1.12 (s, 3 H), 1.00 (s, 3 H).
(70), 285 (40), 283 (48), 267 (18).
1
3
+
C NMR (CDCl ): d = 211.6 (C), 207.6 (C), 206.6 (C), 59.1 (CH),
HRMS-FAB: m/z calcd for C H O [M + H]: 331.1904; found:
331.1910.
3
20 27
4
5
5.3 (C), 51.3 (C), 49.5 (C), 47.2 (CH), 47.1 (CH), 43.2 (CH), 37.8
(
C), 35.3 (CH ), 38.8 (CH ), 34.2 (CH ), 21.6 (CH ), 21.0 (CH ),
2
2
2
2
3
1
9.8 (CH ), 18.8 (CH ), 12.8 (CH ), 12.5 (CH ).
Iodide 26
2
2
3
3
+
+
Mp 130 °C (dec., MeOH), [a] +15.3 (c 0.8, CHCl ).
D
3
MS-FAB: m/z (%) = 395 ([M + H + 2], 29), 393 (M + H, 30), 379
(
–
1
9), 375 (8), 313 (100), 295 (35), 285 (15).
IR (KBr): 3000, 2907, 1705, 1443, 1363, 1181, 903 cm .
7
9
+
1
HRMS-FAB: m/z calcd for C H BrO [M + H]: 393.1060;
found: 393.1054.
H NMR (CDCl ): d = 5.28 (br s, 1 H), 4.36 (s, 1 H), 2.3–2.1 (m, 3
2
0
26
3
3
H), 2.00–1.60 (m, 8 H), 1.59 (s, 3 H), 1.50 (m, 1 H), 1.30–1.15 (m,
2
H), 1.33 (s, 3 H), 0.65 (s, 3 H).
1
8-Iodotrachylobane-3,14,15-trione (14)
13
C NMR (CDCl ): d = 207.4 (C), 134.5 (C), 120.7 (CH), 53.3 (CH),
3
Mp 239–241 °C (dec., toluene); [a] +16 (c 0.5, CHCl ).
D
3
5
2.5 (CH), 50.0 (C), 47.8 (CH), 43.3 (CH), 38.7 (C), 38.0 (CH),
IR (KBr): 2945, 2940, 2931, 1754, 1711, 1694, 1437, 1410, 1220,
36.5 (C), 34.4 (CH ), 28.3 (CH ), 22.3 (CH ), 21.3 (CH ), 21.2
(CH ), 20.5 (CH ), 17.9 (CH ), 10.7 (CH ).
3 2 2 3
2 2 2 3
–1
1
213, 995, 602 cm .
1
+
H NMR (CDCl ): d = 3.59 and 2.98 (AB system, J = 10 Hz, 2 H),
MS-FAB: m/z (%) = 397 (M + H, 30), 269 (20), 255 (14), 220 (10),
173 (16), 154 (100).
3
2
(
(
.61 (d, J = 8 Hz, 1 H), 2.51 (ddd, J = 8, 2, 2 Hz, 1 H), 2.42–2.28
m, 3 H), 2.22 (ddd, J = 12.6, 10.1, 2.5 Hz, 1 H), 2.16 (m, 1 H), 1.99
ddd, J = 12.9, 5.2, 2.4 Hz, 1 H), 1.85–1.70 (m, 4 H), 1.69 (ddd, J =
+
HRMS-FAB: m/z calcd for C H IO [M + H ]: 397.1023; found:
1
9
26
3
97.1031.
1
3.5, 6.1, 2.7 Hz, 1 H), 1.41 (s, 3 H), 1.30 (ddd, J = 13.2, 13.2, 5.1
Hz, 1 H), 1.14 (s, 3 H), 0.96 (s, 3 H).
Formate Ester 27
Mixture of epimers.
1
3
C NMR (CDCl ): d = 211.7 (C), 206.6 (C), 205.6 (C), 59.2 (CH),
3
5
5.3 (C), 50.3 (C), 40.8 (CH), 49.3 (C), 47.1 (CH), 43.2 (CH), 37.8
IR (KBr): 2950, 2910, 1738, 1706, 1448, 1430, 991 cm–1.
1
(
C), 35.4 (CH ), 33.9 (CH ), 21.7 (CH ), 21.1 (CH ), 19.2 (CH ),
2 2 2 3 2
H NMR (C D , only mean signals of the major isomer are given):
1
8.81 (CH ), 15.11 (CH ), 12.8 (CH ), 12.3 (CH ).
6
6
2
2
3
3
d = 7.61 (s, 1 H), 5.28 (br s, 1 H), 5.18 (s, 1 H), 2.15 (m, 1 H), 1.55
+
MS-FAB: m/z (%) = 441 (M + H, 50), 395 (9), 379 (12), 313 (100),
95 (21), 285 (11).
(br s, 3 H), 0.86 (s, 3 H), 0.79 (s, 3 H).
2
+
+
MS (EI): m/z (%) = 315 (M + 1, 4), 314 (M , 16), 286 (5), 268 (28),
+
HRMS-FAB: m/z calcd for C H IO [M + H]: 441.0921; found:
2
0
26
3
2
53 (37), 239 (8), 196 (47), 164 (100).
4
41.0927.
+
HRMS (EI): m/z calcd for C H O [M ]: 314.1882; found:
2
0
26
3
3
14.1895.
1
8-Formyloxytrachylobane-3,14,15-trione (15)
Mp 258–261 °C (hexane–CH Cl ); [a] –17 (c 0.15, CHCl ).
2
2
D
3
Alcohol 28
A mixture of epimers.
IR (KBr): 2951, 2869, 1754, 1732, 1705, 1443, 1328, 1219, 1121,
–
1
9
01, 890, 612 cm .
IR (KBr): 3415, 2923, 2852, 1695, 1438, 1290, 1101, 1077, 1017,
1
H NMR (CDCl ): d = 8.14 (s, 1 H), 4.29 and 3.95 (AB system, J =
–1
3
8
97 cm .
1
2
8 Hz, 2 H), 2.60 (d, J = 7.8 Hz, 1 H), 2.53–2.48 (m, 2 H), 2.40–
.23 (m, 2 H), 2.20 (ddd, J = 12.7, 9.0, 2.3 Hz, 1 H), 2.03 (dd, J =
Synthesis 2005, No. 19, 3355–3361 © Thieme Stuttgart · New York