C. Hollmann, P. Eilbracht / Tetrahedron 56 (2000) 1685–1692
1691
1
1048 (s), 842 (s) cmϪ1. MS (EI, 70 eV) m/z (%)226 (Mϩ,
60), 211 (100), 198 (3), 183 (3), 167 (6), 155 (9), 129 (13),
119 (20), 93 (21), 75 (41). (3aRء
,6Sء
,6aSء
)-Diastereoisomer
Diastereoisomer b: H NMR (400 MHz, CDCl3, 20ЊC)
d0.01 (s, 9 H), 0.90 (s, 3 H), 0.97 (s, 3 H), 1.11 (s, 3
2
H), 1.53 (m, 1 H), 1.59 (dm, J13.3 Hz, 1 H), 1.68 (m, 2
1
2
(9b): H NMR (400 MHz, CDCl3, 20ЊC) d0.08 (s, 9 H),
H), 1.72 (d, J13.3 Hz, 1 H), 1.87 (m, 1 H), 2.06 (dm,
2
1.11 (s, 3 H), 1.35–1.54 (m, 4 H), 1.72 (m, 1 H), 1.84 (m, 1
H), 1.90 (dء
, 2J18.4 Hz, 1 H), 2.04 (dd, 2J18.4,
3J3.5 Hz, 1 H), 2.37 (dm, J9.4 Hz, 1 H), 3.77 (ddd,
2J13.1 Hz, 1 H), 2.19 (d, J13.1 Hz, 1 H), 2.20 (m, 1
H), 4.44 (m, 1 H). 13C NMR (100 MHz, CDCl3, 20ЊC)
dϪ0.2 (CH3), 28.0 (CH3), 32.1 (CH3), 33.2 (CH3), 34.6
(CH2), 35.2 (Cq), 43.1 (Cq), 43.8 (CH2), 51.5 (CH2), 55.5
(CH2), 63.9 (CH), 77.9 (CH), 214.3 (Cq). IR (NaCl, neat)
n~ 2956 (s), 2871 (s), 1706 (s), 1458 (m), 1369 (m), 1251
(s), 1055 (s), 843 (s) cmϪ1. MS (EI, 70 eV) m/z (%)268
(Mϩ, 56), 253 (100), 237 (3), 211 (11), 197 (17), 178 (87),
163 (89), 129 (35), 123 (45), 105 (17), 73 (67).
J9.4 Hz, 3J5.9 Hz, 3J3.3 Hz,
1
H). 13C NMR
(100 MHz, CDCl3, 20ЊC) d0.1 (CH3), 26.6 (CH3), 30.6
(CH2), 36.7 (CH2), 36.9 (Cq), 41.9 (CH2), 50.0 (CH2), 55.8
(CH), 72.4 (CH), 217.4 (Cq). IR (NaCl, neat) n~ 2951 ꢀs;
2903 (s), 2870 (s), 1747 (s), 1459 (m), 1368 (m), 1251 (s),
1165 (m), 1093 (s), 841 (s) cmϪ1. MS (EI, 70 eV) m/z
(%)226 (Mϩ, 4), 211 (100), 193 (2), 183 (4), 170 (7), 155
(9), 129 (44), 119 (19), 94 (30), 75 (40).
6,6,7a-Trimethyl-1,2,5,6,7,7a-hexahydro-inden-4-one (10).
Obtained from trimethyl-(3,5,5-trimethyl-3-vinyl-cyclohex-
1-enyloxy)-silane24 (8c) as a colourless liquid in 91% yield.
1H NMR (400 MHz, CDCl3, 20ЊC) d0.93 (s, 3 H), 1.04 (s,
3 H), 1.12 (s, 3 H), 1.64 (d, 2J14.0 Hz, 1 H), 1.70
(d,2J14.0 Hz, 1 H), 1.86 (m, 1 H), 2.03 (dd, J12.1 Hz,
J6.5 Hz, 1 H), 2.14 (d, 2J16.3 Hz, 1 H), 2.30 (d,
3-Trimethylsilanyloxy-octahydro-inden-4-one
(9c,d).
Obtained from trimethyl-(3-vinyl-cyclohex-1-enyloxy)-si-
lane11 (8b) as a colourless liquid in 51% yield as a 1:1
mixture of diastereoisomers. C12H22O2Si (226.39): Calcd
C, 63.67; H, 9.79; Found C, 63.9; H, 9.7. The diastereo-
isomers were separated by column chromatography on
silica gel using a 8:1 mixture of petrol ether (30/60) and
diethyl ether as eluent. Diastereoisomer a: 1H NMR
(400 MHz, CDCl3, 20ЊC) d0.04 (s, 9 H), 1.22 (m, 1 H),
1.46 (m, 2 H), 1.78 (m, 4 H), 1.96 (m, 1 H), 2.25 (tء
,
2J16.3 Hz, 1 H), 2.42 (m, 2 H), 6.61 (t, J3.1 Hz, 1 H).
3
13C NMR (100 MHz, CDCl3, 20ЊC) d28.5 (CH3), 29.3
(CH3), 30.1 (CH2), 31.7 (CH3), 32.8 (Cq), 45.0 (CH2),
45.1 (Cq), 51.1 (CH2), 52.6 (CH2), 137.5 (CH), 148.3
(Cq), 199.3 (Cq). IR (NaCl, neat) n~ 3055 (w), 2953 (s),
2866 (s), 2843 (s), 1689 (vs), 1617 (s), 1452 (s), 1367 (m),
1266 (s), 1106 (m) cmϪ1. MS (EI, 70 eV) m/z (%)179
(Mϩϩ1, 100), 164 (70), 122 (28), 107 (59), 94 (77), 79
(65), 55 (19). C12H18O (178.27): Calcd C, 80.85; H,
10.18; Found C, 80.6; H, 10.3.
3
3
3J6.8 Hz, 2 H), 2.49 (dd, J8.5 Hz, J3.7 Hz, 1 H),
2.67 (m, 1 H), 4.61 (m, 1 H). 13C NMR (100 MHz,
CDCl3, 20ЊC) dϪ0.1 (CH3), 23.3 (CH2), 27.3 (CH2),
28.4 (CH2), 34.1 (CH2), 40.6 (CH2), 40.7 (CH), 61.5
(CH), 73.7 (CH), 212.2 (Cq). IR (NaCl, neat) n~ 2956
(vs), 2872 (s), 1712 (s), 1463 (m), 1251 (s), 1059 (s),
1029 (s), 841 (s) cmϪ1. GC-MS (EI, 70 eV) m/z (%)227
(Mϩϩ1, 60), 211 (70), 136 (39), 119 (100), 108 (20), 91
4-Methyl-naphthalene-1-ol28 (12a). Obtained from
trimethyl-[1-(2-vinyl-phenyl)-vinyloxy]-silane (11) as
colourless crystals in 37% yield.
1
(41), 80 (32). Diastereoisomer b: H NMR (400 MHz,
CDCl3, 20ЊC) dϪ0.04 (s, 9 H), 1.51 (m, 2 H), 1.65 (m,
4 H), 1.85 (m, 2 H), 2.11 (m, 1 H), 2.25 (m, 2 H), 2.41 (dd,
Trimethyl-(4-methyl-naphthalen-1-yloxy)-silane (12b).
Obtained from trimethyl-[1-(2-vinyl-phenyl)-vinyloxy]-
silane (11) as a colourless oil in 17% yield. 1H NMR
(400 MHz, CDCl3, 20ЊC) d0.39 (s, 9 H), 2.65 (s, 3 H),
6.82 (d, 3J7.7 Hz, 1 H), 7.19 (d,3J7.7 Hz, 1 H), 7.54 (m,
3J8.8 Hz, J5.5 Hz, 1 H), 4.38 (m, 1 H). 13C NMR
3
(100 MHz, CDCl3, 20ЊC) dϪ0.3 (CH3), 23.4 (CH2),
30.4 (CH2), 31.0 (CH2), 35.0 (CH2), 39.3 (CH), 42.1
(CH2), 58.2 (CH), 77.1 (CH), 213.6 (Cq). IR (NaCl, neat)
n~ 2955 (s), 2939 (s), 2866 (m), 1705 (vs), 1449 (w), 1251
(s), 1073 (s), 1044 (s), 842 (vs) cmϪ1. GC-MS (EI, 70 eV)
m/z (%)227 (Mϩϩ1, 60), 211 (80), 129 (38), 119 (100),
107 (8), 91 (62), 75 (26).
3
4
2 H), 7.96 (dd, J7.6 Hz, J1.8 Hz, 1 H), 8.22 (dd,
4
3J7.6 Hz, J1.8 Hz, 1 H). 13C NMR (100 MHz, CDCl3,
20ЊC) d0.3 (CH3), 18.8 (CH3), 112.4 (CH), 123.0 (CH),
124.1 (CH), 124.8 (CH), 125.9 (CH), 126.3 (CH), 127.0
(Cq), 128.0 (Cq), 133.7 (Cq), 149.8 (Cq). IR (NaCl, neat)
n~ 3071 (m), 3034 (w), 2960 (s), 2900 (m), 2869 (m), 1586
(s), 1464 (s), 1391 (s), 1253 (s), 1072 (s), 846 (s) cmϪ1. GC-
MS (EI, 70 eV) m/z (%)231 (Mϩϩ1, 99), 230 (Mϩ, 100),
215 (45), 159 (5), 140 (4), 73 (12).
6,6,7a-Trimethyl-3-trimethylsilanyloxy-octahydro-inden-
4-one (9e). Obtained from trimethyl-(3,5,5-trimethyl-3-
vinyl-cyclohex-1-enyloxy)-silane24 (8c) as a colourless
liquid in 50% yield as a 6:1 mixture of diastereoisomers.
C15H28O2Si (268.47): Calcd. C, 67.11; H, 10.51; Found C,
67.5; H, 10.4. The diastereoisomers were separated by
column chromatography on silica gel using a 15:1 mixture
of n-hexane and methyl t-butyl ether as eluent. (minor)
Diastereoisomer a: 1H NMR (400 MHz, CDCl3, 20ЊC)
d0.03 (s, 9 H), 0.93 (s, 3 H), 0.97 (s, 3 H), 1.21 (s, 3
Acknowledgements
Financial support of this work by the Fonds der Chemischen
Industrie and donations of chemicals by the Degussa-Hu¨ls
AG, Frankfurt a. M., are gratefully acknowledged.
2
2
H), 1.44 (d, J14.9 Hz, 1 H), 1.52 (d, J14.9 Hz, 1 H),
1.58 (m, 3 H), 1.95 (m, 1 H), 2.08 (d, 2J13.3 Hz, 1 H), 2.16
2
3
(d, J13.3 Hz, 1 H), 2.21 (d, J5.0 Hz, 1 H), 4.50 (dt,
3J5.0 Hz, J5.0 Hz, 1 H). 13C NMR (100 MHz, CDCl3,
3
20ЊC) d0.0 (CH3), 29.8 (CH3), 31.2 (CH3), 31.7 (CH3),
34.2 (CH2), 36.0 (Cq), 40.8 (CH2), 45.5 (Cq), 49.1 (CH2),
51.9 (CH2), 67.9 (CH), 76.4 (CH), 212.6 (Cq). (major)
References
¨
1. Eilbracht, P.; Barfacker, L.; Buss, C.; Hollmann, C.; Kitsos-