C(3)H and C(6)H), 2.87–2.84 (2 H, m, C(1)H and C(8)H), 2.35–
2.24 (2 H, m, C(2)H and C(7)H), 1.88–1.75 (2 H, m, C(4)H and
C(5)H), 1.59–1.43 (4 H, m, C(2)H, C(4)H, C(5)H and C(7)H),
0.89 (18 H, s, 2 × CMe3), 0.07 (6 H, s, 2 × SiMe) and 0.06 (6 H,
s, 2 × SiMe); δC(100 MHz) 69.4 (COSi), 53.0 (COC), 36.0
(CH2), 30.4 (CH2), 25.8 (2 × SiCMe3), 18.1 (2 × SiCMe3) and
Ϫ4.8 (4 × SiMe); m/z (CI) 387 (40%), 255 (60), 239 (75), 201
(30), 132 (100), 107 (35), 91 (35) and 74 (45) (Found: M ϩ Hϩ,
387.2750. C20H43O3Si2 requires M, 387.2751).
(4.5 mg, quant.) as a solid; [α]2D3 0.0 (c 0.9, EtOH); Rf 0.45 (20%
MeOH in CH2Cl2); νmax/cmϪ1 3302br s, 2948m, 1468m, 1361m,
1123m, 1037s and 667m; δH(400 MHz, CD3OD) 4.14–4.06 (3 H,
m, C(2)H, C(4)H and C(7)H), 2.57–2.47 (2 H, m, C(1)H and
C(5)H) and 1.99–1.63 (6 H, m, C(3)H2, C(6)H2 and C(8)H2);
δC(100 MHz, CD3OD) 80.2 (CHO), 74.7 (CHO), 45.9 (CH),
40.7 (CH2) and 36.0 (2 × CH2); m/z (CI) 176 (95%) and 159
(100) (Found: M ϩ Hϩ, 159.1026. C8H15O3 requires M,
159.1021).
Products from rearrangement of epoxide 27 following the general
procedure
Products from rearrangement of epoxide 28 following the general
procedure
(1R*,2S*,4R*,5S*,7S*)-4,7-Bis(tert-butyldimethylsilyloxy)-
bicyclo[3.3.0]octan-2-ol 29. Rf 0.3 (10% Et2O in light petrol-
eum); νmax/cmϪ1 3331br m, 2929s, 2858s, 1472w, 1361w, 1256m,
1123m, 1054m, 836s and 775s; δH(400 MHz) 4.28–4.25 (1 H, m,
C(7)H), 4.13–4.07 (2 H, m, C(2)H and C(4)H), 3.11–3.08 (1 H,
m, OH), 2.48–2.39 (2 H, m, C(1)H and C(5)H), 1.94–1.74 (6 H,
m, C(3)H2, C(6)H2 and C(8)H2), 0.90 (9 H, s, SiCMe3), 0.89
(9 H, s, SiCMe3), 0.08 (6 H, s, 2 × SiMe), 0.05 (3 H, s, SiMe) and
0.04 (3 H, s, SiMe); δC(100 MHz) 75.8 (CHO), 72.1 (CHO), 71.6
(CHO), 47.2 (CH), 45.4 (CH), 43.3 (CH2), 35.8 (CH2), 35.0
(CH2), 25.8 (2 × SiCMe3), 18.1 (SiCMe3), 18.0 (SiCMe3), Ϫ4.6
(2 × SiMe), Ϫ4.8 (SiMe), and Ϫ5.0 (SiMe); m/z (CI) 387
(100%), 329 (15), 270 (20), 132 (10), 105 (15) and 92 (15)
(Found: M ϩ Hϩ, 387.2756. C20H43O3Si2 requires M, 387.2751).
The ee was determined on the diol (derived from 2,4-dinitro-
benzoylation followed by desilylation using BF3ؒEt2O)† by
chiral HPLC (60 : 40 EtOH–hexane, 0.75 cm3 minϪ1) tRmj, 18.0;
tRmn, 26.4.
(2S,4R,7S)-4,7-Bis(tert-butyldimethylsilyloxy)cyclooct-2-enol
33. Data from Table 3, entry 2: Rf 0.2 (20% Et2O in light petrol-
eum); νmax/cmϪ1 3315br w, 2931s, 2850s, 1471m, 1358m, 1249s,
1048s, 835m and 774s; δH(400 MHz) 5.60 (1 H, dd, J 12.1, 5.7,
C(2)H), 5.53 (1 H, dd, J 12.1, 5.5, C(3)H), 4.98–4.92 (1 H, m,
C(1)H), 4.69–4.63 (1 H, m, C(4)H), 3.82–3.77 (1 H, m, C(7)H),
2.02–1.89 (3 H, m, C(6)H and C(8)H2), 1.75–1.59 (4 H, m,
C(5)H2, C(6)H and COH), 0.89 (9 H, s, SiCMe3), 0.88 (9 H, s,
SiCMe3), 0.06 (6 H, s, 2 × SiMe) and 0.05 (6 H, s, 2 × SiMe);
δ (100 MHz) 133.2 (C᎐C), 133.1 (C᎐C), 70.0 (CHO), 68.6
᎐
᎐
C
(CHO), 66.0 (CHO), 45.2 (CH2), 33.6 (CH2), 32.9 (CH2), 25.8
(2 × SiCMe3), 18.1 (2 × SiCMe3), Ϫ4.8 (2 × SiMe) and Ϫ4.9
(2 × SiMe); m/z (CI) 387 (30%), 255 (100), 237 (15) and 132
(20) (Found: M ϩ Hϩ, 387.2748. C20H43O3Si2 requires M,
387.2751).
In all other cases a mixture of bicyclic alcohol 32 and allylic
alcohol 33 were formed. The ee of both alcohols was measured
by derivatisation to the diols (derived from 3,5-dinitrobenzoyl-
ation followed by desilylation using BF3ؒEt2O)† by chiral
HPLC (60 : 40 EtOH–hexane, 0.75 cm3 minϪ1). For bicyclic
alcohol 32 derivative: tRmj, 10.4; tRmn, 11.7. For allylic alcohol
33 derivative: tRmj, 15.3; tRmn, 22.7. This mixture was treated
with 10% Pd/charcoal in EtOAc under an atmosphere of H2 for
1 h. After filtration the mixture was evaporated under reduced
pressure. Purification of the residue by column chromatography
(10% Et2O in light petroleum) gave bicyclic alcohol 32 and
ketone 34.
(4R*,7S*)-1-sec-Butyl-4,7-bis(tert-butyldimethylsilyloxy)-
cyclooctene 30 (R ؍
Bus). As an unseparated mixture of stereo-
isomers at the sec-butyl 2-carbon; Rf 0.8 (10% Et2O in light
petroleum); νmax/cmϪ1 2965s, 2922s, 2850s, 1472m, 1462m,
1072m, 839s and 743s; δH(400 MHz) 5.35–4.84 (1 H, m, C(2)H),
4.18–3.46 (2 H, m, C(4)H and C(7)H), 2.81–0.78 (17 H, m),
0.91–0.83 (18 H, m, 2 × SiCMe3) and 0.08–0.01 (12 H, m, 4 ×
SiMe); δ (100 MHz) 144.8 (C C᎐CH), 144.0 (C C᎐CH), 123.8
᎐
᎐
2
C
2
(C C᎐CH), 121.0 (C C᎐CH), 73.7 (CHO), 72.3 (CHO), 72.1
᎐
᎐
2
2
(CHO), 71.8 (CHO), 44.1 (CH), 43.1 (CH2), 41.8 (CH2), 37.8
(CH2), 36.8 (CH2), 36.0 (CH2), 32.3 (CH2), 30.4 (CH2), 25.9
(SiCMe3), 25.7 (SiCMe3), 20.0 (CH2), 19.2 (CH2), 18.1
(SiCMe3), 18.0 (SiCMe3), 12.3 (Me), 12.1 (Me), Ϫ4.6 (SiMe),
Ϫ4.7 (SiMe), Ϫ4.8 (SiMe) and Ϫ5.0 (SiMe).
(1R,2S,4S,5S,7S)-4,7-Bis(tert-butyldimethylsilyloxy)bicyclo-
[3.3.0]octan-2-ol 32. Rf 0.2 (10% Et2O in light petroleum); νmax
/
cmϪ1 3369br w, 2955s, 2929s, 2856s, 1472w, 1361w, 1254m,
1048s, 835s and 774s; δH(400 MHz) 4.52–4.47 (1 H, m, C(4)H),
4.33–4.29 (1 H, m, C(7)H), 3.88–3.64 (1 H, m, C(2)H), 2.88–
2.81 (1 H, m, C(5)H), 2.52–2.45 (1 H, m, C(1)H), 1.90–1.21
(6 H, m, C(3)H2, C(6)H2 and C(8)H2), 0.88 (9 H, s, SiCMe3),
0.87 (9 H, s, SiCMe3), 0.05 (6 H, s, 2 × SiMe) and 0.04 (6 H, s,
2 × SiMe); δC(100 MHz) 77.4 (CHO), 75.4 (CHO), 72.5 (CHO),
50.5 (CH), 43.9 (CH), 42.6 (CH2), 40.6 (CH2), 37.1 (CH2),
25.8 (2 × SiCMe3), 18.1 (2 × CMe3), Ϫ4.5 (2 × SiCH3) and Ϫ4.8
(2 × SiCH3); m/z (CI) 387 (55%), 346 (20), 272 (100), 255 (50),
132 (90) and 90 (25) (Found: M ϩ Hϩ, 387.2752. C20H43O3Si2
requires M, 387.2751).
(4R*,7S*)-4,7-Bis(tert-butyldimethylsilyloxy)-1-isopropyl-
cyclooctene 30 (R ؍
Pri). Rf 0.8 (10% Et2O in light petroleum);
νmax/cmϪ1 2956s, 2934s, 1472w, 1467m, 1067m, 954m, 839s and
699s; δH(400 MHz) 5.41–4.84 (1 H, m, C(2)H), 4.20–3.62 (2 H,
m, C(4)H and C(7)H), 2.87–0.09 (15 H, m), 0.91–0.83 (18 H, m,
2 × SiC(CH3)3) and 0.06–0.02 (12 H, m, 4 × SiCH3); δC(100
MHz) 146.5 (C C᎐CH), 145.9 (C C᎐CH), 123.8 (C C᎐CH),
᎐
᎐
᎐
2
2
2
119.9 (C C᎐C ), 78.7 (CHO), 73.6 (CHO), 72.6 (CHO), 71.9
᎐
2
H
(CHO), 43.2 (CH), 41.7 (CH2), 37.5 (CH2), 37.3 (CH2), 36.0
(CH2), 35.9 (CH2), 35.7 (CH2), 34.9 (CH2), 32.1 (CH2), 31.9
(CH2), 31.5 (CH2), 30.7 (CH2), 30.4 (CH2), 29.9 (CH2), 29.7
(CH2), 26.0 (SiCMe3), 25.9 (SiCMe3), 25.8 (SiCMe3), 24.6 (Me),
22.4 (Me), 21.9 (Me), 21.7 (Me), 18.4 (SiCMe3), 18.2 (SiCMe3),
18.1 (SiCMe3), Ϫ4.6 (2 × SiMe), Ϫ4.8 (SiMe) and Ϫ5.0 (SiMe);
m/z (CI) 430 (M ϩ NH4ϩ, 5%), 281 (10), 166 (45) and 149 (100).
(3R,6S)-3,6-Bis(tert-butyldimethylsilyloxy)cyclooctanone 34.
Rf 0.7 (10% Et2O in light petroleum); νmax/cmϪ1 2929s, 2857s,
1702m, 1472w, 1253m, 1077m, 836s and 775m; δH(400 MHz)
3.89–3.84 (1 H, m, C(3)H), 3.78–3.75 (1 H, m, C(6)H), 2.97–
2.92 (1 H, m, C(2)H), 2.47–2.38 (2 H, m, C(2)H, and C(4)H or
C(5)H), 2.26–2.18 (2 H, m, C(4)H2, or C(4)H and C(5)H, or
C(5)H2), 1.93–1.85 (2 H, m, C(4)H or C(5)H, and C(7)H), 1.75–
1.62 (1 H, m, C(7)H), 1.17–1.08 (2 H, m, C(8)H2), 0.89 (9 H, s,
SiCMe3), 0.88 (9 H, s, SiCMe3), 0.09 (3 H, s, SiMe), 0.08 (3 H, s,
SiMe), 0.04 (3 H, s, SiMe) and 0.03 (3 H, s, SiMe); δC(100 MHz)
(1R*,2S*,4R*,5S*,7R*)-Bicyclo[3.3.0]octane-2,4,7-triol 31
HF (40% w/w in H2O; 0.1 cm3, 4 mmol) was added to a stirred
solution of bicyclic alcohol (ϩ)-29 (12 mg, 0.031 mmol) in
MeCN (2 cm3). After 1 h the reaction was neutralised with the
minimum amount of aq. NaHCO3 and evaporated under
reduced pressure. Purification of the residue by column chrom-
atography (20% MeOH in CH2Cl2) gave the meso triol 31
212.0 (C᎐O), 72.7 (CHO), 70.7 (CHO), 48.9 (CH ), 41.3 (CH ),
᎐
2
2
30.4 (CH2), 29.7 (CH2), 28.7 (CH2), 25.7 (2 × SiCMe3), 18.0
(2 × SiCMe3), Ϫ4.8 (2 × SiMe) and Ϫ4.9 (2 × SiMe); m/z (CI)
404 (80%), 387 (100), 272 (60), 255 (35), 197 (15), 132 (25) and
J. Chem. Soc., Perkin Trans. 1, 2001, 2161–2174
2171