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J. B. Sweeney et al. / Tetrahedron 63 (2007) 2729–2737
170.73, 156.57, 138.03, 129.41, 129.12, 128.98, 128.60,
128.30, 72.63, 66.87, 66.29, 59.33, 39.47, 34.47, 31.17,
18.93; m/z 383 (M+, 0.6%), 240 (48.6), 196 (33.6), 91 (100).
silyl ether, as a colourless viscous liquid (272 mg, 85%).
(Found: C, 67.32; H, 7.64; N, 2.54. C28H39NO5Si requires
C, 67.57; H, 7.90; N, 2.81%.) [a]2D2 ꢁ18.01; nmax (CCl4)/
cmꢁ1 3434, 1727; dH (270 MHz; (CD3)2CO) 0.06 (3H, s),
0.07 (3H, s), 0.89 (9H, s), 1.25–1.85 (8H, m), 3.99–4.10
(1H, m), 5.08 (2H, 2ꢄd, J 3.8), 5.06–5.15 (1H, m), 5.34
(1H, d, J 7.7), 7.10 (1H, d, J 7.7), 7.30–7.50 (10H, m); dC
(67.5 MHz; (CD3)2CO) 170.62, 156.51, 138.09, 137.89,
129.39, 129.09, 128.95, 128.60, 128.25, 72.55, 68.09,
66.87, 59.34, 39.86, 34.59, 30.47, 26.15, 19.43, 18.50,
Data for 22: mp 120 ꢃC. (Found: C, 68.91; H, 6.66; N,
3.69. C22H25NO5 requires C, 68.91; H, 6.57; N, 3.65%.)
[a]2D4 ꢁ24.02; nmax (CCl4)/cmꢁ1 3621, 3435, 1729; dH
(270 MHz; CDCl3) 1.10–1.95 (8H, m), 3.65–3.76 (1H, m),
5.03–5.16 (3H, m), 5.34 (1H, d, J 7.8), 7.14 (1H, d, J 7.8),
7.29–7.48 (10H, m); dC (67.5 MHz; (CD3)2CO) 170.74,
156.6, 138.01, 129.46, 129.17, 129.01, 128.66, 128.31,
72.64, 66.90, 66.12, 59.41, 39.18, 34.45, 30.86, 19.78; m/z
383 (M+, 0.3%), 240 (24.0), 196 (19.8), 91 (100).
t
ꢁ4.66; m/z 440 (M+ꢁ Bu, 5.9%), 342 (26.9), 234 (37.0),
91 (100), 81 (55.2).
(2) The ester from step 1 (230 mg, 0.46 mmol), lithium
hydroxide monohydrate (20 mg, 0.46 mmol), water (3 ml)
and tetrahydrofuran (24 ml) were combined and refluxed
for 12 h. Upon cooling to room temperature Merck Kieselgel
60 (0.5 g) was added and the mixture was evaporated to dry-
ness in vacuo. Flash column chromatography, eluting with
ether/petrol (3:7), yielded (+)-18, as a colourless viscous liq-
uid (92 mg, 87%). (Found: 230.1722. C12H26O2Si requires
230.1702.) [a]2D4 +4.85 (c 1, EtOAc); other data as above,
for (ꢀ)-18.
4.12. (1R,3R)-(L)-1-(tert-Butyldimethylsilyl)oxy-3-
hydroxycyclohexane (L)-18
(1) Hydroxyester 23 (310 mg, 0.81 mmol) and 2,6-lutidine
(0.14 ml, 1.21 mmol) were combined in dry dichlorometh-
ane (30 ml) and cooled on an ice bath. tert-Butyldimethyl-
silylmethanesulfonate (0.37 ml, 1.62 mmol) was added and
stirring was continued for 15 h at room temperature. The
reaction mixture was washed with 5% hydrochloric acid
(1ꢄ10 ml) and saturated aqueous sodium hydrogen carbon-
ate (1ꢄ10 ml), dried (MgSO4) and evaporated in vacuo to
give a colourless viscous liquid. Purification by flash column
chromatography eluting with ether/petrol (1:4) yielded the
silyl ether, as a colourless viscous liquid (338 mg, 84%).
(Found: C, 67.94; H, 7.80; N, 3.11. C28H39NO5Si requires
C, 67.57; H, 7.90; N, 2.81%.) [a]2D2 ꢁ29.34; nmax (CCl4)/
cmꢁ1 3434, 1728; dH (270 MHz; (CD3)2CO) 0.05 (3H, s),
ꢁ0.04 (3H, s), 0.84 (9H, s), 1.20–1.75 (8H, m), 3.77–3.89
(1H, m), 5.08 (2H, s), 5.05–5.16 (1H, m), 5.34 (1H, d,
J 7.7), 7.12 (1H, d, J 7.7), 7.32–7.49 (10H, m); dC
(67.5 MHz; (CD3)2CO) 170.66, 156.54, 138.12, 137.96,
129.49, 129.14, 129.01, 128.63, 128.27, 72.61, 67.96,
66.88, 59.28, 39.63, 34.80, 30.80, 26.12, 19.74, 18.45,
ꢁ4.71; m/z 440 (M+ꢁ57, 5.0%), 342 (29.8), 240 (14.6),
234 (14.5), 196 (10.7), 91 (100).
Acknowledgements
We acknowledge the financial support of the EPSRC (A.F.H.,
J.R.K.). We also acknowledge the advice of Mr. E. Blair
and the technical contributions of Mr. T. McDermott.
References and notes
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therein.
(2) The ester from step 1 (307 mg, 0.62 mmol), lithium
hydroxide monohydrate (26 mg, 0.62 mmol), water (3 ml)
and tetrahydrofuran (24 ml) were combined and refluxed
for 12 h. Upon cooling to room temperature Merck Kieselgel
60 (0.5 g) was added and the mixture was evaporated
to dryness in vacuo. Flash column chromatography eluting
with ether/petrol (3:7) yielded (ꢁ)-18, as a colourless vis-
cous liquid (120 mg, 84%). (Found: 230.1727. C12H26O2Si
requires 230.1702); [a]2D4 ꢁ4.55 (c 1, EtOAc); other data as
above, for (ꢀ)-18.
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(1) Hydroxyester 22 (246 mg, 0.64 mmol), 2,6-lutidine
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sulfonate (0.29 ml, 1.28 mmol) were reacted in dry dichloro-
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ate (1ꢄ10 ml), dried (MgSO4) and evaporated in vacuo, to
give a colourless viscous liquid. Purification by flash column
chromatography, eluting with ether/petrol (1:4), yielded the
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