2576
J. F. Bickley et al. / Tetrahedron 60 (2004) 2569–2576
in vacuo. The product was purified by flash column
chromatography (SiO2; Et2O–n-hexane, 1:15) to yield the
title compound 22 (245 mg, 90%) as a colourless oil;
(SiO2; EtOAc–n-hexane, 7:3) to yield the title compound
14 (36 mg, 44%) as a white solid; mp 52–56 8C;
[a]D¼þ22.6 (c 0.9, MeOH); nmax(film)/cm21 1050, 1132,
1292, 1417, 1715, 2361, 2921, 3372 br.; dH (400 MHz;
CDCl3; Me4Si) 1.86 (3H, d, J¼4.8 Hz, CH3), 4.28 (1H, d,
J¼2.8 Hz, C(5)H), 4.82 (1H, m, C(4)H), 5.98–6.08 (2H, m,
C(10)H and C(20)H), 7.25 (1H, d, J¼2.2 Hz, C(3)H); dC
(100 MHz, CDCl3, Me4Si) 15.8 (CH3), 75.6, 81.6, 117.3,
134.2 (CH), 139.2 (C), 153.2 (CH), 203.6 (C); m/z (CI) 172
([MþNH4]þ, 100%), 155 ([MþH]þ, 79), 154 ([M]þ, 20);
Found: [MþH]þ, 155.07109. C8H11O3 requires [MþH]þ,
155.07082.
n
max(film)/cm21 1724, 2343, 2360, 2857, 2894, 2929, 2955;
dH (400 MHz; CDCl3; Me4Si) 20.01 (3H, s, SiCH3), 0.08
(3H, s, SiCH3), 0.14 (3H, s, SiCH3), 0.15 (3H, s, SiCH3),
0.86 (9H, s, SiC(CH3)3), 0.94 (9H, s, SiC(CH3)3), 1.80 (3H,
d, J¼5.7 Hz, C(30)H), 4.33 (1H, t, J¼4.8 Hz, C(5)H), 4.61
(1H0, m, C(4)H), 5.68–5.78 (3H, m, C(1)H, C(10)H and
C(2 )H), 5.90 (1H, d, J¼4.8 Hz, C(3)H), 7.44 (2H, dd,
J¼7.5 Hz, Ar), 7.56 (1H, tt, J¼1.5, 7.5 Hz, Ar), 8.07 (2H,
dd, J¼1.5, 7.5 Hz, Ar); dC (100 MHz, CDCl3, Me4Si) 24.2,
24.15, 24.04, 24.01, 15.5 (CH3), 18.3, 18.5 (C), 26.1, 26.3
(CH3), 80.8, 83.4, 86.7, 122.4, 128.7, 130.1 (CH), 130.5 (C),
131.3, 132.6, 133.3 (CH), 138.2, 166.5 (C); m/z (ESþ)
23
23
511 ([Mþ Na]þ, 100%); Found: [Mþ Na]þ, 511.2698.
Acknowledgements
23
44
23
C27H NaO4Si2 requires [Mþ Na]þ, 511.2676.
Charterhouse Therapeutics Ltd are thanked for financial
support (T. J. S.) and helpful contributions from Dr. Paul
Evans were important to this project.
4.1.16. (4S,5R)-4,5-Bis-(tert-butyl-dimethyl-silanyloxy)-
2-prop-(Z)-enyl-cyclopent-2-enone (23). To a solution of
benzoate 22 (365 mg, 0.75 mmol) in anhydrous toluene
(8 ml) at 278 8C under an atmosphere of nitrogen was
added diisobutylaluminium hydride (1 M solution in
hexanes, 1.65 ml, 1.65 mmol) slowly and the reaction
stirred for 90 min. The reaction mixture was allowed to
warm to room temperature then cooled to 278 8C and
quenched with methanol (1 ml) and water (5 ml). The
product was extracted with diethyl ether (3£10 ml) and the
combined organic layers dried (MgSO4) and the solvent
removed in vacuo to yield 350 mg of a crude colourless oil.
The crude alcohol (350 mg) was dissolved in dichloro-
References and notes
1. (a) Roberts, S. M.; Santoro, M. G.; Sickle, E. S. J. Chem. Soc.,
Perkin Trans. 1 2002, 1735. (b) Roberts, S. M.; Santoro, M. G.
Chem. Britain 2001, 5, 34. (c) Rossi, A.; Kapahi, P.; Natoli,
G.; Takahashi, T.; Chen, Y.; Karin, M.; Santoro, M. G. Nature
2000, 403, 103. (d) Santoro, M. G. Trends Microbiol. 1997, 5,
276.
˚
methane (8 ml) and 4 A molecular sieves (350 mg) added.
2. Santoro, M. G.; Roberts, S. M. Drug News Perspect. 1999, 12,
395.
After 45 min. at room temperature pyridinium dichromate
(0.71 g, 1.88 mmol) was added and the reaction was stirred
for 16 h. The reaction was filtered through a plug of silica
and the solvent removed in vacuo. The product was purified
by flash column chromatography (SiO2; Et2O–n-hexane,
1:15) to yield the title compound 23 (202 mg, 71% over two
steps) as a colourless oil; [a]D¼þ86.2 (c 1.2, CHCl3);
3. Rossi, A.; Elia, G.; Santoro, M. G. J. Biol. Chem. 1996, 271,
32192.
4. Sagawa, H.; Koyama, N.; Chono, H.; Takesako, K.; Kato, I.
(Takara Shuzo Co.) Kyoto, Japan WO 98/41196.
5. (a) Weidler, M.; Rether, J.; Anke, T.; Erkel, G.; Sterner, D.
J. Antibiot. 2001, 54, 679. (b) Weidler, M.; Rether, J.; Anke,
T.; Erkel, G. Biochem. Biophys. Res. Commun. 2000, 276, 447.
6. cf. Johnson, C. R.; Adams, J. P.; Braun, M. P.; Senanayake,
C. B. W. Tetrahedron Lett. 1992, 33, 919.
n
max(film)/cm21 1472, 1732, 2359, 2857, 2885, 2929, 2955;
dH (400 MHz; CDCl3; Me4Si) 0.15 (3H, s, SiCH3), 0.17
(3H, s, SiCH3), 0.18 (3H, s, SiCH3), 0.20 (3H, s, SiCH3),
0.94 (18H, s, 2£SiC(CH3)3), 1.84 (3H, d, J¼5.7 Hz, CH3),
4.18 (1H, d, J¼2.7 Hz, C(5)H), 4.70 (1H, m, C(4)H), 5.94–
6.03 (2H, m, C(10)H and C(20)H), 7.00 (1H, d, J¼1.8 Hz,
C(3)H); dC (100 MHz, CDCl3, Me4Si) 24.6, 24.19, 24.18,
23.9, 16.0 (CH3), 18.4, 18.7 (C), 26.15, 26.18 (CH3), 77.4,
83.0, 118.3, 133.5 (CH), 139.3 (C), 152.7 (CH), 202.6 (C);
m/z (CI) 383 ([MþH]þ, 100%), 325 ([M2C(CH3)3]þ, 49),
268 ([M22£C(CH3)3]þ, 47); Found: [MþH]þ, 383.24393.
C20H39O3Si2 requires [MþH]þ, 383.24377.
7. Moon, H. R.; Choi, W. J.; Kim, H. O.; Jeong, L. S.
Tetrahedron: Asymmetry 2002, 13, 1189.
8. The trans-stannane was prepared from trans-1-bromo-1-
propene and t-BuLi at 278 8C, quenching the vinyl anion
with tributyltin chloride.
9. Treatment of cis-1-bromo-1-propene and t-BuLi resulted in
the cis-stannane along with large amounts of the inseparable
stannane; tributyl(propynyl)stannane, see Seyferth, D. Prog.
Inorg. Chem. 1962, 3, 129. Therefore, formation of the cis-
stannane was undertaken by performing a hydrozirconation
followed by quenching with water, see Lipshutz, B. H.; Kell,
R.; Barton, J. C. Tetrahedron Lett. 1992, 33, 5861.
10. CCDC reference number 221379. For methodology see Flack,
H. D. Acta Crystallogr. Sect. A Fundam. Crystallogr. 1983,
39, 876. Sheldrick, G.M. Shelx97, Crystal structure determi-
nation program; Gottingen, Germany, 1997.
4.1.17. (4S,5R)-4,5-Dihydroxy-2-prop-(Z)-enyl-cyclo-
pent-2-enone (14).
A solution of bis-silylether 23
(200 mg, 0.52 mmol) in acetic acid–water–tetrahydrfuran
(2 ml, 3:1:1) was heated at 60 8C for 4 h. Ethyl acetate
(10 ml) was added to the cooled reaction mixture and the
solution washed with sat. aq. NaHCO3 (5 ml) and brine
(5 ml). The aqueous layers were combined and washed with
ethyl acetate (3£10 ml) and the organic layers combined,
dried (MgSO4) and the solvent removed in vacuo. The
product was purified by flash column chromatography
11. Smith, A. B., III.; Yokoyama, Y.; Dunlap, N. K. Tetrahedron
Lett. 1987, 28, 3663.
12. Tanaka, H.; Yamada, H.; Matsuda, A.; Takahashi, T. Synlett
1997, 381.