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DOI: 10.1055/s-2005-864803
Formal Synthesis of Linderone and Lucidone Based on One-Pot Cyclizations of 1,3-Bis-Silyl Enol Ethers with Oxalyl Chloride
Publication History
Publication Date:
23 March 2005 (online)
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Abstract
A formal synthesis of the acylcyclopentenediones linderone and lucidone is reported which is based on the cyclization of 2,4-bis(trimethylsilyloxy)-1,3,5-hexatrienes with oxalyl chloride and on the synthesis and functionalization of γ-(2-silyloxypropenylidene)butenolides.
Key words
acylcyclopentenediones - butenolides - cyclizations - natural products - silyl enol ethers
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References
Synthesis of 5a.
To a CH2Cl2 solution (10 mL) of oxalyl chloride (0.090 mL, 1.03 mmol) and 4a (0.332 g, 1.00 mmol) was added a CH2Cl2 solution (5 mL) of Me3SiOTf (0.09 mL, 0.50 mmol) at -78 °C. The temperature of the reaction mixture was allowed to rise to 20 °C over 12 h. After stirring for 2 h at 20 °C, brine (50 mL) was added. The aqueous layer was separated and extracted with CH2Cl2 (2 × 50 mL). The combined organic layers were washed with an aq solution of HCl (10%, 50 mL), dried over anhyd Na2SO4 and filtered. The solvent of the filtrate was removed in vacuo and the residue was purified by column chromatography (silica gel, hexane-EtOAc) to give 5a (0.155 g, 64%) as a yellow solid; mp 128-129 °C; R
f
= 0.27 (hexane-EtOAc = 1:1). IR (KBr): 3002 (br), 1800 (s), 1628 (s), 1612 (s), 1552 (s), 1398 (m), 1267 (s), 1213 (m), 1045 (s), 979 (m), 767 (w) cm-1. 1H NMR (300 MHz, CDCl3): δ = 7.74-7.67 (m, 3 H, ArH, =CH), 7.46-7.42 (m, 3 H, ArH), 7.12-7.03 (m, 2 H, =CH), 6.59 (s, 1 H, =CH). 13C NMR (75 MHz, CDCl3): δ = 188.3, 163.7, 159.3, 151.4 (C), 152.3 (CH), 134.4 (C), 130.5, 128.9 (2 C), 128.5 (2 C), 128.2, 107.7, 103.6 (CH). MS (EI, 70 eV): m/z (%) = 241.9 (1) [M+], 225.9 (2), 213.9 (3), 131.1 (1), 102.8 (1), 77.3 (1), 44.0 (7), 28.0 (100). Anal. Calcd for C14H10O4 (%): C, 69.41; H, 4.16. Found: C, 69.17; H, 4.49.