Wacker oxidation methodology for the synthesis of the benzo-fused acetal core of marticin

Methodology for the synthesis of the benzo-fused acetal core of marticin is described in this paper. Condensation of readily available 1-(2-allyl-3,6-dimethoxyphenyl)ethanone with diethyl oxalate under Claisen condensation conditions furnished (Z)-ethyl 4-(2-allyl-3,6-dimethoxyphenyl)-2-hydroxy-4-oxobut-2-enoate. Treatment of this with LiAlH4 resulted in the formation of the diol, 1-(2-allyl-3,6-dimethoxyphenyl)-3,4-dihydroxybutan-1-one. Conversion of primary alcohol of the diol into the TBDMS ether followed by further reaction with LiAlH4 and exposure to Wacker oxidation conditions resulted in the formation of (3,6-dimethoxy-9-methyl-10,13-dioxatricyclo[7.3.1.0(2.7)]trideca-2,4,6-trien-11-yl)methanol, the core of marticin. (C) 2012 Elsevier Ltd. All rights reserved.