An Alternative Synthetic Route to the C(11)-C(17)-Fragment of Mycinolide IV

Katsuhiko Tomooka; Kazutsugu Matsumoto; Keisuke Suzuki; Gen-ichi Tsuchihashi

doi:10.1055/s-1992-21289

Synlett 1992; 1992(2): 129-130
DOI: 10.1055/s-1992-21289

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An Alternative Synthetic Route to the C(11)-C(17)-Fragment of Mycinolide IV

Katsuhiko Tomooka^* , Kazutsugu Matsumoto, Keisuke Suzuki, Gen-ichi Tsuchihashi

^*Department of Chemistry, Keio University, 3-14-1 Hiyoshi, Yokohama 223, Japan

Abstract

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An efficient chiral synthesis of (4R,5R)-4-(4-methoxybenzyloxymethyl)-2-heptene-1,5-diol (4), which corresponds to the C(11)-C(17) segment of mycinolide IV (1), is described. One of the key steps is the asymmetric pinacol-type rearrangement of a chiral glycerol-derived mesylate 12, promoted by a modified organoaluminum reagent (1:1 mixture of trimethylaluminium and diethyl ether). Stereospecific 1,2-shift of a three-carbon alkenyl group gave (R)-4-(4-methoxybenzyloxymethyl)-5-trimethylsilyl-7-(2-trimethylsilylethoxymethoxy)-5-hepten-3-one (13) 80 % yield. Reduction of 13 with lithium triethylborohydride followed by removal of silyl groups gave 4 in enantio- and diastereomerically pure form.

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