Journal of Organic Chemistry 2005-07-22

Total syntheses of naturally occurring diacetylenic spiroacetal enol ethers.

Naoki Miyakoshi, Daisuke Aburano, Chisato Mukai

Index: J. Org. Chem. 70(15) , 6045-52, (2005)

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Abstract

A highly stereoselective method for constructing a (2E)-methoxymethylidene-1,6-dioxaspiro[4.5]decane skeleton has been developed on the basis of the palladium(II)-catalyzed ring-closing reaction of the 3,4-dioxygenated-9-hydroxy-1-nonyn-5-one derivatives as a crucial step. The newly developed procedures could be successfully applied to the first total synthesis of five diacetylenic spiroacetal enol ether natural products starting from commercially available (R,R)- or (S,S)-diethyl tartrate.