Total syntheses of naturally occurring diacetylenic spiroacetal enol ethers

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.