Studies of the Enantiocontrolled Synthesis of the C(10)–C(25) Subunit of Amphidinolide C

Abstract

A stereocontrolled synthesis of 28, the C(10)-C(25) component of amphidinolide C (1), has been efficiently achieved. Reaction of the dithiane component 21 with nonracemic bis(epoxide) 19 directly affords functionalized 2,5-trans-disubstituted tetrahydrofuran 22. Propargylation is highly diastereoselective for the formation of the desired C(12)-C(13) anti stereochemistry, and the resulting terminal alkyne 25 is utilized for a regioselective syn-silylstannylation. A general strategy is illustrated for sequential replacement of stannyl and silyl substituents of the trisubstituted alkene to yield (E)-alkenyl iodide 28.