Synthesis of Cyclic Alkenyl Dimethylsiloxanes from Alkynyl Benzyldimethylsilanes and Application in Polyene Synthesis

Abstract

Cyclic dimethylalkenylsiloxanes, useful motifs for (<i>Z</i>)-selective Hiyama cross-coupling, are accessed from alkynyl benzyldimethylsilanes featuring adjacent allylic or homoallylic oxygen substituents by semihydrogenation/debenzylation/cyclization. While formation of 5- and 6-membered rings can be achieved from the free alcohols using fluoride or silanolate, allylic acetate precursors to 5-membered rings display distinct modes of activation. The utility of these compounds is demonstrated through the preparation of a variety of (<i>Z</i>)-alkene-containing polyenes and application to a concise total synthesis of leukotriene B₃.