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

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journal contribution
posted on 15.11.2019, 08:13 by Haraldur G. Gudmundsson, Christian J. Kuper, Damien Cornut, Felix Urbitsch, Bryony L. Elbert, Edward A. Anderson
Cyclic dimethylalkenylsiloxanes, useful motifs for (Z)-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 (Z)-alkene-containing polyenes and application to a concise total synthesis of leukotriene B3.