Synthesis of cyclic alkenyl dimethylsiloxanes from alkynyl benzyldimethylsilanes and application in polyene synthesis

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 achi...

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Opis bibliograficzny
Główni autorzy: Gudmundsson, HG, Kuper, CJ, Cornut, D, Urbitsch, F, Elbert, BL, Anderson, EA
Format: Journal article
Język:English
Wydane: American Chemical Society 2019
Opis
Streszczenie: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.