An efficient synthetic strategy for the regio- and stereospecific silylvinylation of internal alkynes via a tethered vinylsilane will be discussed.  The transformation is catalyzed by well-defined ruthenium hydrides and provides dienes that possess a vinylsilane, and a tetrasubstituted alkene.  This reaction occurs by a trans-addition across the alkyne pi-system.  Both intra- and intermolecular reactions will be presented.  Intramolecular reactions require the addition of additives, such as methylvinylketone (MVK), for high conversion and yield. The use of ethylene gas as an additive alters selectivity the nuances of which will be discussed.  The scope of the intermolecular variant of this reaction with regard to coupling partners will be highlighted.  The products of these reactions have been further functionalized and efforts to create new chemical entities from them will be addressed.

Ruthenium hydride catalyzed silylvinylation of alkynes

248th National Meeting (2014)

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