Abstract
New methodology for complete control of stereoselectivity in the hydrosilylation of alk-1-ynes is described. Alk-1-ynes react with triethylsilane to produce both (E)- and (Z)-vinylsilane, depending upon the reaction conditions, with high selectivity (91–97%). A [{Rh(cod)Cl}2]-catalysed reaction using ethanol as a solvent gave rise to Z-selective conditions whilst E-selective conditions were achieved in [{Rh(cod)Cl}2]/PPh3 or [RhCl(PPh3)3]-catalysed reactions using acetonitrile as a solvent. A cationic rhodium(I) phosphine complex generated in situ was found to be the active species in E-selective conditions.
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