The Highly Regioselective Carbonylation of Vinylsilanes

Article abstract of DOI:10.1021/jo00041a025

The hydroesterification of vinylsilanes, catalyzed by transition-metal complexes, afforded both β-silyl esters 2 and α-silyl esters 3 in high yield.The Pd(II) complex-catalyzed reaction showed high β-regioselectivity, whereas the Co2(CO)8-catalyzed reaction showed high α-regioselectivity.Vinylsilanes which bore trialkyl-, diphenylmethyl-, dimethylethoxy-, trimethoxy-, diphenylfluoro-, and difluorophenylsilyl groups were regioselectively, and in some cases regiospecifically, hydroesterified.Pd(II) complexes were also shown to be effective catalysts of the hydrocarboxylation of vinylsilanes.Hydrocarboxylation was β-regiospecific and gave excellent yields of β-silyl carboxylic acids.Reasonable mechanisms for the reactions are described.