Regio‐ and Stereospecific Cleavage of Stannyloxiranes with Lithium Diphenylphosphide

Unsubstituted or C-substituted stannyloxiranes reactedstereospecifically with lithium diphenylphosphide to give either β-hydroxyphosphane oxides resulting from α-opening or β-phosphanyl ketones by β-opening. Furthermore, the reactivities of distannyloxiranes depend on their configurations. The cis isomers afforded the corresponding α,β-diphosphanyl alcohols, while the trans isomers were shown to be unreactive. On the other hand, the regiochemistry of the ring-opening from β-silyl-stannyloxiranes is controlled by the tin group and, depending on the nature of the silyl group, led either to stereodefined β-silylated vinylphosphane oxides or to β-stannyl silyl enol ethers. Finally, the gem-silyl-stannyloxiranes underwent β-opening to give mixtures of β-phosphanyl acylsilanes and silyl enol ethers. All compounds are interesting synthons of great versatility in organic chemistry.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)