STEREOCHEMISTRY OF ASYMMETRIC SILICON .16. TRANSITION METAL CATALYZED SUBSTITUTION REACTIONS OF OPTICALLY ACTIVE ORGANOSILICON HYDRIDES

The stereochemistry of a general class of group VIII metal-catalyzed reactions of the Si-H bond has been studied. The reactions of a variety of reagents containing OH and NH functions with optically active α-NpPhMeSi*H were found to proceed with inversion of configuration at the silicon center in contrast to the noncatalytic cleavages of Si*-H with strong nucleophiles which proceed with retention. The effects of structure on reactivity as well as solvent and catalyst effects were examined. It was shown that substitution reactions were catalyzed by pure palladium metal and may best be regarded as examples of heterogeneous catalysis. A mechanistic interpretation involves initial coordination of α-NpPhMeSi*H with the reactive metal center followed by backside displacement of silicon from the metal surface with inversion. © 1969, American Chemical Society. All rights reserved.