Stereoselective alcohol silylation by dehydrogenative Si-O coupling: scope, limitations, and mechanism of the cu-h-catalyzed non-enzymatic kinetic resolution with silicon-stereogenic silanes.

Ligand-stabilized copper(I)-hydride catalyzes the dehydrogenative Si-O coupling of alcohols and silanes-a process that was found to proceed without racemization at the silicon atom if asymmetrically substituted. The present investigation starts from this pivotal observation since silicon-stereogenic silanes are thereby suitable for the reagent-controlled kinetic resolution of racemic alcohols, in which asymmetry at the silicon atom enables discrimination of enantiomeric alcohols. In this full account, we summarize our efforts to systematically examine this unusual strategy of diastereoselective alcohol silylation.

Kinetic resolution of donor-functionalised tertiary alcohols by Cu-H-catalysed stereoselective silylation using a strained silicon-stereogenic silane.

A series of propargylic tertiary alcohols decorated with an sp2-hybridised nitrogen donor were kinetically resolved by reagent-controlled dehydrogenative Si-O coupling with a strained, highly reactive silicon-stereogenic cyclic silane.