Tandem O–H Insertion/[1,3]-Alkyl Shift of Rhodium Azavinyl Carbenoids with Benzylic Alcohols: A Route To Convert C–OH Bonds into C–C Bonds

Alcohols are among the most abundant and commonly used organic feedstock in industrial processes and academic research. The first tandem O–H insertion/[1,3]-alkyl shift reaction reported is between benzylic alcohols and rhodium azavinyl carbenoids derived from <i>N</i>-sulfonyl-1,2,3-triazoles, which provides a strategically novel way of cleaving C–OH bonds and forming C–C bonds. The substrate scope is broad, capable of covering 1°-, 2°-, and 3°-benzylic alcohols. Moreover, it constitutes a new and powerful synthetic method for constructing α-aminoketones. Mechanistic studies suggest that a [1,3]-alkyl shift of oxonium ylides is responsible for cleavage of the C–OH bonds