Alkenylation and arylation of secondary alcohols enabled by productive merger of β-carbon and β-hydrogen elimination via an isodesmic reaction

Abstract

Transition-metal-catalyzed isodesmic reactions between primary and secondary alcohols to obtain value-added alcohols have recently attracted much attention. However, the counterpart reactions between tertiary and secondary alcohols are largely underdeveloped. Herein, we disclose a Rh-catalyzed isodesmic transformation of secondary alcohols and tertiary alcohols via β-carbon elimination and β-hydrogen elimination. The tertiary alcohols undergo C–C bond cleavage via β-alkenyl/aryl elimination, and then the resultant Rh-carbon species would be inserted into the ketones produced either by the dehydrogenation of secondary alcohols or by the 1,3-hydride isomerization of secondary allylic alcohols. These strategies of α-alkenylation/arylation of secondary alcohols offer a step-economical process for the preparation of a wide range of value-added tertiary alcohols.