Abstract
The mild catalytic partial reduction of amides to imines has proven to be a challenging synthetic transformation, with many transition metals directly reducing these substrates to amines. Herein, we report a mild, catalytic method for the semireduction of both secondary and tertiary amides via zirconocene hydride catalysis. Utilizing just 5 mol % of Cp2ZrCl2, the reductive deoxygenation of secondary amides is demonstrated to furnish a diverse array of imines in up to 94% yield with excel-lent chemoselectivity and without the need for glovebox handling. Moreover, a novel reductive transamination of tertiary amides is also achievable when the catalytic protocol is carried out in the presence of a primary amine at room temperature, providing access to an expanded assortment of imines. Through slight procedural modifications, the single-flask conversion of amides to imines, aldehydes, amines or enamines is feasible, including multicomponent syntheses.
Supplementary materials
Title
Supporting Information
Description
General procedural information, mechanistic studies, characterization data and spectra
Actions