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Journal Articles Angewandte Chemie Year : 2022

Selective Reduction of Secondary Amides to Imines Catalysed by Schwartz’s Reagent

Abstract

The partial reduction of amides is a challenging transformation that must overcome the intrinsic stability of the amide bond, a ubiquitous motif in organic chemistry, and exhibit high chemoselective control. To address this challenge, we describe a zirconium-catalysed synthesis of imines by the reductive deoxygenation of secondary amides. This reaction exploits the excellent chemoselectivity of Schwartz’s reagent (Cp$_2$Zr(H)Cl) to avoid overreduction to amine products and utilises (EtO)$_3$SiH as a mild stoichiometric reductant to enable catalyst turnover. The reaction generally proceeds with high yields (13 examples, 70 to 95% yield) and tolerates a variety of functional groups (alkene, ether, nitro, etc.). Stoichiometric mechanistic investigations suggest the regeneration of the active [Zr]–H catalyst is achieved through the σ-bond metathesis of Si–H and Zr–OR.
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Dates and versions

cea-03571753 , version 1 (14-02-2022)

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Attribution - NonCommercial - NoDerivatives

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Liam J. Donnelly, Jean-Claude Berthet, Thibault Cantat. Selective Reduction of Secondary Amides to Imines Catalysed by Schwartz’s Reagent. Angewandte Chemie, 2022, 61 (33), pp.e202206170. ⟨10.1002/anie.202206170⟩. ⟨cea-03571753⟩
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