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Reduction of secondary amides to imines catalysed by Schwartz’s reagent

Liam J. Donnelly 1 Jean-Claude Berthet 1 Thibault Cantat 1 
1 LCMCE - Laboratoire de Chimie Moléculaire et de Catalyse pour l'Energie (ex LCCEF)
NIMBE UMR 3685 - Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M)
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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https://hal-cea.archives-ouvertes.fr/cea-03571753
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Submitted on : Monday, February 14, 2022 - 8:01:10 AM
Last modification on : Wednesday, February 16, 2022 - 3:42:04 AM
Long-term archiving on: : Sunday, May 15, 2022 - 6:15:46 PM

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Liam J. Donnelly, Jean-Claude Berthet, Thibault Cantat. Reduction of secondary amides to imines catalysed by Schwartz’s reagent. 2022. ⟨cea-03571753⟩

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