Selective reduction of secondary amides to imines catalysed by Schwartz's reagent
Donnelly, Liam J. and Berthet, Jean‐Claude and Cantat, Thibault (2022) Selective reduction of secondary amides to imines catalysed by Schwartz's reagent. Angewandte Chemie International Edition, 61 (33). e202206170. ISSN 1433-7851 (https://doi.org/10.1002/anie.202206170)
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Abstract
The partial reduction of amides is a challenging transformation that must overcome the intrinsic stability of the amide bond and exhibit high chemoselective control to avoid overreduction to amine products. 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 (Cp2Zr(H)Cl) and utilises (EtO)3SiH as a mild stoichiometric reductant to enable catalyst turnover. The reaction generally proceeds with high yields (19 examples, 51 to 95 % yield) and tolerates a variety of functional groups (alkene, ester, nitro, etc.). Stoichiometric mechanistic investigations suggest the regeneration of the active [Zr]−H catalyst is achieved through the metathesis of Si−H and Zr−OR σ-bonds.
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Item type: Article ID code: 83262 Dates: DateEvent15 August 2022Published14 June 2022Published Online18 May 2022AcceptedSubjects: Science > Chemistry Department: Faculty of Science > Pure and Applied Chemistry Depositing user: Pure Administrator Date deposited: 17 Nov 2022 12:37 Last modified: 07 Aug 2024 06:48 Related URLs: URI: https://strathprints.strath.ac.uk/id/eprint/83262