From α,β-Unsaturated Amide to Enamide: Intramolecular Alkene Translocation via Iridium-Catalyzed Transfer Hydrogenation

IF 13.6 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2026-10-16 Epub Date: 2026-09-29 DOI:10.1021/acscatal.6c05353

Yin Xu, Zhi-Zhou Pan, Guangbin Dong

引用次数: 0

Abstract

Site-selective alkene translocation between two separate segments of a molecule has been a rare and mechanistically intriguing transformation. Herein we report the direct conversion of electrophilic α,β-unsaturated amides to nucleophilic enamides via an Ir-catalyzed alkene translocation across an amide linkage. The reaction is redox-neutral, atom-economical and strong base-free, thus showing broad functional group tolerance. Mechanistic studies reveal that the reaction proceeds through an irreversible intramolecular hydrogen transfer pathway. Preliminary success on enantioselective intramolecular transfer hydrogenation of α,β-unsaturated amides has also been achieved.

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从α，β-不饱和酰胺到烯酰胺：通过铱催化转移氢化的分子内烯烃易位

位点选择性烯烃易位在一个分子的两个独立片段之间是一种罕见的和机械上有趣的转化。本文报道了亲电性α，β-不饱和酰胺通过ir催化的烯在酰胺链上易位直接转化为亲核性烯酰胺。该反应为氧化还原中性、原子经济、无强碱反应，具有广泛的官能团耐受性。机理研究表明该反应是通过不可逆的分子内氢转移途径进行的。α，β-不饱和酰胺的分子内转移加氢也取得了初步成功。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.