韩国科学技术院Sukbok Chang团队报道了铑催化酰基硝基转移反应的机理快照。相关研究成果发表在2023年7月20日出版的《科学》。

酰基nitrene铑络合物广泛参与催化C–H酰胺化反应，但尚未分离和结构表征。

为了克服这一挑战，研究人员设计了一种具有双齿二恶唑酮配体的发色八面体铑配合物，其中光诱导的金属到配体的电荷转移引发催化的C–H酰胺化。Rh-二恶唑酮配合物的X射线光结晶学分析使靶向Rh-acylnitrenoid的结构得以阐明，并提供了单线态类氮宾物种主要负责酰氨基转移反应的确凿证据。研究人员还监测了亲核试剂与原位生成的Rh-acylnitrenoid的晶体内反应，提供了一个可在晶体上追踪的反应系统来捕捉硝Renoid转移的机制快照。

附：英文原文

Title: Mechanistic snapshots of rhodium-catalyzed acylnitrene transfer reactions

Author: Hoimin Jung, Jeonguk Kweon, Jong-Min Suh, Mi Hee Lim, Dongwook Kim, Sukbok Chang

Issue&Volume: 2023-07-20

Abstract: Rhodium acylnitrene complexes are widely implicated in catalytic C–H amidation reactions but have eluded isolation and structural characterization. To overcome this challenge, we designed a chromophoric octahedral rhodium complex with a bidentate dioxazolone ligand, in which photoinduced metal-to-ligand charge transfer initiates catalytic C–H amidation. X-ray photocrystallographic analysis of the Rh-dioxazolone complex allowed structural elucidation of the targeted Rh-acylnitrenoid and provided firm evidence that the singlet nitrenoid species is primarily responsible for acylamino transfer reactions. We also monitored in crystallo reaction of a nucleophile with the in situ generated Rh-acylnitrenoid, providing a crystallographically traceable reaction system to capture mechanistic snapshots of nitrenoid transfer.

DOI: adh8753

Source: https://www.science.org/doi/10.1126/science.adh8753