Mechanistic snapshots of rhodium-catalyzed acylnitrene transfer reactions

• 成果类型: Article
• 署名作者: Jung, Hoimin; Kweon, Jeonguk; Suh, Jong-Min; Lim, Mi Hee; Kim, Dongwook; Chang, Sukbok
• 署名单位: Korea Advanced Institute of Science & Technology (KAIST); Institute for Basic Science - Korea (IBS)
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-10658
• DOI: 10.1126/science.adh8753
• 发表日期: 2023-08-04
• 页码: 525-532
• 关键词: effective core potentials; solvation free-energies; c-h amidation; molecular calculations; basis-sets; quantum-chemistry; transition-metal; imido complexes; amido transfer; amination

摘要

Rhodium (Rh) 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 Rh 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, which provided a crystallographically traceable reaction system to capture mechanistic snapshots of nitrenoid transfer.