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Updated: Jul 22, 2025

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Mechanistic snapshots of rhodium-catalyzed acylnitrene transfer reactions
Hoimin Jung1,2, Jeonguk Kweon1,2, Jong-Min Suh1
1Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, South Korea.
Abstract:
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.
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