2023-07-21 韓国基礎科学研究院(IBS)
Figure 1. Capturing the key intermediate of amination catalysis
Researchers at the Institute for Basic Science (IBS) has experimentally confirmed the structure and properties of a transition metal-nitrenoid intermediate produced during catalytic amination reactions.
＜関連情報＞
- https://www.ibs.re.kr/cop/bbs/BBSMSTR_000000000739/selectBoardArticle.do
- https://www.science.org/doi/10.1126/science.adh8753
ロジウム触媒によるアシルニトリンの転移反応の機構解明 Mechanistic snapshots of rhodium-catalyzed acylnitrene transfer reactions
Hoimin Jung,Jeonguk Kweon,Jong-Min Suh,Mi Hee Lim,Dongwook Kim, and Sukbok Chang
Science Published:20 Jul 2023
DOI:https://doi.org/10.1126/science.adh8753
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.
◆光誘起単結晶X線回折分析を用いてロジウム-ジオキサゾロン配位錯体を研究することで、ロジウム-アシルニトレノイド中間体形成の一瞬を捉えた。
◆この成果は、炭化水素を高付加価値製品に変換するための高反応性・高選択性触媒の開発に道を開くもので、さまざまな産業分野への応用が期待される。