Mechanism and selectivity on IrIII/RhIII-catalyzed coupling of terminal alkenes and dioxazolones: A DFT study

•The mechanism and Selectivity on amidation of terminal alkenes with the nitrene precursors was explored with the aid of DFT calculations. Additionally, influence of the catalyst Ir(III) vs Rh(III) on the selectivity of above reactions was also elucidated. The Cp*IrIII-catalyzed coupling of terminal...

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Bibliographic Details
Published inMolecular catalysis Vol. 510; p. 111679
Main Authors Bi, Siwei, Chu, Yichun, Meng, Ran, Wu, Xiaohan, Jiang, Yuan-Ye, Liu, Yuxia, Ling, Baoping
Format Journal Article
LanguageEnglish
Published Elsevier B.V 01.06.2021
Subjects
Amidation
DFT calculations
Dioxazolone
Ir(III)/Rh(III)
Selectivity
Dioxazolone
Ir(III)/Rh(III)
Selectivity
Amidation
DFT calculations
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Summary:•The mechanism and Selectivity on amidation of terminal alkenes with the nitrene precursors was explored with the aid of DFT calculations. Additionally, influence of the catalyst Ir(III) vs Rh(III) on the selectivity of above reactions was also elucidated. The Cp*IrIII-catalyzed coupling of terminal alkenes with dioxazolones to achieve CH amidation was studied theoretically with the aid of the density functional calculations. Employing the Ir=nitrenoid intermediate species involved in the reaction mechanism, the IrNR bonding nature was analyzed based on LUMO/HOMO interactions. Especially, the branch-selectivity with Cp*Ir(III) as the catalyst, the influence of Ir(III) vs Rh(III) on branch/linear selectivity, and the impossibility of aziridination were elucidated. This work provided further understanding and beneficial information for designing novel related selective reactions. [Display omitted]
ISSN:2468-8231
2468-8231
DOI:10.1016/j.mcat.2021.111679