Asymmetric Vicinal and Remote Hydroamination of Olefins by Employing a Heck-Reaction-Derived Hydride Source DOI

Ruijie Mi,

Xuejing Yao, Youzhi Xu

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: May 6, 2025

Metal hydrides are reactive intermediates in numerous catalytic processes. In many processes, metal formed, but their potential reactivity is often wasted by reaction with a base or an oxidant to permit catalyst turnover. this report, the hydroamination of unactivated olefins described coupling Heck between aryl boronic acid, olefin, and nitrene precursor dioxazolone. Initiated olefin arylboroic rhodium hydride intermediate generated retained for second equivalent olefin. Depending on chain length alkyl group α- β-amino amides were obtained excellent regio- enantioselectivity via direct remote (migratory) hydroamination, respectively. The system features broad scope, mild conditions, enantioselectivity, it also represents rare example asymmetric using chiral rhodium(III) cyclopentadienyl catalyst. Mechanistic studies delineated turnover-limiting enantio-determining steps system.

Language: Английский

Asymmetric Vicinal and Remote Hydroamination of Olefins by Employing a Heck-Reaction-Derived Hydride Source DOI

Ruijie Mi,

Xuejing Yao, Youzhi Xu

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: May 6, 2025

Metal hydrides are reactive intermediates in numerous catalytic processes. In many processes, metal formed, but their potential reactivity is often wasted by reaction with a base or an oxidant to permit catalyst turnover. this report, the hydroamination of unactivated olefins described coupling Heck between aryl boronic acid, olefin, and nitrene precursor dioxazolone. Initiated olefin arylboroic rhodium hydride intermediate generated retained for second equivalent olefin. Depending on chain length alkyl group α- β-amino amides were obtained excellent regio- enantioselectivity via direct remote (migratory) hydroamination, respectively. The system features broad scope, mild conditions, enantioselectivity, it also represents rare example asymmetric using chiral rhodium(III) cyclopentadienyl catalyst. Mechanistic studies delineated turnover-limiting enantio-determining steps system.

Language: Английский

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