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Rh(iii)-catalyzed regioselective intermolecular N-methylene Csp3-H bond carbenoid insertion.

ABSTRACT: A Rh(iii)-catalyzed regioselective intermolecular carbenoid insertion into the N-methylene Csp3-H bond of acyclic aliphatic amides has been achieved, taking advantage of bidentate-chelation assistance. This methodology has been successfully applied to a broad range of linear and branched-chain N-alkylamides, thus providing a practical method for the assembly of diverse beta-amino esters. Mechanism studies and density functional theory (DFT) calculations revealed that a singlet Fischer type carbene insertion via an outer-sphere pathway was involved in this N-methylene Csp3-H bond carbenoid insertion.

SUBMITTER: Xie H

PROVIDER: S-EPMC5874982 | biostudies-literature | 2018 Jan

REPOSITORIES: biostudies-literature

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Rh(iii)-catalyzed regioselective intermolecular N-methylene Csp3-H bond carbenoid insertion.

Xie Haisheng H Ye Zongren Z Ke Zhuofeng Z Lan Jianyong J Jiang Huanfeng H Zeng Wei W

Chemical science 20171127 4

A Rh(iii)-catalyzed regioselective intermolecular carbenoid insertion into the N-methylene Csp3-H bond of acyclic aliphatic amides has been achieved, taking advantage of bidentate-chelation assistance. This methodology has been successfully applied to a broad range of linear and branched-chain N-alkylamides, thus providing a practical method for the assembly of diverse beta-amino esters. Mechanism studies and density functional theory (DFT) calculations revealed that a s ...[more]

PMID: 29629165

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