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The merger of electro-reduction and hydrogen bonding activation for a radical Smiles rearrangement.

ABSTRACT: The reductive activation of chemical bonds at less negative potentials provides a foundation for high functional group tolerance and selectivity, and it is one of the central topics in organic electrosynthesis. Along this line, we report the design of a dual-activation mode by merging electro-reduction with hydrogen bonding activation. As a proof of principle, the reduction potential of N-phenylpropiolamide was shifted positively by 218 mV. Enabled by this strategy, the radical Smiles rearrangement of N-arylpropiolamides without external radical precursors and prefunctionalization steps was accomplished. [DBU][HOAc], a readily accessible ionic liquid, was exploited for the first time both as a hydrogen bonding donor and as a supporting electrolyte.

SUBMITTER: Lan L

PROVIDER: S-EPMC11339951 | biostudies-literature | 2024 Aug

REPOSITORIES: biostudies-literature

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The merger of electro-reduction and hydrogen bonding activation for a radical Smiles rearrangement.

Lan Liyuan L Xu Kun K Zeng Chengchu C

Chemical science 20240719 33

The reductive activation of chemical bonds at less negative potentials provides a foundation for high functional group tolerance and selectivity, and it is one of the central topics in organic electrosynthesis. Along this line, we report the design of a dual-activation mode by merging electro-reduction with hydrogen bonding activation. As a proof of principle, the reduction potential of <i>N</i>-phenylpropiolamide was shifted positively by 218 mV. Enabled by this strategy, the radical Smiles rea ...[more]

PMID: 39183920

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