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Radical-mediated C-C cleavage of unstrained cycloketones and DFT study for unusual regioselectivity.

ABSTRACT: The C-C ?-bond activation of unstrained cycloketones represents an ingenious and advanced technique in synthetic chemistry, but it remains a challenging area which has been largely underexplored. Herein we report an efficient strategy for the direct C-C cleavage of cyclohexanones and cyclopentanones. The cyclic C-C ?-bond is readily cleaved under mild conditions with the aid of an in situ formed side-chain aryl radical. Density functional theory calculations are carried out to shed light on the unusual regioselectivity of C-C bond cleavage. The reaction affords a variety of structurally diverse 3-coumaranones and indanones that widely exist in natural products and bioactive molecules, illustrating the synthetic value of this method.

SUBMITTER: Wang M

PROVIDER: S-EPMC6997357 | biostudies-literature | 2020 Feb

REPOSITORIES: biostudies-literature

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Radical-mediated C-C cleavage of unstrained cycloketones and DFT study for unusual regioselectivity.

Wang Mingyang M Li Man M Yang Shan S Xue Xiao-Song XS Wu Xinxin X Zhu Chen C

Nature communications 20200203 1

The C-C σ-bond activation of unstrained cycloketones represents an ingenious and advanced technique in synthetic chemistry, but it remains a challenging area which has been largely underexplored. Herein we report an efficient strategy for the direct C-C cleavage of cyclohexanones and cyclopentanones. The cyclic C-C σ-bond is readily cleaved under mild conditions with the aid of an in situ formed side-chain aryl radical. Density functional theory calculations are carried out to shed light on the ...[more]

PMID: 32015335

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