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

Mingyang Wang, Man Li, Shan Yang, Xiao-Song Xue, Xinxin Wu, Chen Zhu

Nature communications 2020 Feb 03

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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 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.

Citation

Mingyang Wang, Man Li, Shan Yang, Xiao-Song Xue, Xinxin Wu, Chen Zhu. Radical-mediated C-C cleavage of unstrained cycloketones and DFT study for unusual regioselectivity. Nature communications. 2020 Feb 03;11(1):672