Radical-mediated C-C cleavage of unstrained cycloketones and DFT study for unusual regioselectivity
Mingyang Wang1,3, Man Li2,3, Shan Yang1,3, Xiao-Song Xue 2*（薛小松副）, Xinxin Wu1 & Chen Zhu 1 *（朱晨）
1 Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 RenAi Road, 215123 Suzhou, Jiangsu, China.
2 State Key Laboratory of Elemento-organic Chemistry, College of Chemistry, Nankai University, 300071 Tianjin, China.
3 These authors contributed equally: Mingyang Wang, Man Li, Shan Yang.
NATURE COMMUNICATIONS， (2020) 11:672
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.