区域选择性
化学
烯烃
激进的
芳基
炔烃
烷基
芳基
组合化学
自由基环化
有机化学
药物化学
催化作用
作者
Zhipeng Guan,Dongfeng Yang,Zhao Liu,Shuxiang Zhu,Xingxing Zhong,Huamin Wang,Xiangwei Li,Xiaotian Qi,Hong Yi,Aiwen Lei
出处
期刊:Chinese Journal of Catalysis
[China Science Publishing & Media Ltd.]
日期:2023-09-01
卷期号:52: 144-153
被引量:2
标识
DOI:10.1016/s1872-2067(23)64510-3
摘要
Achieving regioselectivity in radical cyclization reactions is of central importance, yet extremely challenging. Although Baldwin's rules provided guidance on the addition of radical species with alkenes/alkynes, the ortho-/ipso-selectivity of the cyclic reaction between radical species (especially alkyl and alkenyl radical) and aryl groups is still ambiguous. Herein, we develop an electrochemically enabled regioselective ortho-(4 + 2)/ipso-(3 + 2) cyclization of alkyl/alkenyl radicals with aryl groups, which provides a series of tetrahydronaphthalene and spirocarbocycle derivatives, exhibiting a broad substrate scope and functional group tolerance. Alkyl/alkenyl radicals are generated by Cp2Fe-mediated electrochemical oxidative radical addition of benzylic malonates with alkenes and alkynes. The method avoids the use of chemical oxidant/base/noble metal, the pre-functionalization of substrates, and the over-oxidation of compounds. Theoretical studies reveal that the dominant factor promoting the alkene-preferred ortho-addition is the favorable interaction energy; the alkyne-preferred ipso-addition regioselectivity is controlled by the distortion energy. Notably, this strategy is regarded as an important supplement to Baldwin's rules for radical cyclization.
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