Unlocking the Nucleophilicity of Strong Alkyl C-H Bonds via Cu/Cr Catalysis

Pan Peng; Yifan Zhong; Cong Zhou; Yongsheng Tao; Dandan Li; Qingquan Lu

doi:10.1021/acscentsci.2c01389

Unlocking the Nucleophilicity of Strong Alkyl C-H Bonds via Cu/Cr Catalysis

ACS Cent Sci. 2023 Mar 27;9(4):756-762. doi: 10.1021/acscentsci.2c01389. eCollection 2023 Apr 26.

Authors

Pan Peng¹, Yifan Zhong¹, Cong Zhou¹, Yongsheng Tao¹, Dandan Li², Qingquan Lu¹

Affiliations

¹ The Institute for Advanced Studies (IAS), Wuhan University, Wuhan 430072, P. R. China.
² Key Laboratory of Micro-Nano Materials for Energy Storage and Conversion of Henan Province, Institute of Surface Micro and Nano Materials, College of Chemical and Materials Engineering, Xuchang University, Henan 461000, P. R. China.

Abstract

Direct functionalization of inert C-H bonds is one of the most attractive yet challenging strategies for constructing molecules in organic chemistry. Herein, we disclose an unprecedented and Earth abundant Cu/Cr catalytic system in which unreactive alkyl C-H bonds are transformed into nucleophilic alkyl-Cr(III) species at room temperature, enabling carbonyl addition reactions with strong alkyl C-H bonds. Various aryl alkyl alcohols are furnished under mild reaction conditions even on a gram scale. Moreover, this new radical-to-polar crossover approach is further applied to the 1,1-difunctionalization of aldehydes with alkanes and different nucleophiles. Mechanistic investigations reveal that the aldehyde not only acts as a reactant but also serves as a photosensitizer to recycle the Cu and Cr catalysts.