Affiliation:
1. Key Laboratory of Functional Molecular Engineering of Guangdong Province School of Chemistry and Chemical Engineering South China University of Technology Guangzhou 510640 China
2. School of Chemistry and Chemical Engineering Zhejiang Sci‐Tech University Hangzhou 310018 China
3. State Key Laboratory of Elemento‐Organic Chemistry Nankai University Tianjin 300071 China
Abstract
Abstract(Difluoromethylated cyclopropane represents an important motif, which is widely found in bioactive and functional molecules. Despite significant progress in modern chemistry, the atom‐economic and enantioselective synthesis of difluoromethylated cyclopropanes is still challenging. Herein, an Rh2(II)‐catalyzed asymmetric enyne cycloisomerization is described to construct chiral difluoromethylated cyclopropane derivatives with up to 99% yield and 99% ee in low catalyst loading (0.2 mol%), which can be easily transformed into highly functionalized difluoromethylated cyclopropanes with vicinal all‐carbon quaternary stereocenters by ozonolysis. Mechanistic studies and the crystal structures of alkyne‐dirhodium complexes reveal that the cooperative weak hydrogen bondings between the substrates and the dirhodium catalyst may play key roles in this reaction.)
Funder
Fundamental Research Funds for the Central Universities
China Postdoctoral Science Foundation
National Natural Science Foundation of China
Subject
General Physics and Astronomy,General Engineering,Biochemistry, Genetics and Molecular Biology (miscellaneous),General Materials Science,General Chemical Engineering,Medicine (miscellaneous)