Rongguo Ren1,Zhen Wu1,Yan Xu1, Chen Zhu1 2(朱晨)
1Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu, China
2Key Laboratory of Synthesis Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Science, Shanghai, China
Angew.Chem. Int. Ed. , 2016, 55,2866 –2869
A novel C−C bond-forming strategy employing manganese-catalyzed ring-opening of cyclobutanol substrates, followed by cyanation or ethynylation, is described. A cyano C1 unit and ethynyl C2 unit are regiospecifically introduced to the γ-position of ketones at room temperature, providing a mild yet powerful method for production of elusive aliphatic nitriles and alkynes. All transformations described are based on a common sequence: 1) oxidative ring-opening of cyclobutanol substrates by C−C bond cleavage; 2) radical addition to triple bonds bearing an arylsulfonyl group; and 3) radical-mediated C−S bond cleavage.
链接://onlinelibrary.wiley.com/doi/10.1002/anie.201510973/abstract