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C−C Bond‐Forming Strategy by Manganese‐Catalyzed Oxidative Ring‐Opening Cyanation and Ethynylation of Cyclobutanol Derivatives
Author(s) -
Ren Rongguo,
Wu Zhen,
Xu Yan,
Zhu Chen
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201510973
Subject(s) - cyanation , ring (chemistry) , chemistry , bond cleavage , triple bond , manganese , catalysis , cleavage (geology) , combinatorial chemistry , medicinal chemistry , stereochemistry , polymer chemistry , organic chemistry , double bond , materials science , fracture (geology) , composite material
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.