Are Copper(I) Carbenes Capable Intermediates for Cyclopropanations? The Case for Ylide Intermediates

作者:Aldajaei Jamal T; Keeffe James R; Swift Christopher A; Gronert Scott*
来源:Chemistry - A European Journal, 2015, 21(36): 12702-12708.
DOI:10.1002/chem.201501550

摘要

A novel approach is used to synthesize a stable, ligated copper(I) carbene in the gas phase that is capable of typical metal carbenoid chemistry. However, it is shown that copper(I) carbenes generally undergo rapid unimolecular rearrangements including insertions into copper-ligand bonds and Wolff rearrangements. The results indicate that most copper(I) carbenes are inherently unstable and would not be viable intermediates in condensed-phase applications; an alternative intermediate that is less prone to rearrangements is required. Computational data suggest that ylides formed by the complexation of the carbene with solvent or other weak nucleophiles are viable intermediates in the reactions of copper(I) carbenes.

  • 出版日期2015-9-1