Acrylate Metathesis via the Second-Generation Grubbs Catalyst: Unexpected Pathways Enabled by a PCy3-Generated Enolate

作者:Bailey Gwendolyn A; Fogg Deryn E*
来源:Journal of the American Chemical Society, 2015, 137(23): 7318-7321.
DOI:10.1021/jacs.5b04524

摘要

The diverse applications of acrylate metathesis range from synthesis of high-value alpha,beta-unsaturated esters to depolymerization of unsaturated polymers. Examined here are unexpected side reactions promoted by the important Grubbs catalyst GII. Evidence is presented for attack of PCy3 on the acrylate olefin to generate a reactive carbanion, which participates in Multiple pathways, including further Michael addition, proton abstraction, and catalyst deactivation. Related chemistry may be anticipated whenever labile metal-phosphine complexes are used to catalyze reactions of substrates bearing an electron-deficient olefin.

  • 出版日期2015-6-17