Acrylate metathesis via the second-generation Grubbs catalyst: unexpected pathways enabled by a PCy3-generated enolate.
作者： Gwendolyn A. Bailey , Deryn E. Fogg
DOI: 10.1021/JACS.5B04524
关键词: Ring-opening metathesis polymerisation 、 Carbanion 、 Acrylate 、 Organic chemistry 、 Grubbs' catalyst 、 Chemistry 、 Michael reaction 、 Catalysis 、 Metathesis 、 Olefin fiber
摘要: The diverse applications of acrylate metathesis range from synthesis high-value α,β-unsaturated esters to depolymerization unsaturated polymers. Examined here are unexpected side reactions promoted by the important Grubbs catalyst GII. Evidence is presented for attack PCy3 on olefin generate a reactive carbanion, which participates in multiple pathways, including further Michael addition, proton abstraction, and deactivation. Related chemistry may be anticipated whenever labile metal–phosphine complexes used catalyze substrates bearing an electron-deficient olefin.
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