Sonye John P, Koide Kazunori
Department of Chemistry, University of Pittsburgh, Pennsylvania 15260, USA.
Org Lett. 2006 Jan 19;8(2):199-202. doi: 10.1021/ol052376t.
[reaction: see text] Since the discovery of organic base-catalyzed isomerization of gamma-hydroxy-alpha,beta-acetylenic esters to gamma-oxo-alpha,beta-trans-alkenyl esters in 1949, the mechanism has not been elucidated. This study shows that the mechanism involves cumulene formation, protonation with the conjugate acid of the amine, and protonation of the resulting allenol with water.
[反应：见正文] 自1949年发现有机碱催化γ-羟基-α,β-炔酸酯异构化为γ-氧代-α,β-反式烯基酯以来，其机理尚未阐明。本研究表明，该机理涉及累积烯烃的形成、胺的共轭酸进行质子化以及所得联烯醇与水的质子化。
