Lai Luhao, Li A-Ni, Zhou Jiawei, Guo Yarong, Lin Li, Chen Wei, Wang Rui
School of Life Sciences, School of Basic Medical Sciences, Institute of Biochemistry and Molecular Biology, and Key Laboratory of Preclinical Study for New Drugs of Gansu Province, Lanzhou University, Lanzhou 730000, China.
The first laboratory of Lanzhou Institute of Biological Products Co., Ltd, Lanzhou 730046, China.
Org Biomol Chem. 2017 Mar 8;15(10):2185-2190. doi: 10.1039/c7ob00131b.
This work concerns the Mg(OMe) promoted allylic isomerization of γ-hydroxy-α,β-alkenoic esters with TMEDA as an additive. The isomerization proceeded under mild conditions and afforded γ-keto esters in high yield (up to 96%) within 2 h. Both (Z)- and (E)-γ-hydroxy-α,β-alkenoic esters were tolerated under the reaction conditions. This transformation involves the in situ formation of a dienolate intermediate from the easily accessible γ-hydroxy-α,β-alkenoic ester. The in situ generated dienolate can react with benzaldehyde and undergo a practical, useful tandem allylic isomerization-Aldol reaction to afford more functionalized compounds.
本研究涉及以TMEDA作为添加剂，由Mg(OMe)促进的γ-羟基-α,β-烯酸酯的烯丙基异构化反应。该异构化反应在温和条件下进行，2小时内可高产率（高达96%）地得到γ-酮酯。在该反应条件下，(Z)-和(E)-γ-羟基-α,β-烯酸酯均能适用。此转化过程涉及由易于获得的γ-羟基-α,β-烯酸酯原位形成双烯醇盐中间体。原位生成的双烯醇盐可与苯甲醛反应，并进行实用且有用的串联烯丙基异构化-羟醛反应，以得到更多官能化的化合物。
