期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 128, 期 31, 页码 10326-10336出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja062147h
关键词
-
资金
- NIGMS NIH HHS [R01 GM039764] Funding Source: Medline
Structural, kinetic, and computational studies reveal the mechanistic complexities of a lithium diisopropylamide (LDA)-mediated ester enolization. Hemilabile amino ether MeOCH2CH2NMe2, binding as an eta(1) (ether-bound) ligand in the reactant and as an eta(2) (chelating) ligand in the transition structure, accelerates the enolization 10,000-fold compared with n-BuOMe. At the onset of the reaction, a dimer-based enolization prevails. As the reaction proceeds, significantly less reactive LDA-enolate mixed dimers appear and divert the reaction through monomer-and mixed dimer-based pathways. The mechanistic and computational investigations lead to a proof-of-principle ligand-catalyzed enolization in which an ancillary ligand allows the catalytic ligand to re-enter the catalytic cycle.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据