Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 128, Issue 31, Pages 10326-10336Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja062147h
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Funding
- NIGMS NIH HHS [R01 GM039764] Funding Source: Medline
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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.
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