Chemistry and Physics Faculty Articles

Title

Lithium Hexamethyldisilazide-Mediated Enolization of Acylated Oxazolidinones: Solvent, Cosolvent, and Isotope Effects on Competing Monomer- and Dimer-Based Pathways

Document Type

Article

Publication Date

1-25-2017

Publication Title

Journal of the American Chemical Society

ISSN

0002-7863

Volume

139

Issue/No.

3

First Page

1233

Last Page

1244

Abstract

Lithium hexamethyldisilazide (LiHMDS)-mediated enolization of (+)-4-benzyl-3-propionyl-2-oxazolidinone in THF–hydrocarbon mixtures shows unusual sensitivity to the choice of hydrocarbon cosolvent (hexane versus toluene) and to isotopic labeling. Four mechanisms corresponding to monosolvated monomers, trisolvated dimers, octasolvated monomers, and octasolvated dimers were identified. Even under conditions in which the LiHMDS monomer was the dominant observable form, dimer-based metalation was significant. The mechanism-dependent isotope and cosolvent effects are discussed in the context of ground-state stabilization and transition-state tunneling.

Comments

©2017 American Chemical Society

Additional Comments

NIH grant #s: GM039764, GM077167

ORCID ID

0000-0002-0566-0820

ResearcherID

V-6501-2018

DOI

10.1021/jacs.6b11354

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