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.
Additional Comments
NIH grant #s: GM039764, GM077167
NSUWorks Citation
Reyes-Rodriguez, G. J., Algera, R. F., & Collum, D. B. (2017). Lithium Hexamethyldisilazide-Mediated Enolization of Acylated Oxazolidinones: Solvent, Cosolvent, and Isotope Effects on Competing Monomer- and Dimer-Based Pathways. Journal of the American Chemical Society, 139, (3), 1233 - 1244. https://doi.org/10.1021/jacs.6b11354. Retrieved from https://nsuworks.nova.edu/cnso_chemphys_facarticles/260
ORCID ID
0000-0002-0566-0820
ResearcherID
V-6501-2018
DOI
10.1021/jacs.6b11354
Comments
©2017 American Chemical Society