Experimental evidence for chair-like transition states in aldol reactions of methyl ketone lithium enolates: stereoselective synthesis and utilization of a deuterium-labeled enolate as a probe of reaction stereochemistry

Christopher M Liu; William J Smith 3rd; Darin J Gustin; William R Roush

doi:10.1021/ja050730c

Experimental evidence for chair-like transition states in aldol reactions of methyl ketone lithium enolates: stereoselective synthesis and utilization of a deuterium-labeled enolate as a probe of reaction stereochemistry

J Am Chem Soc. 2005 Apr 27;127(16):5770-1. doi: 10.1021/ja050730c.

Authors

Christopher M Liu¹, William J Smith 3rd, Darin J Gustin, William R Roush

Affiliation

¹ Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109-1055, USA.

PMID: 15839658
DOI: 10.1021/ja050730c

Abstract

Aldol reactions of methyl ketone lithium enolates proceed via chairlike Zimmerman-Traxler transition states with 7:1 to 50:1 preference over alternative, boatlike transition structures, as determined by studies involving the configurationally stable deuterium-labeled enol silane 18 as the lithium enolate precursor.

Publication types

Research Support, N.I.H., Extramural
Research Support, U.S. Gov't, P.H.S.

MeSH terms

Alcohols / chemical synthesis*
Aldehydes / chemistry*
Deuterium
Ketones / chemical synthesis*
Ketones / chemistry
Lithium / chemistry*
Molecular Conformation
Organometallic Compounds / chemistry
Pentanones / chemistry*
Stereoisomerism

Substances

Alcohols
Aldehydes
Ketones
Organometallic Compounds
Pentanones
Lithium
Deuterium

Grants and funding

GM 38436/GM/NIGMS NIH HHS/United States