Configurational and conformational preferences in oximes and oxime carbanions. Ab initio study of the syn effect in reactions of oxyimine enolate equivalents

Journal Article · Wed Sep 13 00:00:00 EDT 1989 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00201a010· OSTI ID:7069588

Glaser, R; Streitwieser, A ^[1]

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1. Univ. of California, Berkeley (USA)

Geometries and relative energies of stationary structures of several conformers of geometrical isomers of NO s-trans-configured acetaldoxime are reported. The calculated energies and geometries agree well with comparable experimental data. Effects of the theoretical model on the NO band lengths are discussed for formaldoxime. The theoretical results suggest that the regiochemistry of enolate equivalents of oxyimines in dissociating solvents is due to the thermodynamic syn preference of the anions. Syn/anti isomerization of the anions (E{sub a} < 26 kcal mol{sup {minus}1}) is rapid even at low temperatures. In contrast, the anti preference of the radicals of acetaldoxime indicates that the formation of the syn products in oxidative coupling reactions of the anions of oxime ethers is a kinetic effect.

• OSTI ID: 7069588
• Journal Information: Journal of the American Chemical Society; (USA), Vol. 111:19; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
OXIMES
CONFORMATIONAL CHANGES
BOND LENGTHS
CALCULATION METHODS
CHEMICAL REACTIONS
DATA ANALYSIS
MATHEMATICAL MODELS
THEORETICAL DATA
AMINES
DATA
DIMENSIONS
HYDROXY COMPOUNDS
INFORMATION
LENGTH
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
400201* - Chemical &amp; Physicochemical Properties