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A DFT study of the mechanisms and regio- and stereochemistry of the lewis acid-catalyzed reactions of 5-alkoxyoxazoles with aldehydes: aryl substitution at the 2-position of 5-alkoxyoxazole is critical to the formation of 4-alkoxycarbonyl-2-oxazoline.

Research paper by Zhi-Xiang ZX Yu, Yun-Dong YD Wu

Indexed on: 18 Jan '03Published on: 18 Jan '03Published in: Journal of Organic Chemistry



Abstract

Density functional theory at the B3LYP/6-31G level has been used to study the mechanisms and regio- and stereochemistry of the Lewis acid-catalyzed reactions of aldehydes with 5-alkoxyoxazoles. Similar to the uncatalyzed reaction between aldehyde and 5-methoxyoxazole, which has an activation energy of 30.5 kcal/mol and intrinsically favors production of 2-alkoxycarbonyl-3-oxazoline, the Lewis acid-catalyzed reaction also prefers to generate 2-alkoxycarbonyl-3-oxazoline in a more efficient way with an activation energy of about 3 kcal/mol (with respect to separated acetaldehyde-AlCl3 complex and 5-methoxyoxazole) in the gas phase. Only when an aryl group is introduced to the 2 position of 5-alkoxyoxazoles can the Lewis acid-catalyzed reactions furnish 4-alkoxycarbonyl-2-oxazolines. The reasons for this switch of regiochemistry and the factors affecting the stereochemistry are discussed.