Mechanism of Amination of β-Keto Esters by Azadicarboxylates Catalyzed by an Axially Chiral Guanidine: Acyclic Keto Esters React through an E Enolate

L Simón, JM Goodman

Index: Grayson, Matthew N.; Pellegrinet, Silvina C.; Goodman, Jonathan M. Journal of the American Chemical Society, 2012 , vol. 134, # 5 p. 2716 - 2722

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Citation Number: 18

Abstract

The mechanism of the reaction between di-tert-butyl azadicarboxylate and 1, 3-dicarbonyl compounds catalyzed by an axially chiral guanidine is investigated by density functional theory methods. The results show that the catalyst acts simultaneously as a Brønsted base and an acid catalyst, and the mechanism is similar to that of the related BINOP organocatalysts. Surprisingly, cyclic and acyclic β-keto esters yield opposite enantiomers; ...

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