Mechanism of chorismate mutase: Contribution of conformational restriction to catalysis in the Claisen rearrangement

NA Khanjin, JP Snyder, FM Menger

Index: Khanjin, Nikolai A.; Snyder, James P.; Menger Journal of the American Chemical Society, 1999 , vol. 121, # 50 p. 11831 - 11846

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Citation Number: 82

Abstract

The mechanism of the enzyme-and antibody-catalyzed Claisen rearrangement of chorismate to prephenate was investigated experimentally on model compounds and by using quantum chemistry calculations at the Becke3LYP/6-31G* level of theory. Conformational restriction of the allyl vinyl ether fragment to the reactive chairlike conformation in 1 induces a 2× 105-fold rate acceleration (ΔΔ G⧧= 7.3 kcal/mol) of the ...

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