Enzyme–Substrate Complementarity Governs Access to a Cationic Reaction Manifold in the P450BM3??Catalysed Oxidation of Cyclopropyl Fatty Acids

MJ Cryle, PY Hayes, JJ De Voss

Index: Cryle, Max J.; Hayes, Patricia Y.; De Voss, James J. Chemistry - A European Journal, 2012 , vol. 18, # 50 p. 15994 - 15999

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Citation Number: 3

Abstract

Abstract The products of cytochrome P450 BM3-catalysed oxidation of cyclopropyl- containing dodecanoic acids are consistent with the presence of a cationic reaction intermediate, which results in efficient dehydrogenation of the rearranged probes by the enzyme. These results highlight the importance of enzyme–substrate complementarity, with a cationic intermediate occurring only when the probes used begin to diverge from ideal ...