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Aromatic Claisen Rearrangements of O-prenylated tyrosine and model prenyl aryl ethers: Computational study of the role of water on acceleration of Claisen rearrangements.

ABSTRACT: LynF, an enzyme from the TruF family, O-prenylates tyrosines in proteins; subsequent Claisen rearrangements give C-prenylated tyrosine products. These reactions in tyrosines and model phenolic systems have been explored with DFT and SCS-MP2 calculations. Various ab initio benchmarks have been computed (CBS-QB3, MP2, SCS-MP2) to examine the accuracy of commonly used density functionals, such as B3LYP and M06-2X. Solvent effects from water were considered using implicit and explicit models. Studies of the ortho-C-prenylation and Claisen rearrangement of tyrosine, and the Claisen rearrangement of ?,?-dimethylallyl (prenyl) coumaryl ether establish the energetics of these reactions in the gas phase and in aqueous solution.

SUBMITTER: Osuna S

PROVIDER: S-EPMC3873100 | biostudies-literature | 2013 May

REPOSITORIES: biostudies-literature

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Aromatic Claisen Rearrangements of O-prenylated tyrosine and model prenyl aryl ethers: Computational study of the role of water on acceleration of Claisen rearrangements.

Osuna Sílvia S Kim Seonah S Bollot Guillaume G Houk K N KN

European journal of organic chemistry 20130501 14

LynF, an enzyme from the TruF family, O-prenylates tyrosines in proteins; subsequent Claisen rearrangements give C-prenylated tyrosine products. These reactions in tyrosines and model phenolic systems have been explored with DFT and SCS-MP2 calculations. Various ab initio benchmarks have been computed (CBS-QB3, MP2, SCS-MP2) to examine the accuracy of commonly used density functionals, such as B3LYP and M06-2X. Solvent effects from water were considered using implicit and explicit models. ...[more]

PMID: 24376368

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