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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
Author(s) -
Osuna Sílvia,
Kim Seonah,
Bollot Guillaume,
Houk Kendall N.
Publication year - 2013
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201201738
Subject(s) - prenylation , claisen rearrangement , chemistry , aryl , stereochemistry , computational chemistry , organic chemistry , enzyme , alkyl
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 used (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 by using implicit and explicit models. Studies of the ortho ‐ C ‐prenylation and Claisen rearrangement of tyrosine, and the Claisen rearrangement of α,α‐dimethylallyl (prenyl) coumaryl ether establish the energetics of these reactions both in the gas phase and in aqueous solution.