title: 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. Variousab initiobenchmarks 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 theortho-C-prenylation and Claisen rearrangement of tyrosine, and the Claisen rearrangement of α,α-dimethylallyl (prenyl) coumaryl ether establish the energetics of these reactions in the gas phase and in aqueous solution.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569.
authors.forename: Sílvia
authors.initials: S
authors.lastname: Osuna
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569.
authors.forename: Seonah
authors.initials: S
authors.lastname: Kim
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569.
authors.forename: Guillaume
authors.initials: G
authors.lastname: Bollot
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569.
authors.forename: K N
authors.initials: KN
authors.lastname: Houk
keywords: CPCM; DFT; aromatic Claisen; prenylation