Aromatic Claisen Rearrangements of O-Prenylated Tyrosine and Model Prenyl Aryl Ethers: Computational Study of the Role of Water on Acceleration of Claisen Rearrangements

作者：Osuna Slvia; Kim Seonah; Bollot Guillaume; Houk Kendall N^*

来源：European Journal of Organic Chemistry, 2013, 2013(14): 2823-2831.

DOI：10.1002/ejoc.201201738

• Enzyme catalysis
• Solvent effects
• Density functional calculations
• Hydrogen bonding
• Rearrangement

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 ,-dimethylallyl (prenyl) coumaryl ether establish the energetics of these reactions both in the gas phase and in aqueous solution.

• 出版日期2013-5