Large transition state stabilization from a weak hydrogen bond
Erik C. Vik, Ping Li, Josef M. Maier, Daniel O. Madukwe, Vitaly A. Rassolov, Perry J. Pellechia, Eric Masson, Ken D. Shimizu
Abstract
experimental substituent effect and computational perturbation analyses. Energy decomposition analysis of the hydrogen bonding interaction revealed a significant reduction in the repulsive component of the hydrogen bonding interaction. The rigid framework of the molecular rotors positions and preorganizes the interacting groups in the transition state. This study demonstrates that with proper design a single hydrogen bond can lead to a TS stabilization that is greater than the intrinsic interaction energy, which has applications in catalyst design and in the study of enzyme mechanisms.
Topics & Concepts
Intramolecular forceHydrogen bondMeasure (data warehouse)Series (stratigraphy)ChemistryBondHydrogenLow-barrier hydrogen bondState (computer science)Computational chemistryChemical physicsMoleculeStereochemistryOrganic chemistryComputer scienceEconomicsData miningPaleontologyBiologyAlgorithmFinanceCrystallography and molecular interactionsSupramolecular Chemistry and ComplexesMolecular Sensors and Ion Detection