Computational Design of a Tetrapericyclic Cycloaddition and the Nature of Potential Energy Surfaces with Multiple Bifurcations
Ana Martín‐Sómer, Xiao‐Song Xue, Cooper S. Jamieson, Yike Zou, K. N. Houk
Abstract
An ambimodal transition state (TS) that leads to formation of four different pericyclic reaction products ([4 + 6]-, [2 + 8]-, [8 + 2]-, and [6 + 4]-cycloadducts) without any intervening minima has been designed and explored with DFT computations and quasiclassical molecular dynamics. Direct dynamics simulations propagated from the ambimodal TS show the evolution of trajectories to give the four cycloadducts. The topography of the PES is a key factor in product selectivity. A good correlation is observed between geometrical resemblance of the products to the ambimodal TS (measured by the RMSD) and the ratio of products formed in the dynamics simulations.
Topics & Concepts
Pericyclic reactionChemistryMaxima and minimaCycloadditionMolecular dynamicsComputational chemistryTransition statePotential energyPotential energy surfaceProduct (mathematics)ComputationChemical physicsStatistical physicsMoleculeAtomic physicsOrganic chemistryPhysicsGeometryComputer scienceMathematicsCatalysisAlgorithmMathematical analysisOrganic Chemistry Cycloaddition ReactionsAdvanced Chemical Physics StudiesPhotochemistry and Electron Transfer Studies