Source of Rate Acceleration for Carbocation Cyclization in Biomimetic Supramolecular Cages
Q. N. Nguyen, Kay T. Xia, Yue Zhang, Nanhao Chen, Mariko Morimoto, Xiaokun Pei, Yang Ha, Jinghua Guo, Wanli Yang, Lee‐Ping Wang, Robert G. Bergman, Kenneth N. Raymond, F. Dean Toste, Dean J. Tantillo
Abstract
The results of quantum chemical and molecular dynamics calculations reveal that polyanionic gallium-based cages accelerate cyclization reactions of pentadienyl alcohols as a result of substrate cage interactions, preferential binding of reactive conformations of substrate/H3O+ pairs, and increased substrate basicity. However, the increase in basicity dominates. Experimental structure–activity relationship studies in which the metal vertices and overall charge of the cage are varied confirm the model derived via calculations.
Topics & Concepts
ChemistryCarbocationSubstrate (aquarium)Supramolecular chemistryQuantum chemicalCageComputational chemistryStereochemistryGalliumMoleculeAccelerationCage effectPhotochemistryOrganic chemistryGeologyCombinatoricsOceanographyClassical mechanicsPhysicsMathematicsSupramolecular Chemistry and ComplexesMass Spectrometry Techniques and ApplicationsDendrimers and Hyperbranched Polymers