Metal Bound or Free Ylides as Reaction Intermediates in Metal-Catalyzed [2,3]-Sigmatropic Rearrangements? It Depends
Croix J. Laconsay, Dean J. Tantillo
Abstract
Density functional theory calculations were applied to study four previously published metal-catalyzed [2,3]-rearrangements from onium ylide intermediates, in pursuit of generalizations about when, during these types of reactions, catalysts dissociate. Our results corroborate past studies where free-ylide mechanisms were proposed to be operative. Results of calculations on case studies indicate that the origin of metal–catalyst dissociation can be attributed primarily to the steric bulkiness of functional groups adjacent to the carbene carbon.
Topics & Concepts
YlideChemistryCarbeneCatalysisSteric effectsSigmatropic reactionDensity functional theoryMetalDissociation (chemistry)PhotochemistryOniumComputational chemistryMedicinal chemistryOrganic chemistryIonCyclopropane Reaction MechanismsCatalytic C–H Functionalization MethodsSynthesis and Catalytic Reactions