Activation Model and Origins of Selectivity for Chiral Phosphoric Acid Catalyzed Diradical Reactions
Ying Wang, Weichi Chen, Yilei Lai, Abing Duan
Abstract
To develop new radical synthesis strategies, a profound understanding of the electronic transfer mechanism is critical. An activation model called relayed proton-coupled electron transfer (relayed-PCET) was developed and investigated for chiral phosphoric acid-catalyzed diradical reactions by density functional theory (DFT). The driving force of electron transfer from the nucleophile to the electrophile is the proton transfer that occurs via the chiral phosphoric acid (CPA) catalyst to the electrophile. Moreover, the origins of the selectivity can be explained by distortion of the catalyst, favorable hydrogen bonding, and strong interactions of the substrates with substituents of the CPAs.
Topics & Concepts
ChemistryDiradicalElectrophilePhosphoric acidNucleophileCatalysisSelectivityElectron transferDensity functional theoryPhotochemistryComputational chemistryAcid catalysisCombinatorial chemistryOrganic chemistryNuclear physicsSinglet stateExcited statePhysicsRadical Photochemical ReactionsCO2 Reduction Techniques and CatalystsOxidative Organic Chemistry Reactions