Regulatory Mechanism of the Enantioselective Intramolecular Enone [2+2] Photocycloaddition Reaction Mediated by a Chiral Lewis Acid Catalyst Containing Heavy Atoms

Abstract

The asymmetric catalysis of the intramolecular enone [2+ +2] photocycloaddition has been subject of extensive experimental studies,h owever theoretical insight to its regulatory mechanismi ss till sparse.A ccurate quantum chemical calculations at the CASPT2//CASSCF level of theory associated with energy-consistent relativistic pseudopotentials provide ab asis for the first regulation theory that the enantioselective reaction is predominantly controlled by the presence of relativistic effects,t hat is,s pin-orbit coupling resulting from heavy atoms in the chiral Lewis acid catalyst. Scheme 1. Enantioselective intramolecular [2+ +2] photocycloaddition reaction for 2,m ediated by the chiral Lewis acid 1.

Methods and Models of Theoretical Calculation for Single-Molecule Magnets

“…Three varieties of orbitals are segregated from the whole orbitals in molecule systems, such as closed space, active space and virtual space (Figure 2). In this method, dynamic correlation is not originally fully taken into account, while the complete active space perturbation theory (CASPT2) [36][37][38], N-electron valence state perturbation theory (NEVPT2) [39,40] and multi-reference configuration interaction method (MRCI) CASSCF is one of the central methods in dealing with metal complexes, successful at possessing the static correlation of multibody wave functions through fine zeroth-order wavefunction. Three varieties of orbitals are segregated from the whole orbitals in molecule systems, such as closed space, active space and virtual space (Figure 2).…”

“…Three varieties of orbitals are segregated from the whole orbitals in molecule systems, such as closed space, active space and virtual space (Figure 2). In this method, dynamic correlation is not originally fully taken into account, while the complete active space perturbation theory (CASPT2) [36][37][38], N-electron valence state perturbation theory (NEVPT2) [39,40] and multi-reference configuration interaction method (MRCI) [41,42] can realize the approximation of the full configuration interaction (CI) to recover dynamic correlation effect and acquire relatively pinpoint parameters. It is noted that the pivot of this approach in actual calculation processes is to determine appropriate and reasonable active space, which is relevant to the properties we study, namely active orbitals and electrons.…”