title: 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, however theoretical insight to its regulatory mechanism is still sparse. Accurate quantum chemical calculations at the CASPT2//CASSCF level of theory associated with energy-consistent relativistic pseudopotentials provide a basis for the first regulation theory that the enantioselective reaction is predominantly controlled by the presence of relativistic effects, that is, spin-orbit coupling resulting from heavy atoms in the chiral Lewis acid catalyst.
authors.affiliation: Key Laboratory of Theoretical and Computational Photochemistry of Ministry of Education, Department of Chemistry, Beijing Normal University, Xin-wai-da-jie No. 19, Beijing 100875 (China).
authors.forename: Hongjuan
authors.initials: H
authors.lastname: Wang
authors.affiliation: Theoretical Chemistry, University of Cologne, Greinstrasse 4, 50939 Cologne (Germany).
authors.forename: Xiaoyan
authors.initials: X
authors.lastname: Cao
authors.affiliation: Key Laboratory of Theoretical and Computational Photochemistry of Ministry of Education, Department of Chemistry, Beijing Normal University, Xin-wai-da-jie No. 19, Beijing 100875 (China). xuebochen@bnu.edu.cn.
authors.forename: Xuebo
authors.initials: X
authors.lastname: Chen
authors.affiliation: Key Laboratory of Theoretical and Computational Photochemistry of Ministry of Education, Department of Chemistry, Beijing Normal University, Xin-wai-da-jie No. 19, Beijing 100875 (China).
authors.forename: Weihai
authors.initials: W
authors.lastname: Fang
authors.affiliation: Theoretical Chemistry, University of Cologne, Greinstrasse 4, 50939 Cologne (Germany). m.dolg@uni-koeln.de.
authors.forename: Michael
authors.initials: M
authors.lastname: Dolg
keywords: Lewis acids; ab initio calculations; cycloaddition; enantioselectivity; heterocycles