Mechanism of the Enantioselective Intramolecular [2+2] Photocycloaddition Reaction of Coumarin Catalyzed by a Chiral Lewis Acid: Comparison with Enone Substrates

被引：17

作者：

Wang, Hongjuan ^{[1
]}

Fang, Wei-Hai ^{[1
]}

Chen, Xuebo ^{[1
]}

机构：

[1] Beijing Normal Univ, Dept Chem, Minist Educ, Key Lab Theoret & Computat Photochem, Xin Wai Da Jie 19, Beijing 100875, Peoples R China

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2016年 / 81卷 / 16期

关键词：

VISIBLE-LIGHT PHOTOCATALYSIS; 2ND-ORDER PERTURBATION-THEORY; DIELS-ALDER REACTIONS; PHOTOCHEMICAL-REACTIONS; PHOTOREDOX CATALYSIS; BETA-CYCLODEXTRINS; ORGANIC-SYNTHESIS; ENANTIODIFFERENTIATING PHOTOISOMERIZATION; SUPRAMOLECULAR PHOTOCHIROGENESIS; CYCLOBUTANE DERIVATIVES;

D O I：

10.1021/acs.joc.6b00980

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The asymmetric catalysis of the intramolecular enone [2 + 2] photocycloaddition reaction relies on a complicated regulation mechanism to control its reactivity and selectivity as well as quantum yield: The multiconfiguration perturbation theory associated with energy-consistent relativistic pseudopotentials offers a mechanistic comparison between representative coumarin and enone substrates. A pair of bright pi pi* states govern the unselective background reaction of the free coumarin through the direct cycloaddition in the singlet hypersurface and the elimination of the reaction channel in the triplet manifold due to the existence of anti El Sayed type singlet-triplet crossing. The opening of a reaction channel in the triplet state is repeatedly verified to depend on the presence of relativistic effects, i.e., spin-orbit coupling due to heavy atoms in the chiral Lewis acid catalyst.

引用

页码：7093 / 7101

页数：9

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