Regulatory Mechanism of the Enantioselective Intramolecular Enone [2+2] Photocycloaddition Reaction Mediated by a Chiral Lewis Acid Catalyst Containing Heavy Atoms
Regulatory Mechanism of the Enantioselective Intramolecular Enone [2+2] Photocycloaddition Reaction Mediated by a Chiral Lewis Acid Catalyst Containing Heavy Atoms
复制标题
含重原子手性路易斯酸催化剂介导的对映选择性分子内烯酮[2 2]光环加成反应的调控机制
DOI：
10.1002/anie.201505931
复制
发表时间：
2015
影响因子：
16.6
通讯作者：
Dolg Michael
中科院分区：
文献类型：
--
作者：
Wang Hongjuan;Cao Xiaoyan;Chen Xuebo;Fang Weihai;Dolg Michael
分子内烯酮[2+2]光环加成反应的不对称催化已经得到了广泛的实验研究，但对其调控机理的理论认识还很少。在与能量一致的相对论赝势相关的CASPT2//CASSCF理论水平上的精确量子化学计算为第一调节理论提供了基础，该理论认为对映选择性反应主要受相对论效应的存在，即手性Lewis酸催化剂中重原子引起的自旋-轨道耦合。
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.