The carbonyl-olefin ring-closing metathesis reactions have become a powerful tool for carbon-carbon bond formation.In this work,the halogen bond catalysis and classical Lewis acid catalysis on the carbonyl-olefin ring...The carbonyl-olefin ring-closing metathesis reactions have become a powerful tool for carbon-carbon bond formation.In this work,the halogen bond catalysis and classical Lewis acid catalysis on the carbonyl-olefin ring-closing metathesis reaction were investigated by density function theory.For both the halogen bond catalysis and classical Lewis acid catalysis,the carbonyl-olefin ring-closing me-tathesis reaction occurs by[2+2]-cycloaddition process and[2+2]-cycloreversion process,the reaction energy barriers are low,there-fore,it can be performed easily at room temperature.The essential difference of the two kinds of catalysts is that the catalytic mecha-nism of halogen bond catalysis is mainly contribution of electrostatic interaction,while that of classical Lewis acid catalysis is mainly catalyzed by orbital interaction.The halogen bond donor catalysts(ICI_(3),IF_(3))are expected to be efficient catalysts for the reaction and further promote the chemical synthesis of carbonyl-olefin ring-closing metathesis reaction.展开更多
基金This work was supported by the Natural Science Foundation of Hebei Province(B2019205113,B2019205061)the National Natural Science Foundation of China(21973025)the Science Foundation of Hebei Normal University(L2020Z04).
文摘The carbonyl-olefin ring-closing metathesis reactions have become a powerful tool for carbon-carbon bond formation.In this work,the halogen bond catalysis and classical Lewis acid catalysis on the carbonyl-olefin ring-closing metathesis reaction were investigated by density function theory.For both the halogen bond catalysis and classical Lewis acid catalysis,the carbonyl-olefin ring-closing me-tathesis reaction occurs by[2+2]-cycloaddition process and[2+2]-cycloreversion process,the reaction energy barriers are low,there-fore,it can be performed easily at room temperature.The essential difference of the two kinds of catalysts is that the catalytic mecha-nism of halogen bond catalysis is mainly contribution of electrostatic interaction,while that of classical Lewis acid catalysis is mainly catalyzed by orbital interaction.The halogen bond donor catalysts(ICI_(3),IF_(3))are expected to be efficient catalysts for the reaction and further promote the chemical synthesis of carbonyl-olefin ring-closing metathesis reaction.
