南方科技大学知识苑(SUSTech KC): Mechanism and origin of regioselectivity in Rh-catalyzed desymmetric [2+2+2] cycloaddition: charge versus pi-pi stacking interaction

题名	Mechanism and origin of regioselectivity in Rh-catalyzed desymmetric [2+2+2] cycloaddition: charge versus pi-pi stacking interaction
作者	Shen, Boming ; Chen, Yu ; Yu, Peiyuan1
通讯作者	Yu, Peiyuan
发表日期	2022-07-01
DOI	10.1039/d2qo00682k
发表期刊	Organic Chemistry Frontiers 影响因子和分区
ISSN	2052-4129
卷号	9页码:4625-4632
摘要	Density functional theory (DFT) calculations have been performed to investigate the mechanism and origin of the enantio- and regioselectivity of Rh-catalyzed desymmetric [2 + 2 + 2] cycloaddition of enynes with terminal alkynes. The computational results show that the catalytic cycle involves oxidative cyclization of cyclohexadienone alkynes (rate- and enantioselectivity-determining step), alkyne insertion (regioselectivity-determining step), and reductive elimination/catalyst regeneration. Natural population analysis and independent gradient model analysis show that for para-electron donating group-substituted aryl alkynes, the charge distribution of alkynes is the dominant factor controlling the regioselectivity, while for strong electron withdrawing group-substituted aryl alkynes, the regioselectivity is controlled by enhanced pi-pi stacking interactions between the phenyl group of the aromatic alkyne moiety and the phenyl group of the ligand. Distortion/interaction analysis shows that the interaction energy between the rhodacycle complex and the cyclohexadienone alkyne is the determining factor controlling the enantioselectivity.
相关链接	[来源记录]
收录类别	SCI ; EI
语种	英语
学校署名	通讯
资助项目	SUSTech start-up fund[Y01216143] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002]
WOS研究方向	Chemistry
WOS类目	Chemistry, Organic
WOS记录号	WOS:000827639600001
出版者	ROYAL SOC CHEMISTRY
EI入藏号	20223012420490
EI主题词	Catalysis ; Computation theory ; Cyclization ; Density functional theory ; Factor analysis ; Hydrocarbons ; Regioselectivity ; Rhodium compounds
EI分类号	Computer Theory, Includes Formal Logic, Automata Theory, Switching Theory, Programming Theory:721.1 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Organic Compounds:804.1 ; Probability Theory:922.1 ; Mathematical Statistics:922.2 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4
来源库	Web of Science
引用统计	被引频次[WOS]：3
成果类型	期刊论文
条目标识符	http://sustech.caswiz.com/handle/2SGJ60CL/359469
专题	理学院_化学系深圳格拉布斯研究院
作者单位	1.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China 2.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Peoples R China
通讯作者单位	化学系
推荐引用方式 GB/T 7714	Shen, Boming,Chen, Yu,Yu, Peiyuan. Mechanism and origin of regioselectivity in Rh-catalyzed desymmetric [2+2+2] cycloaddition: charge versus pi-pi stacking interaction[J]. Organic Chemistry Frontiers,2022,9:4625-4632.
APA	Shen, Boming,Chen, Yu,&Yu, Peiyuan.(2022).Mechanism and origin of regioselectivity in Rh-catalyzed desymmetric [2+2+2] cycloaddition: charge versus pi-pi stacking interaction.Organic Chemistry Frontiers,9,4625-4632.
MLA	Shen, Boming,et al."Mechanism and origin of regioselectivity in Rh-catalyzed desymmetric [2+2+2] cycloaddition: charge versus pi-pi stacking interaction".Organic Chemistry Frontiers 9(2022):4625-4632.