Title | Mechanism and origin of regioselectivity in Rh-catalyzed desymmetric [2+2+2] cycloaddition: charge versus pi-pi stacking interaction |
Author | |
Corresponding Author | Yu, Peiyuan |
Publication Years | 2022-07-01
|
DOI | |
Source Title | |
ISSN | 2052-4129
|
Volume | 9Pages:4625-4632 |
Abstract | 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. |
URL | [Source Record] |
Indexed By | |
Language | English
|
SUSTech Authorship | Corresponding
|
Funding Project | SUSTech start-up fund[Y01216143]
; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002]
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WOS Research Area | Chemistry
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WOS Subject | Chemistry, Organic
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WOS Accession No | WOS:000827639600001
|
Publisher | |
EI Accession Number | 20223012420490
|
EI Keywords | Catalysis
; Computation theory
; Cyclization
; Density functional theory
; Factor analysis
; Hydrocarbons
; Regioselectivity
; Rhodium compounds
|
ESI Classification Code | 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
|
Data Source | Web of Science
|
Citation statistics |
Cited Times [WOS]:3
|
Document Type | Journal Article |
Identifier | http://kc.sustech.edu.cn/handle/2SGJ60CL/359469 |
Department | Department of Chemistry 深圳格拉布斯研究院 |
Affiliation | 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 |
Corresponding Author Affilication | Department of Chemistry |
Recommended Citation 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.
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