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Title

Mechanistic study of nickel-catalyzed intramolecular [4+2] cycloaddition of cyclobutanone with allene: origin of selectivity and ligand effect

Author
Corresponding AuthorQu, Shuanglin
Publication Years
2023
DOI
Source Title
ISSN
2052-4129
Abstract
The transition metal catalyzed cycloaddition reaction is one of the most powerful tools for the construction of carbon- and heterocycles. Comprehensive computational studies are employed to investigate the mechanism and the origins of the regio-, chemo-, Z/E-, and enantioselectivities, as well as the ligand effect in the Ni-catalyzed intramolecular [4 + 2] cycloaddition of cyclobutanone with allene. The reaction is found to follow the oxidative addition/migratory insertion pathway instead of the originally proposed cyclometallation/beta-carbon elimination pathway, in which the oxidative addition is the rate- and enantioselectivity-determining step. Detailed electronic and geometric analysis reveals that the regio- and chemoselectivities are controlled by the electronic effect, while the Z/E selectivity is primarily determined by the steric effect. Further distortion/interaction analysis shows that the (S,S)-enantioselectivity originated predominantly due to the lower distortion energy of the Ni-chiral ligand fragment in the C-C bond oxidative addition transition state. Finally, the calculations show that it is critical to produce a free coordination site by phosphine ligand dissociation during the reaction pathway. This requisite phosphine ligand dissociation is available for monodentate phosphine ligands but highly disfavored for bidentate phosphine ligands because of the chelation effect, which agrees well with the experimentally observed decreased reactivity of bidentate phosphine ligands.
URL[Source Record]
Indexed By
Language
English
SUSTech Authorship
Others
Funding Project
National Natural Science Foundation of China[21903022] ; Hunan Youth Talent[2021RC3053]
WOS Research Area
Chemistry
WOS Subject
Chemistry, Organic
WOS Accession No
WOS:000916742500001
Publisher
Data Source
Web of Science
Citation statistics
Cited Times [WOS]:1
Document TypeJournal Article
Identifierhttp://kc.sustech.edu.cn/handle/2SGJ60CL/430741
DepartmentDepartment of Chemistry
Affiliation
1.Hunan Univ, Coll Chem & Chem Engn, State Key Lab Chemo Biosensing & Chemometr, Changsha 410082, Peoples R China
2.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
Recommended Citation
GB/T 7714
Li, Jinxia,Luo, Jinbo,Tong, Wenyan,et al. Mechanistic study of nickel-catalyzed intramolecular [4+2] cycloaddition of cyclobutanone with allene: origin of selectivity and ligand effect[J]. Organic Chemistry Frontiers,2023.
APA
Li, Jinxia.,Luo, Jinbo.,Tong, Wenyan.,Tang, Dingyi.,Zhang, Jin.,...&Qu, Shuanglin.(2023).Mechanistic study of nickel-catalyzed intramolecular [4+2] cycloaddition of cyclobutanone with allene: origin of selectivity and ligand effect.Organic Chemistry Frontiers.
MLA
Li, Jinxia,et al."Mechanistic study of nickel-catalyzed intramolecular [4+2] cycloaddition of cyclobutanone with allene: origin of selectivity and ligand effect".Organic Chemistry Frontiers (2023).
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