NDLI: Mechanisms for nickel(0)/N-heterocyclic carbene-catalyzed intramolecular alkene hydroacylation: insights from a DFT study

Content Provider	Springer Nature Link
Author	Meng, Qingxi Wang, Fen
Copyright Year	2016
Abstract	Density functional calculations have been applied to study and elucidate nickel(0)/N-heterocyclic carbene-catalyzed intramolecular alkene hydroacylation. The calculations showed that nickel(0)-catalyzed intramolecular alkene hydroacylation involved four potential reaction channels (I, II, III, and IV), and pathway IV was predicted to be more favorable than the other three. Two pathways, I and II, had three steps (oxidative addition, hydrogen migration, reductive elimination), and the rate-determining step was hydrogen migration. Pathway III proceeded through oxidative cyclization, β-hydride elimination, and hydrogen migration, and the rate-determining step was β-hydride elimination. Pathway IV included four steps (oxidative cyclization, dimerization, β-hydride elimination, hydrogen migration), and the rate-determining step was again β-hydride elimination. Oxidative cyclization was easy and led to rapid dimerization, greatly reducing the free energy of β-hydride elimination. The binuclear nickelacycle intermediate was observed in Ogoshi’s experiments, and it was identified by nuclear magnetic resonance (NMR). The dominant product was the five-membered benzocyclic ketone p1. All results agreed with Ogoshi’s experiments. Graphical Abstract Nickel(0)-catalyzed intramolecular alkene hydroacylation involved four potential reaction channels. The binuclear nickelacycle intermediate was important, and the dimerization greatly reduced the free energy of the β-hydride elimination.
Starting Page	1
Ending Page	7
Page Count	7
File Format	PDF
ISSN	16102940
Journal	Journal of Molecular Modeling
Volume Number	23
Issue Number	1
e-ISSN	09485023
Language	English
Publisher	Springer Berlin Heidelberg
Publisher Date	2016-12-21
Publisher Place	Berlin, Heidelberg
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Nickel N-heterocyclic carbene Hydroacylation Alkene DFT Computer Applications in Chemistry Molecular Medicine Computer Application in Life Sciences Characterization and Evaluation of Materials Theoretical and Computational Chemistry
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Physical and Theoretical Chemistry Computational Theory and Mathematics Catalysis Inorganic Chemistry Computer Science Applications

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