Abstract
Density functional theory calculations have been used to investigate the catalytic role of nickel(0) in the decarbonylative addition of phthalimides to alkynes. According to Kurahashi et al. the plausible reaction mechanism involves a nucleophilic attack of nickel at an imide group, giving a six-membered metallacycle, followed by a decarbonylation and insertion of an alkyne leading to a seven-membered metallacycle. Finally a reductive elimination process produces the desired product and regenerates the nickel(0) catalyst. In this paper, we present a full description of the complete reaction pathway along with possible alternative pathways, which are predicted to display higher upper barriers. Our computational results substantially confirm the proposed mechanism, offering a detailed geometrical and energetical understanding of all the elementary steps. © 2013 American Chemical Society.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 6330-6336 |
| Number of pages | 7 |
| Journal | Organometallics |
| Volume | 32 |
| Issue number | 21 |
| DOIs | |
| State | Published - Oct 30 2013 |
Bibliographical note
KAUST Repository Item: Exported on 2020-10-01Acknowledgements: A.P. and L.C. thank the HPC team of Enea for using the ENEA-GRID and the HPC facilities CRESCO in Portici (Italy) for access to remarkable computational resources. A.P. thanks the Spanish MICINN for a Ramon y Cajal contract (RYC-2009-05226), European Commission for a Career Integration Grant (CIG09-GA-2011-293900), and Generalitat de Catalunya (2012BE100824).
ASJC Scopus subject areas
- Organic Chemistry
- Physical and Theoretical Chemistry
- Inorganic Chemistry