Mechanism and Transition-State Structures for Nickel-Catalyzed Reductive Alkyne−Aldehyde Coupling Reactions
Journal of the American Chemical Society2009Vol. 131(19), pp. 6654–6655
Citations Over TimeTop 10% of 2009 papers
Abstract
The mechanism of nickel-catalyzed reductive alkyne-aldehyde coupling reactions has been investigated using density functional theory. The preferred mechanism involves oxidative cyclization to form the nickeladihydrofuran intermediate followed by transmetalation and reductive elimination. The rate- and selectivity-determining oxidative cyclization transition state is analyzed in detail. The d --> pi*(perpendicular) back-donation stabilizes the transition state and leads to higher reactivity for alkynes than alkenes. Strong Lewis acids accelerate the couplings with both alkynes and alkenes by coordinating with the aldehyde oxygen in the transition state.
Related Papers
- → Mechanism of Ni-Catalyzed Selective C−O Bond Activation in Cross-Coupling of Aryl Esters(2009)279 cited
- → Oxidative Addition, Transmetalation, and Reductive Elimination at a 2,2′-Bipyridyl-Ligated Gold Center(2018)125 cited
- → Decarbonylative Fluoroalkylation at Palladium(II): From Fundamental Organometallic Studies to Catalysis(2021)45 cited
- → Computational Analysis of Enantioselective Pd-Catalyzed α-Arylation of Ketones(2020)19 cited
- → Mechanisms of chemoselectivity for acyl and decarbonylative Suzuki–Miyaura coupling of N-acetyl amide with arylboronic acid catalyzed by Pd and Ni catalysts: Insights from DFT calculations(2020)10 cited