Mechanism and Transition-State Structures for Nickel-Catalyzed Reductive Alkyne−Aldehyde Coupling Reactions
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Jamison_Mechanism and transition.pdf
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Author(s)
McCarren, Patrick R.
Liu, Peng
Cheong, Paul Ha-Yeon
Jamison, Timothy F.
Houk, K. N.
Date Issued
April 2009
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Citation
McCarren, P. R., Peng Liu, Paul Ha-Yeon Cheong, Timothy F. Jamison, and K. N. Houk. “Mechanism and Transition-State Structures for Nickel-Catalyzed Reductive Alkyne−Aldehyde Coupling Reactions.” Journal of the American Chemical Society 131, no. 19 (May 20, 2009): 6654-6655.
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Author's final manuscript
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 → π* 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.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/ja900701g
