Origins of Regioselectivity and Alkene-Directing Effects in Nickel- Catalyzed Reductive Couplings of Alkynes and Aldehydes
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Author(s)
Jamison, Timothy F.
Cheong, Paul Ha-Yeon
Houk, K. N.
Liu, Peng
McCarren, Patrick R.
Date Issued
January 2010
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Citation
Jamison, Timothy F. et al. "Origins of Regioselectivity and Alkene-Directing Effects in Nickel-Catalyzed Reductive Couplings of Alkynes and Aldehydes." Journal of the American Chemical Society 132.6 (2010): 2050-2057.
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Author's final manuscript
Abstract
The origins of reactivity and regioselectivity in nickel-catalyzed reductive coupling reactions of alkynes and aldehydes were investigated with density functional calculations. The regioselectivities of reactions of simple alkynes are controlled by steric effects, while conjugated enynes and diynes are predicted to have increased reactivity and very high regioselectivities, placing alkenyl or alkynyl groups distal to the forming C−C bond. The reactions of enynes and diynes involve 1,4-attack of the Ni−carbonyl complex on the conjugated enyne or diyne. The consequences of these conclusions on reaction design are discussed.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/ja909562y
