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. 2010 Feb 17;132(6):2050-7.
doi: 10.1021/ja909562y.

Origins of regioselectivity and alkene-directing effects in nickel-catalyzed reductive couplings of alkynes and aldehydes

Peng Liu  1 , Patrick McCarren, Paul Ha-Yeon Cheong, Timothy F Jamison, K N Houk
Affiliations

Origins of regioselectivity and alkene-directing effects in nickel-catalyzed reductive couplings of alkynes and aldehydes

Peng Liu et al. J Am Chem Soc. .

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.

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Figures

Figure 1
Figure 1
Oxidative addition transition states for the reaction with 1,3-butenyne 1k and acetaldehyde.
Figure 2
Figure 2
Oxidative addition transition states in alternative pathways for the reaction with 1,3-butenyne 1k and acetaldehyde.
Figure 3
Figure 3
Distortion energy of enyne (Edist(enyne)) and interaction energy of enyne with nickel and aldehyde (Eint) as a function of the forming C–C bond length in the reaction of 1,3-butenyne 1k and acetaldehyde.
Scheme 1
Scheme 1
Ni-catalyzed reductive coupling reactions.
See this image and copyright information in PMC

References

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