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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

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References

    1. For reviews, see Montgomery J. Acc Chem Res. 2000;33:467.Ikeda S. Angew Chem, Int Ed. 2003;42:5120.Montgomery J. Angew Chem, Int Ed. 2004;43:3890.Montgomery J, Sormunen GJ. In: Metal Catalyzed Reductive C-C Bond Formation: A Departure from Preformed Organometallic Reagents. Krische MJ, editor. Springer; Berlin / Heidelberg: 2007. pp. 1–23.Moslin RM, Miller-Moslin K, Jamison TF. Chem Commun. 2007:4441.

    1. Huang WS, Chan J, Jamison TF. Org Lett. 2000;2:4221. - PubMed
    1. Mahandru GM, Liu G, Montgomery J. J Am Chem Soc. 2004;126:3698. - PubMed

    1. For more examples of Ni-catalyzed intermolecular alkyne-aldehyde coupling, see: Colby EA, Jamison TF. J Org Chem. 2003;68:1456.Miller KM, Huang WS, Jamison TF. J Am Chem Soc. 2003;125:3442.Miller KM, Molinaro C, Jamison TF. Tetrahedron-Asymmetry. 2003;14:3619.Takai K, Sakamoto S, Isshiki T. Org Lett. 2003;5:653.Luanphaisarnnont T, Ndubaku CO, Jamison TF. Org Lett. 2005;7:2937.Moslin RM, Miller KM, Jamison TF. Tetrahedron. 2006;62:7598.Moslin RM, Jamison TF. Org Lett. 2006;8:455.Sa-Ei K, Montgomery J. Org Lett. 2006;8:4441.Chaulagain MR, Sormunen GJ, Montgomery J. J Am Chem Soc. 2007;129:9568.Yang Y, Zhu SF, Zhou CY, Zhou QL. J Am Chem Soc. 2008;130:14052.Trenkle JD, Jamison TF. Angew Chem, Int Ed. 2009;48:5366.

    1. For Ni-catalyzed intermolecular coupling reactions with enynes and carbonyl compounds, see: Miller KM, Luanphaisarnnont T, Molinaro C, Jamison TF. J Am Chem Soc. 2004;126:4130.Miller KM, Jamison TF. J Am Chem Soc. 2004;126:15342.Miller KM, Jamison TF. Org Lett. 2005;7:3077.Miller KM, Colby EA, Woodin KS, Jamison TF. Adv Synth Catal. 2005;347:1533.

    2. also see ref. 3