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. 2010 May 12;132(18):6304-5.
doi: 10.1021/ja102262v.

A general strategy for regiocontrol in nickel-catalyzed reductive couplings of aldehydes and alkynes

Hasnain A Malik  1 , Grant J Sormunen, John Montgomery
Affiliations

A general strategy for regiocontrol in nickel-catalyzed reductive couplings of aldehydes and alkynes

Hasnain A Malik et al. J Am Chem Soc. .

Abstract

A strategy for catalyst-controlled regioselectivity in aldehyde-alkyne reductive couplings has been developed. This strategy is the first where either regiochemical outcome may be selected for a broad range of couplings, without relying on substrate biases or directing effects. The complementary use of small cyclopropenylidene carbene ligands or highly hindered N-heterocyclic carbene ligands allows the regiochemical reversal with unbiased internal alkynes, aromatic internal alkynes, conjugated enynes, or terminal alkynes.

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Figures

Figure 1
Figure 1
Ligand Steric Control of Regiochemistry.
See this image and copyright information in PMC

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    1. (a) Many examples with aromatic, terminal, and silyl alkynes are described in reference . For ynamides: Saito N, Katayama T, Sato Y. Org. Lett. 2008;10:3829. For diynes: Huddleston RR, Jang HY, Krische MJ. J. Am. Chem. Soc. 2003;125:11488. For enynes: Mahandru GM, Liu G, Montgomery J. J. Am. Chem. Soc. 2004;126:3698. Miller KM, Luanphaisarnnont T, Molinaro C, Jamison TF. J. Am. Chem. Soc. 2004;126:4130. Jang HY, Huddleston RR, Krische MJ. J. Am. Chem. Soc. 2004;126:4664.

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