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. 2009 May 20;131(19):6654-5.
doi: 10.1021/ja900701g.

Mechanism and transition-state structures for nickel-catalyzed reductive alkyne-aldehyde coupling reactions

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

Mechanism and transition-state structures for nickel-catalyzed reductive alkyne-aldehyde coupling reactions

P R McCarren et al. J Am Chem Soc. .

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 --> pi*(perpendicular) 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.

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Figures

Figure 1
Figure 1
Oxidative cyclization of alkyne and aldehyde. Bond lengths are in Å. Energies are with respect to the catalyst resting state 3.
Figure 2
Figure 2
a) An alternative pathway of alkyne-aldehyde oxidative cyclization: borane coordination to the aldehyde oxygen. Bond lengths are in Å. Energies are with respect to the catalyst resting state 3. Hydrogens in BEt3 are not shown. b) Oxidative cyclization of ethylene and acetaldehyde. Bond lengths are in Å. Energies are with respect to the catalyst resting state alkene(bisphosphane)nickel(0) complex 3'.
Scheme 1
Scheme 1
The oxidative cyclization mechanism of Ni-catalyzed reductive coupling between alkynes and aldehydes.
See this image and copyright information in PMC

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