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. 2009 Aug 5;131(30):10366-7.
doi: 10.1021/ja904124b.

All-carbon quaternary centers via ruthenium-catalyzed hydroxymethylation of 2-substituted butadienes mediated by formaldehyde: beyond hydroformylation

Tomas Smejkal  1 , Hoon Han, Bernhard Breit, Michael J Krische
Affiliations

All-carbon quaternary centers via ruthenium-catalyzed hydroxymethylation of 2-substituted butadienes mediated by formaldehyde: beyond hydroformylation

Tomas Smejkal et al. J Am Chem Soc. .

Abstract

Ruthenium-catalyzed transfer hydrogenation of 2-substituted dienes 1a-i in the presence of paraformaldehyde results in reductive coupling at the 2-position to furnish the hydroxymethylation products 3a-i, which embody all-carbon quaternary centers. Reductive coupling of diene 1g to paraformaldehyde under standard conditions, but employing deuterio-paraformaldehyde, 2-propanol-d(8), or both, corroborated a catalytic mechanism involving rapid, reversible diene hydrometalation with incomplete regioselectivity in advance of C-C coupling. The present method provides an alternative to the hydroformylation of conjugated dienes, for which efficient, regioselective catalytic systems remain undeveloped.

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Figures

Scheme 1
Scheme 1
Plausible catalytic mechanism accounting for the results of isotopic labelling.
See this image and copyright information in PMC

References

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