Hydrogen-Mediated C-C Coupling to form Allylic Alcohols

“Direct Vinylation of Alcohols or Aldehydes Employing Alkynes as Vinyl Donors: A Ruthenium Catalyzed C-C Bond Forming Transfer Hydrogenation”  Patman, R. L.; Chaulagain, M. R.; Williams, V. M.; Krische, M. J. J. Am. Chem. Soc. 2009131, 2066-2067. DOI: 10.1021/ja809456u

In their 2007 JOC perspective on hydrogen-mediated C-C bond formation, Krische and co-workers point out that “upon consideration of the E-factor for various segments of the chemical industry, a strong inverse correlation between process volume and waste generation is observed.”(1) Given that the lower volume fine chemical and pharmaceutical sectors typically focus on the production of chemicals with higher degrees of molecular complexity then their bulk chemical counterparts, the authors propose that there is a persistent need for the development of selective, atom-economical reactions capable of producing these relatively specialized chemicals. As luck would have it, the Krische group has come to the rescue with a number of reactions that might fit the bill.

One such reaction is their recent report of the ruthenium-catalyzed vinylation of alcohols or aldehydes using alkynes as the vinyl donors (shown above).

I think this reaction is neat because it represents a departure from how people have typically gone about bringing alkynes and alcohols together to form allylic alcohols. In this early example from the Wipf group, Continue reading