Deoxygenation of Alcohols Employing Water as the Hydrogen Atom Source
journal contributionposted on 14.09.2005, 00:00 by David A. Spiegel, Kenneth B. Wiberg, Laura N. Schacherer, Matthew R. Medeiros, John L. Wood
Trialkylboranes (BMe3, BEt3, and BBu3) have been shown to mediate reductive deoxygenation reactions of O-alkyl-S-methyl dithiocarbonates (methyl xanthates) in which water or deuterium oxide functions as the source of hydrogen or deuterium. This method has proven versatile with regard to substrate scope and is capable of providing protio- or deuterioalkane products in high yields with excellent levels of D-incorporation. Ab initio calculations suggest that the trialkylborane−water complex possesses an unusually low O−H bond dissociation energy (73 kcal/mol) and support a radical chain mechanism for this process. Taken together, this report provides evidence for fundamentally novel and previously overlooked modes of reactivity for water and trialkylboranes of wide ranging importance in both theoretical and applied investigations.
Read the peer-reviewed publication
Hydrogen Atom Source Trialkylboraneschain mechanismevidencemethyl xanthatesprotiodissociationsubstrate scopeDeoxygenationsourceBMe 3Ab initio calculationsmethodreductive deoxygenation reactionsdeuterioalkane productsregardAlcohols Employing WaterBBu 3investigationimportancedeuterium oxide functionstrialkylboranekcalreactivityyieldBEt 3modebondmethyl dithiocarbonates