CL : Vol. 37 (2008) , No. 11 p.1102

Formation of C–C Bonds via Ruthenium-catalyzed Transfer Hydrogenation: Carbonyl Addition from the Alcohol or Aldehyde Oxidation Level

Fumitoshi Shibahara¹⁾ and Michael J. Krische¹⁾

1) Department of Chemistry and Biochemistry, University of Texas at Austin

(Received August 4, 2008)

Under the conditions of ruthenium-catalyzed transfer hydrogenation employing isopropyl alcohol as terminal reductant, π-unsaturated compounds (1,3-dienes, allenes, 1,3-enynes, and alkynes) reductively couple to aldehydes to furnish products of carbonyl addition. In the absence of isopropyl alcohol, π-unsaturated compounds couple directly from the alcohol oxidation level to form identical products of carbonyl addition. Such “alcohol-unsaturate C–C couplings” enable carbonyl allylation, propargylation and vinylation from the alcohol oxidation level in the absence of stoichiometric organometallic reagents or metallic reductants. Thus, direct catalytic C–H functionalization of alcohols at the carbinol carbon is achieved.