Direct vinylation of alcohols or aldehydes employing alkynes as vinyl donors: a ruthenium catalyzed C-C bond-forming transfer hydrogenation.
Under the conditions of ruthenium catalyzed transfer hydrogenation, 2-butyne couples to benzylic and aliphatic alcohols 1a-1l to furnish allylic alcohols 2a-2l, constituting a direct C-H vinylation of alcohols employing alkynes as vinyl donors. Under related transfer hydrogenation conditions employing formic acid as terminal reductant, 2-butyne couples to aldehydes 4a, 4b, and 4e to furnish identical products of carbonyl vinylation 2a, 2b, and 2e. Thus, carbonyl vinylation is achieved from the alcohol or the aldehyde oxidation level in the absence of any stoichiometric metallic reagents. Nonsymmetric alkynes 6a-6c couple efficiently to aldehyde 4b to provide allylic alcohols 2m-2o as single regioisomers. Acetylenic aldehyde 7a engages in efficient intramolecular coupling to deliver cyclic allylic alcohol 8a.
Patman
Ryan L
RL
Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, Texas 78712, USA.
Chaulagain
Mani Raj
MR
Williams
Vanessa M
VM
Krische
Michael J
MJ
D000438:Alcohols / Q000138:chemical synthesis / Q000737:chemistry*; D000447:Aldehydes / Q000737:chemistry*; D000480:Alkynes / Q000737:chemistry*; D002384:Catalysis; D006865:Hydrogenation; D012428:Ruthenium; D014753:Vinyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry
D000438:Alcohols; D000447:Aldehydes; D000480:Alkynes; D014753:Vinyl Compounds; D012428:Ruthenium