Sodium bicarbonate-catalyzed stereoselective isomerizations of electron-deficient propargylic alcohols to (Z)-enones.
Redox isomerization is a synthetically important process because it creates two new functional groups in the product, among which is the isomerization of propargylic alcohols to conjugated enones. Although E-enones have been prepared by this approach, Z-enones could not be accessed. We previously reported DABCO-catalyzed E-selective isomerization of electron-deficient propargylic alcohols to enones and its mechanism. Based on this mechanism, we have now developed the first Z-selective redox isomerization of electron-deficient propargylic alcohol to enone using sodium bicarbonate as a catalyst.
Sonye
John P
JP
Department of Chemistry, University of Pittsburgh, 219 Parkman Avenue, Pittsburgh, PA 15260, USA.
Koide
Kazunori
K
D000438:Alcohols / Q000737:chemistry*; D000475:Alkenes / Q000737:chemistry; D002384:Catalysis; D004121:Dimethyl Sulfoxide; D004583:Electrons; D007202:Indicators and Reagents; D007510:Isatin / Q000031:analogs & derivatives* / Q000737:chemistry*; D007536:Isomerism; D009682:Magnetic Resonance Spectroscopy; D063065:Organophosphonates / Q000737:chemistry; D017693:Sodium Bicarbonate / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D013237:Stereoisomerism
D000438:Alcohols; D000475:Alkenes; D007202:Indicators and Reagents; D063065:Organophosphonates; D007510:Isatin; D017693:Sodium Bicarbonate; D004121:Dimethyl Sulfoxide