A stereoselective synthesis of digitoxin and digitoxigen mono- and bisdigitoxoside from digitoxigenin via a palladium-catalyzed glycosylation.
A convergent and stereocontrolled route to trisaccharide natural product digitoxin has been developed. The route is amenable to the preparation of both the digitoxigen mono- and bisdigitoxoside. This route featured the iterative application of the palladium-catalyzed glycosylation reaction, reductive 1,3-transposition, diastereoselective dihydroxylation, and regioselective protection. The natural product digitoxin was fashioned in 15 steps starting from digitoxigenin 2 and pyranone 8a or 18 steps from achiral acylfuran.
Zhou
Maoquan
M
Department of Chemistry, West Virginia University, Morgantown, West Virginia 26506, USA.
O'Doherty
George A
GA
D002240:Carbohydrate Sequence; D004073:Digitoxigenin / Q000737:chemistry*; D004074:Digitoxin / Q000031:analogs & derivatives* / Q000138:chemical synthesis*; D006031:Glycosylation; D008969:Molecular Sequence Data; D010165:Palladium / Q000737:chemistry*; D013237:Stereoisomerism
C520898:digitoxigen bisdigitoxoside; D004073:Digitoxigenin; D010165:Palladium; D004074:Digitoxin