De novo approach to 2-deoxy-beta-glycosides: asymmetric syntheses of digoxose and digitoxin.
A highly enantioselective and straightforward route to trisaccharide natural products digoxose and digitoxin has been developed. Key to this approach is the iterative application of the palladium-catalyzed glycosylation reaction, reductive 1,3-transposition, diastereoselective dihydroxylation, and regioselective protection. The first total synthesis of natural product digoxose was accomplished in 19 total steps from achiral 2-acylfuran, and digitoxin was fashioned in 15 steps starting from digitoxigenin 2 and pyranone 8beta. This flexible synthetic strategy also allows for the preparation of mono- and disaccharide analogues of digoxose and digitoxin.
Zhou
Maoquan
M
Department of Chemistry, West Virginia University, Morgantown, West Virginia 26506, USA.
O'Doherty
George A
GA
D002236:Carbohydrate Conformation; D002384:Catalysis; D004074:Digitoxin / Q000138:chemical synthesis* / Q000737:chemistry; D004187:Disaccharides / Q000737:chemistry; D005947:Glucose / Q000737:chemistry; D006031:Glycosylation; D010100:Oxygen / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry; D013237:Stereoisomerism; D014312:Trisaccharides / Q000138:chemical synthesis* / Q000737:chemistry
D004187:Disaccharides; D014312:Trisaccharides; C519426:digoxose; D010165:Palladium; C002055:allose; D004074:Digitoxin; D005947:Glucose; D010100:Oxygen