Synthesis of carbasugar C-1 phosphates via Pd-catalyzed cyclopropanol ring opening.
The stereoselective syntheses of 2,3-dideoxy-4-oxo-5a-carba-alpha- d-rhamnopyanose 1-phosphate, 2,3-dideoxy-5a-carba-alpha- d-rhamnopyranose 1-phosphate, 5a-carba-alpha- d-rhamnopyranose 1-phosphate, 5a-carba-beta- d-digitoxopyranose 1-phosphate, and 5a-carba-alpha- l-rhamnopyranose 1-phosphate have been achieved from d-quinic acid. The routes rely upon a Simmons-Smith cyclopropanation and diastereospecific ring opening of cyclopropanol under Pd/C hydrogenation condition to set up the alpha-methyl ketone. A sequence of diastereoselective reduction, dihydroxylation, and/or Myers' reductive 1,3-rearrangement were used to install the desired stereochemistry.
Shan
Mingde
M
Department of Chemistry, West Virginia University, Morgantown, West Virginia 26506, USA.
O'Doherty
George A
GA
D002236:Carbohydrate Conformation; D002384:Catalysis; D004988:Ethers, Cyclic / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D010710:Phosphates / Q000138:chemical synthesis* / Q000737:chemistry; D012210:Rhamnose / Q000031:analogs & derivatives / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
D004988:Ethers, Cyclic; D010710:Phosphates; C043657:cyclopropanol; D010165:Palladium; D012210:Rhamnose