From common carbohydrates to enantiopure cyclooctane polyols and glycomimetics via deoxygenative zirconocene ring contraction.
D-Arabinose and D-glucose are transformed into the identical vinyl furanoside, whose role is to serve as the precursor to enantiopure cyclooctadienone 6. The key steps of this relay involve a zirconocene-promoted ring contraction and [3,3] sigmatropic rearrangement of an enynol. Subsequently defined are convenient synthetic routes to several cyclooctane-1,2,3-triols, 1,2,3,4,5-pentaols, and structurally related glycomimetics.
Paquette
Leo A
LA
Evans Chemical Laboratories, Ohio State University, Columbus, Ohio 43210, USA. paquette.1@osu.edu
Zhang
Yunlong
Y
D000438:Alcohols / Q000138:chemical synthesis*; D001089:Arabinose / Q000737:chemistry; D002241:Carbohydrates / Q000737:chemistry*; D034242:Cyclooctanes / Q000737:chemistry*; D005947:Glucose / Q000737:chemistry; D018716:Molecular Mimicry; D013237:Stereoisomerism; D014753:Vinyl Compounds / Q000737:chemistry
D000438:Alcohols; D002241:Carbohydrates; D034242:Cyclooctanes; D014753:Vinyl Compounds; D001089:Arabinose; D005947:Glucose; C474479:cyclooctane