title: Bio-inspired synthesis of rare and unnatural carbohydrates and cyclitols through strain driven epimerization.
abstract: We report a bio-inspired, strain driven epimerization of trans-ketals to cis-ketals through an enolate intermediate. Swern oxidation of a hydroxyl group adjacent to a trans-ketal effects both oxidation and its epimerization to cis-ketal. This novel and general strategy allows inversion of up to three contiguous stereocenters and has been illustrated by the synthesis of several unnatural/rare isomers of carbohydrates/cyclitols from their naturally abundant isomers.
authors.affiliation: School of Chemistry, Indian Institute of Science Education and Research, Thiruvananthapuram, CET-Campus, Thiruvananthapuram-695016, India. kms@iisertvm.ac.in.
authors.forename: Raja
authors.initials: R
authors.lastname: Mohanrao
authors.forename: Aromal
authors.initials: A
authors.lastname: Asokan
authors.forename: Kana M
authors.initials: KM
authors.lastname: Sureshan
mesh_terms: D000447:Aldehydes / Q000737:chemistry; D001688:Biological Products / Q000138:chemical synthesis; D002241:Carbohydrates / Q000138:chemical synthesis*; D054812:Cyclitols / Q000138:chemical synthesis*; D003512:Cyclohexanones / Q000138:chemical synthesis; D007294:Inositol / Q000737:chemistry; D007535:Isomerases / Q000737:chemistry; D010084:Oxidation-Reduction; D013237:Stereoisomerism
chemical_list: D000447:Aldehydes; D001688:Biological Products; D002241:Carbohydrates; D054812:Cyclitols; D003512:Cyclohexanones; C574885:gabosine J; D007294:Inositol; D007535:Isomerases