title: Executing and rationalizing the synthesis of a difluorinated analogue of a ring-expanded calystegine B2.
abstract: A difluorinated analogue of a ring-expanded calystegine B(2) and some N-protected species were prepared via microwave-mediated transannular ring-opening of an epoxyketone. The diastereofacial selectivity of the epoxidation reaction, which delivers the key intermediate, and the regioselectivity of the transannular reactions were analyzed by density functional theory (DFT) methods. The epoxidation stereoselectivity arises from simple steric control, whereas the ring-closure reactions are subject to thermodynamic control.
authors.affiliation: WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, UK.
authors.forename: Sara H
authors.initials: SH
authors.lastname: Kyne
authors.forename: Jonathan A L
authors.initials: JA
authors.lastname: Miles
authors.forename: Jonathan M
authors.initials: JM
authors.lastname: Percy
authors.forename: Kuldip
authors.initials: K
authors.lastname: Singh
mesh_terms: D017611:Fluorine Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D009662:Nortropanes / Q000138:chemical synthesis* / Q000737:chemistry; D012991:Solanaceous Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D013816:Thermodynamics
chemical_list: D017611:Fluorine Compounds; D009662:Nortropanes; D012991:Solanaceous Alkaloids; C095613:calystegine B(2)