title: Asymmetric catalytic oxidative cleavage of polycyclic systems: the synthesis of atropisomeric diazonanes and diazecanes.
abstract: Oxidative cleavage of internal double bonds in polycyclic systems can give access to compounds containing medium- to large-sized rings. In this example, the nine- and ten-membered ring containing compounds that resulted from the mCPBA-mediated (mCPBA=meta-chloroperoxybenzoic acid) oxidative cleavage reaction were shown to exhibit atropisomerism. The reaction of the polycyclic system with catalytic amounts of ruthenium tetraoxide followed by diol cleavage achieved the same synthetic goal. Use of the Nishiyama-Beller ruthenium-based catalysts enabled the synthesis of optically-enriched samples, providing the first example of an atropselective oxidative cleavage reaction.
authors.affiliation: School of Chemistry and Biomedical Sciences Research Complex, University of St Andrews, North Haugh, St Andrews, KY16 9ST, UK.
authors.forename: Alan M
authors.initials: AM
authors.lastname: Jones
authors.forename: Gu
authors.initials: G
authors.lastname: Liu
authors.forename: Magali M
authors.initials: MM
authors.lastname: Lorion
authors.forename: Stephen
authors.initials: S
authors.lastname: Patterson
authors.forename: Tomas
authors.initials: T
authors.lastname: Lebl
authors.forename: Alexandra M Z
authors.initials: AM
authors.lastname: Slawin
authors.forename: Nicholas J
authors.initials: NJ
authors.lastname: Westwood
mesh_terms: D001372:Aza Compounds / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D006576:Heterocyclic Compounds, 4 or More Rings / Q000138:chemical synthesis* / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D010084:Oxidation-Reduction; D011084:Polycyclic Aromatic Hydrocarbons / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D001372:Aza Compounds; D006576:Heterocyclic Compounds, 4 or More Rings; D011084:Polycyclic Aromatic Hydrocarbons; D012428:Ruthenium