First chemo-enzymatic synthesis of the ( R )-Taniguchi lactone and substrate profiles of CAMO and OTEMO, two new Baeyer– Villiger monooxygenases

This study investigates the substrate profile of cycloalkanone monooxygenase and 2-oxo-Δ3-4,5,5-trimethylcyclopentenylacetyl-coenzyme A monooxygenase, two recently discovered enzymes of the Baeyer–Villiger monooxygenase family, used as whole-cell biocatalysts. Biooxidations of a diverse set of ketones were performed on analytical scale: desymmetrization of substituted prochiral cyclobutanones and cyclohexanones, regiodivergent oxidation of terpenones and bicyclic ketones, as well as kinetic resolution of racemic cycloketones. We demonstrated the applicability of the title enzymes in the enantioselective synthesis of (R)-(−)-Taniguchi lactone, a building block for the preparation of various natural product analogs such as ent-quinine.Austrian Scientific Foundation (FWF)EU-FP7 Oxygree

Polycyclic Aromatic Triptycenes: Oxygen Substitution Cyclization Strategies

The cyclization and planarization of polycyclic aromatic hydrocarbons with concomitant oxygen substitution was achieved through acid catalyzed transetherification and oxygen-radical reactions. The triptycene scaffold enforces proximity of the alcohol and arene reacting partners and confers significant rigidity to the resulting π-system, expanding the tool set of iptycenes for materials applications.Natural Sciences and Engineering Research Council of CanadaNational Institutes of Health (U.S.) (NIH BRP grant R01 AG026240-01A1)Natural Sciences and Engineering Research Council of Canada (NSERC) (Postdoctoral Fellowship)United States. Air Force Office of Scientific Research (FA9550-10-1- 0395