Photochemical Oxidation of Thioketones by Singlet Molecular Oxygen Revisited: Insights into Photoproducts, Kinetics, and Reaction Mechanism.

Photosensitized oxidation of trimethyl[2.2.1]bicycloheptane thioketones by (1)O2 can yield more photoproducts than exclusively ketones and sulfines.

Cheap and long-life reusable polymer for asymmetric organozinc catalysis based on camphor-derived hydroxyamides.

Polystyrene grafted with a chiral zinc-complexing camphor-derived N,N-disubstituted hydroxyamide is proposed as a new type of functional polymer of high reusability for the development of sustainable organozinc-catalyzed asymmetric reactions. The main goal of this new functional polymer is the ease of the hydroxyamide-moiety preparation (cheap chiral ligand obtained straightforwardly from an enantiopure starting material coming from the chiral pool), as well as its chemical robustness when compared with other related zinc-complexing functional groups. The latter allows the polymer to be active after multiple applications, without significant loss of its catalytic activity.

Electron ionization mass spectral studies of bridgehead-substituted norbornan-2-ones: camphor derivatives.

The electron ionization (EI) mass spectra of a series of bridgehead-substituted 3,3-dimethylnorbornan-2-ones, derived from natural (1R)-(+)-camphor, have been studied and their cleavage mechanisms rationalized on the basis of the substituent shifts as well as on the identification of relevant peaks through accurate mass measurements and collision-induced dissociation (CID) tandem mass spectrometric experiments. The fragmentation patterns are very dependent on both the structural nature and the electronic properties of the bridgehead substituent. The driving force for the main fragmentation pathways are competitive cleavages of the C(1)-C(2) and C(2)-C(3) bonds directed by the bridgehead substituent and either the gem-dimethyl or carbonyl groups.

Electron ionisation mass spectral studies of bridgehead-fused Delta2-norbornanethiazolines.

The electron ionisation (EI) mass spectra of a series of bridgehead-fused Delta2-norbornanethiazolines, a new class of bridgehead-norbornane derivatives, have been studied and their cleavage mechanisms rationalised on the basis of the substituent shifts as well as on the identification of relevant peaks through accurate mass measurements and collision-induced dissociation tandem mass spectrometric experiments. The fragmentation patterns of isomeric pairs of 6,6- and 10,10-dimethylnorbornanethiazolines are almost identical, probably due to an initial isomerisation of molecular ion previous to the fragmentation. In general, the dominant peaks in the spectra of all the studied compounds originate from initial alpha-cleavages of C(5)-C(6) or C(1)-C(10) bonds, followed by concomitant homolytic cleavage of C(1)-C(9) and C(7)-C(10) bonds.