We report herein the synthesis of a fully functionalized B,C,D-ring system of lancifodilactone F. The key transformations involve an arene-olefin meta-photocycloaddition reaction and a palladium-catalyzed oxidative C-C cleavage reaction to establish its B,C-rings.

Under the influence of ethanolic acetic acid the aplysiatoxins rearrange with retention of all carbon atoms. An osmate of the anhydrotoxins can be rediced to a glycol which resists oxidative cleavage but loses water and rearranges with acid. Consideration of PMR and reactivity datalead to partialassignment of relative stereochemistry of

An efficient synthetic method of 1,3-bis(arylethynyl)isobenzofurans is developed. Nucleophilic addition of alkynyllithium to benzocyclobutenone and subsequent oxidative ring cleavage of the four-membered ring gave a keto-aldehyde, which, in turn, accepted the second nucleophile to produce isobenzofurans after acid treatment.

Dissociation of disulfide is normally mandatory prior to disulfide peptide sequencing via electrospray ionization collision induced dissociation mass spectrometry (ESI-CID-MS). Herein, a facile method for directly sequencing intact disulfide peptides was proposed. The basic principles involved were electrolyte-enhanced corona discharge in ESI and the following oxidative cleavage reaction.

Exposure of 3-hydroxyflavonolate complexes of the group 12 metals to UV light under aerobic conditions results in oxidative carbon-carbon bond cleavage and CO release. This reactivity is novel in that it occurs under mild reaction conditions and suggests that light-induced CO-release reactivity involving metal flavonolate species may be possible in biological systems.

The rhodium-catalyzed oxidative C2-olefination of indoles and pyrroles containing N-arylcarboxamide directing groups with a range of alkenes and subsequent cleavage of directing groups is described. This method provides direct and efficient access to C2-functionalized free (NH)-heterocycles.

An efficient CuBr catalyzed cleavage of C-N bonds in the oxidative cross-dehydrogenative-coupling (CDC) of N-benzyl amines with indoles mediated by tert-butyl hydroperoxide (TBHP) was reported. A series of methine-bridged bis-indole derivatives were successfully synthesized under the optimized reaction conditions.

The first report of a biocatalytic regioselective oxidative mono-cleavage of dialkenes was successfully achieved employing a cell-free enzyme preparation from Trametes hirsuta at the expense of molecular oxygen. Selected reactions were performed on a preparative scale affording high to excellent conversions and chemoselectivities.

The palladium-catalyzed Sonogashira-type aerobic oxidative coupling of arylhydrazines with terminal alkynes via C-N bond cleavage has been developed; internal alkynes were afforded with a broad substrate scope. This reaction proceeds under copper- and base-free conditions with molecular oxygen as the sole oxidant and nitrogen and water as the only by-products.

The sequential introduction of two carbon nucleophiles on the same alpha-carbon of nitrogen by using selective oxidative cleavage of two silyl groups as electroauxilialies has been accomplished. The combination of this expedient transformation and ring-closing metathesis enables reliable and straightforward syntheses of nitrogen-containing spiro compounds, such as cephalotaxine.