A new oxidation reaction based on two simple catalysts, namely, alloxan and a Cu^I salt, is highly effective for the aerobic oxidation and oxidative cross-coupling of amines. The reaction is operationally simple, reaction atmospheres enriched in dioxygen are obviated, and neither catalyst component requires prior synthesis. Mechanistic investigations have been performed and point towards a complex reaction manifold with evidence that supports a catalytic cycle that does not proceed through a quinone-imine step. Additionally, this dual catalyst system is efficient to effect diimide-mediated hydrogenation reactions of alkenes and alkynes, a transformation that has not been reported previously in the context of quinone catalyst systems.

The flavoenzyme monoamine oxidase (MAO) regulates mammalian behavioral patterns by modulating neurotransmitters such as adrenaline and serotonin. The mechanistic basis which underpins this enzyme is far from agreed upon. Reported herein is that the combination of a synthetic flavin and alloxan generates a catalyst system which facilitates biomimetic amine oxidation. Mechanistic and electron paramagnetic (EPR) spectroscopic data supports the conclusion that the reaction proceeds through a radical manifold. This data provides the first example of a biorelevant synthetic model for monoamine oxidase B activity.

The flavoenzyme monoamine oxidase (MAO) regulates mammalian behavioral patterns by modulating neurotransmitters such as adrenaline and serotonin. The mechanistic basis which underpins this enzyme is far from agreed upon. Reported herein is that the combination of a synthetic flavin and alloxan generates a catalyst system which facilitates biomimetic amine oxidation. Mechanistic and electron paramagnetic (EPR) spectroscopic data supports the conclusion that the reaction proceeds through a radical manifold. This data provides the first example of a biorelevant synthetic model for monoamine oxidase B activity.

Poly(mandelic acid) (PMA) is an aryl analogue of poly(lactic acid) (PLA) and a biodegradable analogue of polystyrene. The preparation of stereoregular PMA was realized using a pyridine/mandelic acid adduct (Py⋅MA) as an organocatalyst for the ring-opening polymerization (ROP) of the cyclic O-carboxyanhydride (manOCA). Polymers with a narrow polydispersity index and excellent molecular-weight control were prepared at ambient temperature. These highly isotactic chiral polymers exhibit an enhancement of the glass-transition temperature (T_g) of 15 °C compared to the racemic polymer, suggesting potential future application as high-performance commodity and biomedical materials.

Poly(mandelic acid) (PMA) is an aryl analogue of poly(lactic acid) (PLA) and a biodegradable analogue of polystyrene. The preparation of stereoregular PMA was realized using a pyridine/mandelic acid adduct (Py⋅MA) as an organocatalyst for the ring-opening polymerization (ROP) of the cyclic O-carboxyanhydride (manOCA). Polymers with a narrow polydispersity index and excellent molecular-weight control were prepared at ambient temperature. These highly isotactic chiral polymers exhibit an enhancement of the glass-transition temperature (T_g) of 15 °C compared to the racemic polymer, suggesting potential future application as high-performance commodity and biomedical materials.

The gold-catalysed double functionalisation of indoles is presented. Enynones are used to annulate indoles via a double sodium tetrachloroaurate-catalysed process involving a mixture of CH activation and alkyne activation modes of promotion. Good yields for the formation of medicinally relevant [6,5,7]-tricyclic indoles are realised.