The synthesis of densely functionalised α-acyloxy enaminals and enaminones via a novel homogeneous silver(i) catalysed rearrangement.

A synthesis of densely functionalised α-acyloxy enaminals and enaminones via a novel homogeneous silver(i) catalyzed rearrangement of 1-acyloxy-3-azido ketones is reported. This silver catalyzed reaction involves an internal redox process comprised of four net transformations: loss of nitrogen, reductive cleavage of the azide, 1,2-acyl migration and oxidation of the acyloxy position to an aldehyde (enaminal) or ketone (enaminone). These mild reaction conditions have been applied to acyclic, cyclic, and chiral substrates yielding the rearranged enaminals or enaminones in up to 91% yield, all of which prove to be stable, isolatable products.

Synthesis of the cyanobacterial metabolite nostodione A, structural studies and potent antiparasitic activity against Toxoplasma gondii.

A total synthesis of the cyanobacterial natural product nostodione A is reported involving a convergent, diversity-oriented route, enabling the assembly of a mini-library of structural analogues. The first single crystal X-ray structural determination on a member of this series is reported along with SAR studies identifying potent inhibitors of invasion and replication of the parasitic protozoan Toxoplasma gondii.

Discovery of a new class of cinnamyl-triazole as potent and selective inhibitors of aromatase (cytochrome P450 19A1).

Synthesis of a novel class of natural product inspired cinnamyl-containing 1,4,5-triazole and the potent inhibition of human aromatase (CYP 450 19A1) by select members is described. Structure-activity data generated provides insights into the requirements for potency particularly the inclusion of an aryl bromide or chloride residue as a keto-bioisostere.

High yielding synthesis of carboranes under mild reaction conditions using a homogeneous silver(I) catalyst: direct evidence of a bimetallic intermediate.

Methods used to prepare functionalized carboranes generally require heating to high temperatures, and thus limits the range of derivatives which can be prepared directly from alkynes. We show here that by using a homogeneous silver(I) catalyst it is now possible to prepare carboranes in good to excellent yield at temperatures below 40 °C, including at room temperature. The process is general and provides an important new synthetic strategy for the preparation of functionalized boron clusters.

Phthalide: a direct building-block towards P,O and P,N hemilabile ligands. Application in the palladium-catalysed Suzuki-Miyaura cross-coupling of aryl chlorides.

The direct synthesis of new hemilabile ligands from the economical, readily available lactone phthalide is described. Pd-complexes of one such ligand were found highly effective in general Suzuki-Miyaura cross-coupling reactions, including deactivated and hindered aryl chlorides.

Isolation of flavonoids from the heartwood and resin of Prunus avium and some preliminary biological investigations.

An investigation of the constituents in heartwood and resin of Prunus avium is reported. A mini-library of structurally diverse flavanones and flavones was screened for human cytochrome P450 1A1, 3A4 and 19 (aromatase) inhibition, and for antifungal activity against a panel of pathogenic fungi. The defensive role of these natural plant flavonoids as antifungal phytoalexins and phytoanticipins is discussed.