Total Synthesis of Conulothiazole A.

An efficient total synthesis of the chlorinated thiazole-containing natural product conulothiazole A is reported. Key features of this synthesis include a novel rhodium-catalyzed enantioselective hydrogenation of a 2-enamido-thiazole and a vinylic Finkelstein reaction that could be implemented at all stages of the synthesis to install the chlorinated alkene.

Copper-Mediated N-Arylations of Hydantoins.

A set of two broadly applicable procedures for the N-arylation of hydantoins is reported. The first one relies on the use of stoichiometric copper(I) oxide under ligand- and base-free conditions and enables a clean regioselective arylation at the N nitrogen atom, while the second one is based on the use of catalytic copper(I) iodide and trans- N, N'-dimethylcyclohexane-1,2-diamine and promotes arylation at the N nitrogen atom. Importantly, the combination of these two procedures affords a straightforward entry to diarylated hydantoins.

Cationic polycyclization of ynamides: building up molecular complexity.

Polycyclization reactions are among the most efficient synthetic tools for the synthesis of complex, polycyclic molecules in a single operation from simple starting materials. We report in this manuscript a full account on the discovery and development of a novel cationic polycyclization from readily available ynamides. Simple activation of these building blocks under acidic conditions enables the generation of highly reactive activated keteniminium ions, which triggers an unprecedented cationic polycyclization yielding highly substituted polycyclic nitrogen heterocycles possessing up to seven fused cycles and three contiguous stereocenters.