Total Synthesis of Crocagin A.

Crocagin A (1) combines an attractive molecular structure with an unusual biosynthesis and bioactivity. An efficient synthesis of crocagin A is presented that hinges on an early formation of the heterotricyclic core, an electrophilic amination, and the stereoselective hydrogenation of a tetrasubstituted double bond. This synthesis confirms the absolute configuration of crocagin A and provides access to the natural product and derivatives thereof for further biological testing.

Photochemical formation of intricarene.

Sunlight is the ultimate driver of biosynthesis but photochemical steps late in biosynthetic pathways are very rare. They appear to play a role in the formation of certain furanocembranoids isolated from Caribbean corals. One of these compounds, intricarene, has been suspected to arise from an intramolecular 1,3-dipolar cycloaddition involving an oxidopyrylium.

The crystal structure of the Dess-Martin periodinane.

We report the elusive X-ray structure of the Dess-Martin periodinane (DMP), a hypervalent iodine reagent popular amongst synthetic chemists. In the solid state, the highly crystalline compound forms an intricate coordination polymer held together by intermolecular halogen and hydrogen bonds.