Short,Enantioselective Total Synthesis of Chatancin

An enantioselective total synthesis of the polycyclic diterpene (+)‐chatancin, a potent PAF antagonist, is reported. Proceeding in seven steps from dihydrofarnesal, this synthetic route was designed to circumvent macrocyclization‐based strategies to complex, cyclized cembranoids. The described synthesis requires only six chromatographic purifications, is high yielding, and avoids protecting‐group manipulations. An X‐ray crystal structure of this fragile marine natural product was obtained.     

A Palladium(II)‐Catalyzed C?H Activation Cascade Sequence for Polyheterocycle Formation

Polyheterocycles are found in many natural products and are useful moieties in functional materials and drug design. As part of a program towards the synthesis of Stemona alkaloids, a novel palladium(II)‐catalyzed C H activation strategy for the construction of such systems has been developed. Starting from simple 1,3‐dienyl‐substituted heterocycles, a large range of polycyclic systems containing pyrrole, indole, furan and thiophene moieties can be synthesized in a single step.     

Rhodium(III)‐Catalyzed [3+2]/[5+2] Annulation of 4‐Aryl 1,2,3‐Triazoles with Internal Alkynes through Dual C(sp2)?H Functionalization

A rhodium(III)‐catalyzed [3+2]/[5+2] annulation of 4‐aryl 1‐tosyl‐1,2,3‐triazoles with internal alkynes is presented. This transformation provides straightforward access to indeno[1,7‐cd]azepine architectures through a sequence involving the formation of a rhodium(III) azavinyl carbene, dual C(sp²) H functionalization, and [3+2]/[5+2] annulation.