The simultaneous construction of a CS and a CC bond under catalytic conditions forms the basis of an efficient route to diversely functionalized benzothiophenes from gem‐dihalovinyl thiophenols. The CC bond can be formed in this tandem catalytic process with an organoboron reagent as shown in the scheme (R1=H, Me, F, Cl, Br, OCH2O; R2=H, Me; R3=aryl, heteroaryl, alkenyl, alkyl), or by Heck or Sonogashira coupling with an alkene or alkyne.

Highly useful halogenated benzofurans and benzothiophenes are prepared from readily available gem-dibromoolefins using a mild, ligand-free copper catalyzed cross-coupling procedure.

The natural products cochliomycin A (1) and cochliomycin B (2), two resorcylic acid lactones obtained from marine sources, have been prepared in a concise and stereocontrolled manner from the readily accessible building blocks 4-6. Olefin cross-metathesis, trans-esterification and Nozaki-Hiyama-Kishi (NHK) macrocyclization reactions were employed in the key steps. Hydrolysis of the immediate precursor to cochliomycin B affords the resorcylic acid lactone zeaenol (24).

Compounds 1−6 and 11 representing key members of the marinoquinoline family of natural products, together with the related marine alkaloid aplidiopsamine A (12), have been synthesized using various combinations of palladiumcatalyzed Ullmann cross-coupling and reductive cyclization processes involving a C3-arylated pyrrole as the common intermediate. These natural products have been characterized by single-crystal X-ray analyses and evaluated as inhibitors of acetylcholinesterase (AChE) with congener 2 proving to be the most active.

The methylenindene scaffold can be prepared from readily available gem-dibromoolefins using an efficient palladium-catalyzed tandem intermolecular Suzuki/intramolecular Heck reaction. The reaction is highly modular and proceeds under mild conditions. The choice of ligand was found to be crucial to control the selectivity of the reaction. Isolation of intermediates under different conditions provides insight into the mechanism.