The progress of the metal-catalyzed annulation reactions toward construction of various π-conjugated polycyclic cores with high conjugation extension is described. This article gives a brief overview of various annulation reactions promoted by metal catalysts including C-H bond functionalization, [2+2+2] cycloaddition, cascade processes, ring closing metathesis, electrophilic aromatization, and various cross-coupling reactions. A variety of conjugated polycycles with planar, bowl-shaped, and helical structures have been constructed in high efficiency and selectivity.

The reaction of silylaryl triflates, CsF, and ortho-heteroatom-substituted benzoates affords a general and efficient way to prepare biologically interesting xanthones, thioxanthones, and acridones. This chemistry presumably proceeds by a tandem intermolecular nucleophilic coupling of the benzoate with an aryne and a subsequent intramolecular electrophilic cyclization.

Biologically interesting fluoren-9-one and xanthen-9-one derivatives have been prepared by a novel aryl to imidoyl palladium migration, followed by intramolecular arylation. The fluoren-9-one synthesis appears to involve both a palladium migration mechanism and a C-H activation process proceeding through an unprecedented organopalladium(IV) hydride intermediate. The results from deuterium labeling experiments are consistent with the proposed dual mechanism.

A novel catalytic property of nanoporous gold for activation of bis(pinacolato)diboron has been reported that allows the direct diboration of alkynes to proceed sufficiently in a heterogeneous process. The experimental results revealed that the nanoporous gold catalyst is able to cleave the B-B bond of bis(pinacolato)diboron without using any additives.