CO2, as a sustainable, feasible, abundant one-carbon synthon, has been utilized in carboxylative cyclization, carbonylative cyclization, and reductive cyclization.

An efficient synthetic approach to variously substituted thiophenes has been developed through copper-catalyzed tandem S-alkenylation of potassium sulfide with 1,4-diiodo-1,3-dienes.

Metalloles are derivatives of cyclopentadiene in which the methylene unit is replaced by a heteroatom, such as S, Se, Te, N, P, As, Sb, Bi, Si, Ge, Sn, B, Al, Ga, and so on. Many metallole derivatives have been widely used as photovoltaic cells, organic light emitting diodes (OLEDs), chemical sensors, electrochromic devices, microelectronic actuators, and organic field effect transistors (OFETs). In the meantime, many of them showed promising biological actives. Due to the similarity to cyclopentadiene, the anionic forms of metalloles were also widely explored in coordination chemistry. As a result, development of a general method for the formation of metalloles from available starting materials is highly desired. In this Account, we outline formation of various p-block element metalloles from zirconacyclopentadienes. The zirconacyclopentadienes can be easily prepared from two molecules of alkynes and a low-valent zirconocene species "Cp2Zr(II)" (Cp = cyclopentadienyl). Fagan and Nugent first reported the formation of main group metalloles from zirconacyclopentadiene, which provided a versatile approach for the construction of metalloles, especially for the formation of metalloles in heavier p-block elements. To further expand the substrate scope, a number of stepwise conversions were developed, which involve 1,4-dimetallo- or dihalo-1,3-butadiene as intermediates from zirconacyclopentadienes. Here, four processes are classified based on direct and indirect conversion of zirconacyclopentadienes into metalloles. Direct reaction of zirconacyclopentadienes with element halides afforded heterocycles of main group elements, which provided a versatile method for the synthesis of metalloles. Nonetheless, the reaction scope was restricted to heavier p-block elements such as S, Se, P, As, Sb, Bi, Ge, Sn, Ga, and In. And these reactions usually suffered low yields and long reaction time. Transmetalation of zirconacyclopentadiene with copper chloride greatly enriched the zirconacyclopentadiene chemistry. The synthesis of stannoles and pyrroles from zirconacyclopentadienes has been developed in the presence of CuCl. The direct reaction of the zirconacyclopentadienes with SiCl4 or R2SiCl2 does not give the desired silacyclopendadiene derivatives, even in the presence of CuCl. It can be circumvented by using dilithiated dienes from diiododienes, which are easily prepared by the iodination of zirconacyclopentadienes using CuCl as an additive. Finally, an umpolung strategy, reaction of electrophilic 1,4-diiodo-1,3-butadiene with nucleophilic amine or sulfide reagents, was successfully used in the formation of pyrroles and thiophenes.