SYNTHESIS OF UNSYMMETRIC HetAr-X-HetAr' COMPOUNDS BY RHODIUM-CATALYZED HETEROARYL EXCHANGE REACTIONS

Unsymmetric HetAr-X-HetAr' compounds have flexible and chiral structures, and are expected to exhibit various biological activities by interacting with proteins and nucleic acids. Unsymmetric HetAr-X-HetAr' compounds were efficiently synthesized by rhodium-catalyzed heteroaryl exchange reactions, which involved equilibrium control by judicious design of organic heteroaryl reagents. By using this method, unsymmetric HetAr-O-HetAr', HetAr-S-HetAr', and HetAr-CH(2-)HetAr' compounds as well as HetAr-F compounds were obtained from heteroaryl aryl ethers and various heteroaryl reagents. The rhodium-catalyzed synthesis has a broad applicability, which gives novel unsymmetric HetAr-X-HetAr' compounds containing five- and six-membered heteroarenes.