Visible-Light-Triggered Radical-Addition/Ring-Opening Cascade Reactions of 2H-Indazoles to Access ortho-Alkoxycarbonylated Azobenzenes.

A series of asymmetric azobenzenes have been synthesized by radical-addition/ring-opening cascade reactions from 2H-indazole in the presence of PIFA and alcohols under blue light irradiation and nitrogen protection. Furthermore, a wide range of functional groups were tolerated and the corresponding products were obtained in 30% to 95% isolated yields. The protocol is characterized by its visible-light initiation, avoidance of metals and photocatalysts, mild reaction conditions, and may find potential use in materials science and medicinal chemistry.

Trace amounts of palladium catalysed the Suzuki-Miyaura reaction of deactivated and hindered aryl chlorides.

Electron-rich and hindered aryl chlorides are the most challenging substrates in Suzuki-Miyaura cross-coupling (SMC) reactions. Herein, we report a highly efficient catalytic system for the SMC reaction using trace amounts of commercially available catalysts [Pd(PPh3)4/(t-Bu)PCy2; Pd loading as low as 9.5 × 10-5 mol%]. This catalytic system can efficiently couple deactivated and sterically hindered aryl chlorides with various substituted phenylboronic acids, even in one-pot multiple coupling reactions (yield of products up to 92%). The impact of solvents on SMC reactions and the mechanisms of by-product formation in aryl boronic acid couplings are analyzed using density functional theory (DFT). Utilizing trace amounts of commercially available catalysts avoids complex synthesis, reduces costs, and minimizes metal residues.