Silylation of 2H-indazoles by photoinduced hydrogen atom transfer catalysis.

A metal-free, visible-light-mediated C-H silylation of 2H-indazoles with triphenylsilane has been developed employing 4CzIPN as a photocatalyst and triisopropylsilanethiol as a hydrogen atom transfer (HAT) reagent under aerobic reaction conditions. This method shows tolerance toward many functional groups and affords a variety of silylated indazoles at up to 89% yield. The experimental results suggest that the reaction progresses through a radical pathway.

Late-stage ortho-C-H alkenylation of 2-arylindazoles in aqueous medium by Manganese(i)-catalysis.

Earth-abundant and water-tolerant manganese(i) catalyzed alkenylation of 2-arylindazole with alkyl and aryl alkynes through C-H bond activation is described with a unique level of E-selectivity. The reaction proceeds through the control of C3 nucleophilicity of 2-aryl indazoles. This method is applied to the late-stage functionalization of complex molecules including ethinylestradiol, norethisterone, and N-protected amino acid derivatives. The kinetic isotope studies suggest that the C-H bond activation step may not be the rate-determining step.

Organocatalytic Oxidative C-H Amination of Aldehyde Hydrazones with Azoles at Ambient Temperature.

An efficient, metal-free, and direct oxidative amination of aldehyde-derived hydrazones with azoles has been developed using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone as an organocatalyst at ambient temperature. This protocol provides a wide range of aminated hydrazone derivatives in a step and atom economical fashion. The reaction possibly follows a radical mechanism.