Redox catalysis has been broadly utilized in electrochemical synthesis due to its kinetic advantages over direct electrolysis. Quality Control of Cuprous thiocyanate. Introducing a new discovery about 1111-67-7, Name is Cuprous thiocyanate, The appropriate choice of redox mediator can avoid electrode passivation and overpotential, which strongly inhibit the efficient activation of substrates in electrolysis.
Copper-catalyzed intramolecular C(sp3)-H and C(sp2)-H amidation by oxidative cyclization
The first copper-catalyzed intramolecular C(sp3)-H and C(sp 2)-H oxidative amidation has been developed. Using a Cu(OAc) 2 catalyst and an Ag2CO3 oxidant in dichloroethane solvent, C(sp3)-H amidation proceeded at a terminal methyl group, as well as at the internal benzylic position of an alkyl chain. This reaction has a broad substrate scope, and various beta-lactams were obtained in excellent yield, even on gram scale. Use of CuCl2 and Ag2CO3 under an O2 atmosphere in dimethyl sulfoxide, however, leads to 2-indolinone selectively by C(sp2)-H amidation. Kinetic isotope effect (KIE) studies indicated that C-H bond activation is the rate-determining step. The 5-methoxyquinolyl directing group could be removed by oxidation. Silver ox: By using a Cu(OAc)2 catalyst and an Ag2CO3 oxidant in dichloroethane solvent, C(sp3)-H amidation proceeded at a terminal methyl group as well as at the internal benzylic position of an alkyl chain. This reaction has a broad substrate scope, and various beta-lactams were obtained in excellent yield, even on a gram scale. Use of CuCl2 and Ag2CO3 under an O2 atmosphere led to 2-indolinone selectively synthesized by C(sp2)-H amidation. DMSO=dimethylsulfoxide.
The catalyzed pathway has a lower Ea, but the net change in energy that results from the reaction is not affected by the presence of a catalyst. In my other articles, you can also check out more blogs about 1111-67-7
Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”