Electrochemical S–H and O–H insertion reactions from thiols or salicylic acids with diazo esters

Abstract

An electrochemical carbenoid insertion reaction of diazo compounds into C-S and C-O bonds with electricity as oxidant has been reported in this work. In this protocol, this transformation proceeded smoothly...

Electrochemical Construction of C–S Bond: A Green Approach for Preparing Sulfur-Containing Scaffolds

“…18 ). 54 The S–H insertion reaction was performed at room temperature under 5 mA constant current in an undivided electrolytic cell equipped with a graphite anode and a graphite cathode using TBAB as the electrolyte and DCE as the solvent. A variety of thiols underwent S–H insertion reactions with diazo esters, giving the desired product in moderate to high yields.…”

O–H Insertion of Hydrogenphosphate Derivatives and α-Diazo Compounds

“…However, the costs and toxicity of these metals as well as the ligands involved restrict this traditional methodology, thus making it necessary and attractive to develop metal-free strategies. Recently, Brønsted acid catalysis, Lewis acid catalysis, , photosynthesis, and electrosynthesis have been applied in the O–H insertions successfully (Scheme b), which provide environmentally benign and economical alternatives for this important transformation.…”

Unveiling catalyst-free electro-photochemical reactivity of aryl diazoesters and facile synthesis of oxazoles, imide-fused pyrroles and tetrahydro-epoxy-pyridines via carbene radical anions

“…In one recent example, Huang et al used diazoesters in an electrochemical reaction but the diazoester was not electrochemically activated or explored in that work. 11 Careful curation of the literature revealed that there are only a few reports to date demonstrating the generation of carbene anion radicals. The McDonald research group (1986) and later Parker and Bethell et al (1989) reported the electrochemical generation of the diazoalkane radical followed by thermal loss of dinitrogen to form the carbene anion radical.…”

“…In one recent example, Huang et al used diazoesters in an electrochemical reaction but the diazoester was not electrochemically activated or explored in that work. 11 …”