Air Oxidative Radical Oxysulfurization of Alkynes Leading to α-Thioaldehydes.

Air oxidative radical oxysulfurization of alkynes initiated by 0.5 mol % tert-butyl hydroperoxide with arylthiols is described. The reaction proceeded at room temperature in the presence of 5% mol water to afford selective α-thioaldehydes.

Manganese(III)-mediated selective diphenylphosphinoyl radical reaction of 1,4-diaryl-1-butynes for the synthesis of 2-phosphinoylated 3,4-dihydronaphathalenes.

A diphenylphosphinoyl radical-initiated sequential reaction of 1,4-diaryl-1-butynes and analogues is developed for the synthesis of 2-phosphinoylated 3,4-dihydronaphathalenes and related compounds.

Manganese(III)-mediated phosphinoyl radical reactions for stereoselective synthesis of phosphinoylated tetrahydronaphthalenes.

Reactions of diphenylphosphinoyl radicals with 5-aryl-2-pentenoates or ß-phenylethylene styrenes generate trans-substituted tetrahydronaphthalenes through a cascade reaction sequence.

Manganese(III)-mediated direct phosphonation of arylalkenes and arylalkynes.

Mn(iii)-mediated phosphonations of carbon-carbon double and triple bonds to form alkenylphosphonates are introduced.

Manganese(III)-promoted reactions for formation of carbon-heteroatom bonds.

Manganese(III) reagent is an important one- electron oxidant for initiation of free-radical reactions and formation of carbon-carbon bonds. The reactions are usually carried out under mild conditions, have high regio- and stereo-selectivities, and good functional group tolerance. Summarized in this article are the developments of manganese (III)-based reactions for the formation of carbon-heteroatom bonds including carbon-oxygen, carbon-phosphorus, carbon-sulfur, and carbon-nitrogen bonds, and their applications for the synthesis of related heterocyclic systems.