Copper-Catalyzed Vicinal Thiocyanosulfonylation of Alkenes and Alkynes.

Efficient copper-catalyzed radical thiocyanosulfonylation of alkenes and alkynes with potassium thiocyanate and sodium phenylsulfinate is described. The reactions provide general and convenient methods toward the synthesis of β-thiocyanoalkyl sulfones and β-thiocyanoalkenyl sulfones, respectively, in satisfactory yields. Based on conducted mechanistic experiments, a mechanism involving oxidative generation of sulfonyl radicals and subsequent addition to alkenes followed by Cu-assisted thiocyanation is proposed.

Copper-Catalyzed Radical Hydrazono-Phosphorylation of Alkenes.

An efficient copper-catalyzed radical hydrazono-phosphorylation of alkenes with hydrazine derivatives and diarylphosphine oxides is described. The reaction provides a general and convenient method toward the synthesis of diverse β-hydrazonophosphine oxides in satisfactory yields. Based on conducted mechanistic experiments, a mechanism involving Ag-catalyzed oxidative generation of phosphinoyl radicals and subsequent addition to alkenes followed by Cu-assisted hydrazonation is proposed.

Copper-Catalyzed Stereoselective Radical Phosphono-hydrazonation of Alkynes.

A copper-catalyzed stereoselective phosphono-hydrazonation of terminal alkynes with alkyl carbazates and diarylphosphine oxides is described. This methodology provides facile access to a variety of β-hydrazonophosphine oxides in satisfactory yields. The reaction proceeds under mild conditions and exhibits good functional group tolerance.