Metal-Free Deoxygenation and Reductive Disilylation of Nitroarenes by Organosilicon Reducing Reagents

A metal-free deoxygenation and reductive disilylation of nitroarenes was achieved using N,N-bis(trimethylsilyl)-4,4'-bipyridinylidene (1) under mild and neutral reaction conditions, and a broad functional group tolerance was possible in this reaction. Mono-deoxygenation, giving a synthetically valuable N,O-bis(trimethylsilyl)phenylhydroxylamine (7a) as a readily available and safe phenylnitrene source from nitrobenzene, and double-deoxygenation, giving N,N-bis(trimethylsilyl)anilines 8, were easily controlled by varying the amounts of 1 and reaction temperature as well as adding dibenzothiophene (DBTP). Reaction of 2-arylnitrobenzenes with 1 resulted in the formation of the corresponding carbazoles 14 via in situ-generated phenylnitrene species derived by thermolysis of N,O-bis(trimethylsilyl)phenylhydroxylamines 7, followed by their subsequent intramolecular C-H insertion. In addition, the intramolecular N-N coupling reaction proceeded in the reduction of 2,2'-dinitrobiphenyl derivatives by 1, giving the corresponding benzo[c]cinnolines.