Addition reactions of organometallic reagents to nitrogen trifluoride and enhanced alkyl–alkyl coupling by NF3

• R-NF2 were prepared in moderate yields by treating solutions of NF3 with R-Mg and R-Li reagents.
• R2CuX and R2Zn reagents undergo R–R coupling when reacted with solutions NF3.
• R-Ca and R3Al reagents are unreactive to solutions of NF3.

A survey of the reaction of nitrogen trifluoride (NF3) with various organometallic reagents finds that organomagnesium (Grignard) reagents are the most useful for producing N,N-difluoroaminoalkanes. Alkyl–alkyl coupling is a persistant side reaction. Organolithiums are marginally effective. Organocopper, organozinc reagents undergo primarily alkyl–alkyl coupling catalyzed by the presence of NF3. Organocalcium and organoaluminum reagents are unreactive.

Figure optionsDownload as PowerPoint slide