Functionalized anilines are difficult to prepare using diaryliodonium salt intermediates, because the strong electron-donating ability of aryl amino substituents tends to divert incoming nucleophiles away from the electron rich ring. To circumvent this problem, we have installed readily cleaved carbamate and amide protecting groups (acetyl, trifluoroacetyl, and BOC) on the aniline nitrogen, and have prepared unsymmetrical diaryliodonium triflate salts therefrom. Following counterion exchange with TBAX (X=N3, OAc, OPh, SPh, NCO, SCN, Cl, Br), thermal decomposition of the ArAr'IX salts yielded the functionalized protected anilines in good to excellent yields. The decomposition products were subsequently deprotected to give the desired functionalized anilines. This synthetic approach lends itself to functionalization of a variety of natural products and pharmaceutical targets containing the aniline moiety.

Functionalization of anilines via diaryliodonium salts

246th National Meeting (2013)

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