A regioselective C_sp2–H dual functionalization of indoles, which underlies bromo-amination via the 1,3-migration of imide groups on indolyl(phenyl)iodonium imides, has been developed to provide 2-bis(sulfonyl)amino-3-bromo-indoles under the metal-free conditions.

The Hofmann-type rearrangement of aromatic and aliphatic imides using KBr as the catalyst proceeded to provide aromatic and aliphatic amino acid derivatives. We have also developed a new synthetic route to gabapentin with this method.

Various [(diacetoxy)iodo]arenes bearing 4-methylphenyl, phenyl, 4-nitrophenyl, 3-nitrophenyl, 4-cyanophenyl, 4-bromophenyl, 4-methoxycarbonyphenyl, 3,5-bis(trifluoromethyl)phenyl, and 4-(N,N,N-trimethylammonium)methylphenyl groups were efficiently prepared by the treatment of iodoarenes with m-chloroperoxybenzoic acid in acetic acid. The great advantage of the present method is the easy preparation and isolation of [(diacetoxy)-­iodo]arenes bearing electron-withdrawing groups, such as 4-nitro, 4-cyano, 4-methoxycarbonyl, and 3,5-bis(trifluoromethyl) groups, on the aromatic ring.