Trimethoxyphenyl (TMP) iodonium(III) acetate functionated as an efficient arylation reagent for N,O-protected hydroxylamines, generating aniline derivatives in the absence of transition metal catalysts. Various N-methoxysulfonamides participated in the amination reaction to produce the corresponding N-methoxysulfonylanilines. This amination reaction was compatible with several protecting groups, including Troc (2,2,2-trichloroethoxycarbonyl), Cbz (benzyloxycarbonyl), Boc (tert-butoxycarbonyl), benzyl, acetyl, and silyl groups. This method uses TMP-iodonium(III) acetate and efficiently synthesizes various aniline derivatives, that are versatile synthetic intermediates for functional organic molecules.

Herein, we develop a metal catalyst‐free protocol for O‐arylation of benzamide hydroxamate esters. The chemoselective O‐ versus N‐arylation of the amides was tuned by varying the electronic and/or steric properties of the diaryliodonium salt and/or the substrate. The O‐arylation reaction would preferentially occur for sterically and electronically diverse substrates. This study, which reveals the possibility of substituent‐ and reagent‐controlled chemoselectivity, with diaryliodonium salts might attract interest in the area of hypervalent iodine chemistry.magnified image

Utilization of α,α-dihalocarbonyl compounds as synthetic equivalents to α-halocarbonyl compounds has been explored in the synthesis of a wide range of highly useful heterocycles and α-functionalized ketones. The continuously growing demand of α,α-dibromoketones, as highly reactive and mild synthetic precursors/intermediates, to carry out selective organic transformations, prompted us to investigate their potential application for the synthesis of thiazolo[3,2-a]benzimidazoles. In this study, a remarkable application of α,α-dibromoacetophenones 5a-g in the development of a facile protocol for the synthesis of thiazolo[3,2-a]benzimidazoles 4a-g by avoiding the use of lachrymatory α-haloketones is described. Although the mechanism for the debromination from the intermediate compound 6 under these conditions is not confirmed, possible pathways have been suggested.