Amino‐ and Alkoxybenziodoxoles: Facile Preparation and Use as Arynophiles

Abstract

We report here on the facile synthesis of amino‐ and alkoxy‐λ3‐iodanes supported by a benziodoxole (BX) template and their use as arynophiles. The amino‐ and alkoxy‐BX derivatives can be readily synthesized by reacting the respective amines or alcohols with chlorobenziodoxole in the presence of a suitable base. Unlike previously known nitrogen‐ and oxygen‐bound iodane compounds, which have primarily been employed as electrophilic group transfer agents or oxidants, the present amino‐ and alkoxy‐BX reagents manifest themselves as nucleophilic amino and alkoxy transfer agents toward arynes. This reactivity leads to the aryne insertion into the N–I(III) or O–I(III) bond to afford ortho‐amino‐ and ortho‐alkoxyarylbenziodoxoles, iodane compounds nontrivial to procure by existing methods. The BX group in these insertion products exhibits excellent leaving group ability, enabling diverse downstream transformations.