Laying the way to meta-functionalization of naphthalene proton sponge via the use of Schlosser's superbase

Publication date: Available online 12 December 2017 Source:Journal of Organometallic Chemistry Author(s): Alexander S. Antonov, Victor G. Bardakov, Alexander F. Pozharskii, Mikhail A. Vovk, Alexander D. Misharev Lithiation of 1,8-bis(dimethylamino)naphthalene (DMAN) with Schlosser's superbase (n-BuLi–t-BuOK) in the presence of TMEDA in hexane was examined. It has been shown that, compared with previously studied n-BuLi–TMEDA or t-BuLi–TMEDA mixtures, this reagent provides much more selective meta-lithiation. A variety of 3-substituted and 3,6-disubstituted derivatives of DMAN has been prepared in a good to reasonable yield after quenching the reaction mass with different electrophiles. A possibility of further functionalization of thus introduced meta-substituents to synthesize more complex 3-substituted derivatives of DMAN is also demonstrated. Graphical abstract

Source: Journal of Organometallic Chemistry - December 12, 2017 Category: Chemistry Source Type: research