TY - JOUR

T1 - Ring Lithiation of 1,8-Bis(dimethylamino)naphthalene: Another Side of the ‘Proton Sponge Coin’

AU - Antonov, Alexander S.

AU - Pozharskii, Alexander F.

AU - Ozeryanskii, Valery A.

AU - Filarowski, Aleksander

AU - Suponitsky, Kyrill Yu.

AU - Tolstoy, Peter M.

AU - Vovk, Mikhail A.

PY - 2015

Y1 - 2015

N2 - It has been found that 1,8-bis(dimethylamino)naphthalene (DMAN), unlike N,N-dimethylaniline, undergoes ring metallation in the n-BuLi–TMEDA–Et2O system with a low selectivity and in poor total yields. The situation is significantly improved in the t-BuLi–TMEDA–n-hexane system when 3- and 4-lithium derivatives become the only reaction products obtained in good yields. The formation of 3-Li-DMAN is especially desired since no method of direct meta-functionalization of DMAN is known to date. The relative stability and structure of DMAN lithium derivatives have been examined with the help of X-ray and multinuclear NMR measurements as well as DFT calculations.

AB - It has been found that 1,8-bis(dimethylamino)naphthalene (DMAN), unlike N,N-dimethylaniline, undergoes ring metallation in the n-BuLi–TMEDA–Et2O system with a low selectivity and in poor total yields. The situation is significantly improved in the t-BuLi–TMEDA–n-hexane system when 3- and 4-lithium derivatives become the only reaction products obtained in good yields. The formation of 3-Li-DMAN is especially desired since no method of direct meta-functionalization of DMAN is known to date. The relative stability and structure of DMAN lithium derivatives have been examined with the help of X-ray and multinuclear NMR measurements as well as DFT calculations.

KW - Спектроскопия ЯМР

KW - протонные губки

U2 - 10.1039/C5DT02482J

DO - 10.1039/C5DT02482J

M3 - Article

VL - 44

SP - 17756

EP - 17766

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 49

ER -