10.1021/jo102566e.s003 Yuka Nakamura Yuka Nakamura Shinya Tanaka Shinya Tanaka Ryuichi Serizawa Ryuichi Serizawa Naoya Morohashi Naoya Morohashi Tetsutaro Hattori Tetsutaro Hattori Synthesis of Mono- and 1,3-Diaminocalix[4]arenes via Ullmann-Type Amination and Amidation of 1,3-Bistriflate Esters of Calix[4]arenes American Chemical Society 2011 stoichiometric conditions monoamine 4 b acidic conditions 17 b 2 b bistriflate 4 b triflate monoamine 4 hydrogenolysi bi 7 b diamine reaction conditions benzylamino moiety monoamines 4 Tf moiety amidation compounds 4 disubstitution 5 b hydrolysis 1 b compounds 1 ester amination 2011-04-01 00:00:00 Dataset https://acs.figshare.com/articles/dataset/Synthesis_of_Mono_and_1_3_Diaminocalix_4_arenes_via_Ullmann_Type_Amination_and_Amidation_of_1_3_Bistriflate_Esters_of_Calix_4_arenes/2672605 Practical methods are described for the preparation of monoamines <b>4</b> and 1,3-diamines <b>5</b>, bearing one or two amino group(s) instead of the hydroxy group(s) at the 28-position or at both the 26- and 28-positions of <i>p</i>-<i>tert</i>-butylcalix[4]arene (<b>1a</b>) and <i>p</i>-<i>tert</i>-butylthiacalix[4]arene (<b>1b</b>), via the Ullmann-type amination or amidation. Thus, the copper-catalyzed or mediated amination of the 1,3-bistriflate ester (<b>2a</b>) of <b>1a</b> with benzylamine affords either mono(benzylamino) triflate <b>7a</b> or 1,3-bis(benzylamine) <b>8</b> in a high yield, depending on the reaction conditions. On the other hand, the 1,3-bistriflate ester (<b>2b</b>) of <b>1b</b> resists disubstitution and produces, under stoichiometric conditions, mono(benzylamino) triflate <b>7b</b>. The disubstitution of <b>2b</b> is achieved by amidation with tosylamide, giving 1,3-bis(tosylamide) <b>17b</b>. The hydrogenolysis of the benzylamino moiety of <b>7a</b>, followed by the hydrolysis of the Tf moiety, affords monoamine <b>4a</b>, while the hydrogenolysis of <b>8</b> affords 1,3-diamine <b>5a</b>. The amino moiety of <b>7b</b> can be deprotected under acidic conditions to give, after hydrolysis, monoamine <b>4b</b>. The hydrolysis of <b>17b</b> affords 1,3-diamine <b>5b</b>. The overall yields of compounds <b>4a</b>, <b>4b</b>, <b>5a</b>, and <b>5b</b> are 72%, 45%, 78%, and 24%, respectively, based on commercially available compounds <b>1</b> and are much higher than the ones previously reported in the literature.