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.