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Helvetica Chimica Acta Vol. 86 (2003)
(br. s, 6 H). 13C-NMR (50 MHz, (CD3)2SO): 147.21; 131.75; 127.63; 122.29; 120.26; 117.44; 114.55; 113.37; 90.11;
84.39. HR-MALDI-MS: 423.172 (100, M , C30H21N3 ; calc. 423.173).
Tri-(tert-butyl) N,N',N''-(Benzene-1,3,5-triyl)tris{(S)-[(ethyne-1,2-diyl)-(1,3-phenylene)iminocarbonyl](2-
methylpropyl)methylene}tricarbamate ((S,S,S)-18). A soln. of 17 (600 mg, 1.42 mmol), N-Boc-L-Leu (645 mg,
2.79mmol), DMAP (30 mg, 0.24 mmol), and EDC ¥ HCl (760 mg, 3.96 mmol) in dry DMF (50 ml) was stirred
for 24 h at 08. Additional N-Boc-l-Leu (645 mg, 2.79mmol) and EDC ¥ HCl (760 mg, 3.96 mmol) were added,
and stirring was continued at 08 for 24 h. After repeating once more this addition and stirring for 24 h, the
mixture was evaporated in vacuo, and the residue was taken up in CH2Cl2. The org. phase was washed with 1m
HCl (3Â), sat. aq. NaHCO3 soln. (3Â), and dried (MgSO4). Evaporation in vacuo and FC (SiO2; CH2Cl2/
AcOEt 4 :1) afforded (S,S,S)-18 (772 mg, 51%). M.p. 1768. [a]2D3 71.8 (c 1, CHCl3). IR (KBr): 3310 (br.),
2957m, 1669s, 1607m, 1584m, 1551w, 1367m, 1250m, 1166s, 1122w, 1047w, 876m, 788m, 683m. 1H-NMR
(500 MHz, (CD3)2SO): 10.08 (s, 3 H); 7.9 3 (s, 3 H); 7.77 (s, 3 H); 7.58 (d, J 7.8, 3 H); 7.38 (dd, J 7.8, 7.8, 3 H);
7.28 (d, J 7.8, 3 H); 7.04 (d, J 7.7, 3 H); 4.14 4.11 (m, 3 H); 1.66 1.33 (m, 3 H); 1.57 1.55 (m, 3 H); 1.48
1.42 (m, 3 H); 1.37 (s, 27 H); 0.89( t, J 4.8, 18 H). 13C-NMR (125 MHz, (CD3)2SO): 172.1; 155.4; 142.7; 139.2;
133.8; 129.3; 126.4; 124.3; 123.6; 121.9; 121.8; 120.1; 90.7; 87.1; 78.0; 53.6; 28.1; 24.3; 22.8; 21.5. HR-MALDI-MS:
1085.573 (100, [M Na] , C63H78N6O9Na ; calc. 1085.573). Anal. calc. for C63H78N6O9: C 71.16, H 7.39, N 7.09;
found: C 71.24, H 7.53, N 7.73.
(5S,17S,24S)-5,17,24-Triisobutyl-3,6,16,19,22,25-hexaaza-1,11(1,3,5),2,8,14,20,21,27(1,3)-octabenzenabicy-
clo[9.9.9]nonacosaphane-9,12,28-triyne-4,7,15,18,23,26-hexaone ((S,S,S)-2). A soln. of (S,S,S)-8 (1.486 mg,
1.51 mmol) in CH2Cl2/TFA 1:1 (10 ml) was stirred for 3 h under Ar. Evaporation in vacuo provided a residue,
which was taken up in EtOH, and the soln. was again evaporated to give (S,S,S)-6, which was dried at 10À2 Torr.
In parallel, 14 (0.760 g, 1.51 mmol) was suspended in SOCl2, and the mixture was heated to reflux for 24 h.
Excess SOCl2 was removed by distillation, and crude 9 was dried at 10À2 Torr. A soln. of 9 in THF (20 ml) and a
soln. of (S,S,S)-6 in THF (20 ml) containing Et3N (1.8 ml, 13.5 mmol) were added synchronously over 8 h via
syringe pump to THF (1.5 l) containing Et3N (1.8 ml, 13.5 mmol). The mixture was stirred for 3 d at r.t., and the
solvent was evaporated in vacuo. FC (SiO2; CH2Cl2/AcOEt 2 :1), followed by prep. GPC and multiple FC (10 Â
SiO2, CH2Cl2/AcOEt 4 :1) yielded (S,S,S)-2 (ca. 85 mg, 5%). Colorless powder. M.p. > 3008. Rf (SiO2; CH2Cl2/
AcOEt 4 :1) 0.45. tR (GPC): 17.86 min. [a]2D3 À153 (c 0.1, THF). IR (KBr): 2410 (br.), 2955m, 2364w, 2336w,
1653s, 1531m, 1397m, 1300w, 1166w, 1090w, 877w, 787w, 69 6w. 1H-NMR (500 MHz, (CD3)2SO): 10.17 (s, 3 H);
8.68 (d, J 8.5, 3 H); 8.13 (s, 3 H); 7.82 (s, 3 H); 7.78 (d, J 7.8, 3 H); 7.68 (s, 3 H); 7.65 (d, J 7.7, 3 H); 7.57 (s,
3 H); 7.51 (dd, J 7.7, 7.7, 3 H ) ; 7.46 ( m, 3 H); 7.41 (m, 6 H); 4.80 (m, 3 H); 1.72 1.58 (m, 9 H); 0.94 (s, 18 H).
13C-NMR (125 MHz, (CD3)2SO): 170.76; 166.12; 142.13; 141.18; 139.52; 135.50; 134.31; 132.85; 131.27; 129.36;
129.17; 128.53; 125.12; 123.35; 122.66; 121.46; 118.75; 118.33; 90.06; 87.79; 52.92; 24.57; 22.78; 22.01. HR-
MALDI-MS; 1169.493 (100, [M Na] , C75H66N6O6Na ; calc. 1169.494).
(5S,17S,24S)-5,17,24-Triisobutyl-4,7,15,18,23,26-hexaaza-1,11(1,3,5),2,8,14,20,21,27(1,3)-octabenzenabicy-
clo[9.9.9]nonacosaphane-9,12,28-triyne-3,6,16,19,22,25-hexaone ((S,S,S)-3). A soln. of (S,S,S)-18 (809mg,
0.761 mmol) in CH2Cl2/TFA 1:1 (10 ml) was stirred for 3 h at r.t. under Ar. After evaporation in vacuo,
EtOH was added, the solvent was evaporated again, and the resulting crude (S,S,S)-10 was dried at 10À2 Torr. In
parallel, 7 (0.332 g, 0.761 mmol) was suspended in SOCl2 (10 ml), and the mixture was heated to reflux for 24 h.
After evaporation of excess SOCl2, crude 5 was dried at 10À2 Torr. A soln. of 5 in THF (20 ml) and a soln. of
(S,S,S)-10 in THF (20 ml) containing Et3N (0.9ml, 6.8 mmol) were added synchronously over 8 h via syringe
pump to THF (750 ml) containing Et3N (0.9ml, 6.8 mmol). After stirring for 3 d at r.t., the mixture was filtered
over Celite and evaporated in vacuo. FC (SiO2; CH2Cl2/AcOEt 2 :1), followed by GPC and multiple FC (5 Â
SiO2; CH2Cl2/AcOEt 4 :1), provided (S,S,S)-3 (87 mg, 10%). Colorless powder. M.p. > 3008. Rf (SiO2; CH2Cl2/
AcOEt 4 :1) 0.76. tR (GPC) 17.64 min. [a]2D3 À9 0 (c 0.1, THF). IR (KBr): 3312 (br.), 2955m, 2212w, 1675s,
1604s, 1581s, 1526s, 1432w, 1401m, 1303w, 1247w, 1169w, 1082w, 9 9w5, 878m, 786m, 749m, 684m. 1H-NMR
(500 MHz, (CD3)2SO): 10.21 (s, 3 H); 8.87 (d, J 7.8, 3 H); 8.14 (s, 3 H); 8.11 (s, 3 H); 7.9 1 (s, 3 H); 7.89( d, J
7.6, 6 H); 7.60 (dd, J 7.6, 7.6, 3 H); 7.53 (s, 3 H); 7.34 (dd, J 7.8, 7.8, 3 H); 7.22 (d, J 7.2, 3 H); 7.14 (d, J 7.7,
3 H); 4.62 (m, 3 H); 1.79( m, 6 H); 1.59 (m, 3 H); 0.95 (s, 18 H). 13C-NMR (125 MHz, (CD3)2SO): 171.91; 167.37;
141.95; 140.73; 139.04; 135.09; 134.02; 130.63; 129.34; 129.11; 127.10; 126.40; 125.83; 124.81; 124.55; 123.65;
122.08; 120.16; 91.22; 87.42; 53.02; 24.71; 23.25; 21.29. HR-MALDI-MS: 1169.494 (100, [M Na] ,
C75H66H6O6Na ; calc. 1169.494.
(7S,19S,30S)-7,19,30-Triisobutyl-5,8,18,21,28,31-hexaaza-1,13(1,3,5),4,10,16,22,27,33(1,3)-octabenzenabicy-
clo[11.11.11]pentatriacontaphane-2,11,14,23,25,34-hexayne-6,9,17,20,29,32-hexaone ((S,S,S)-4).
A soln. of
(S,S,S)-18 (700 mg, 0.658 mmol) in CH2Cl2/TFA 1 :1 (10 ml) was stirred for 3 h at r.t. under Ar. After
evaporation in vacuo, EtOH was added, the solvent was evaporated again, and the resulting crude (S,S,S)-10 was