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170.9, 143.3, 143.0, 142.2, 138.0, 136.8, 135.8 (7s); 129.6, 129.5, 127.0, 126.9, 51.5 (5d, 13 CH); 48.8, 46.7, 42.4, 40.6,
36.4, 34.5, 31.8, 29.5, 29.4, 29.3, 29.2, 29.0, 28.6, 28.3, 26.5, 25.6, 22.5 (17t, 18 CH2); 21.3, 14.0 (2q, 4 Me). ESI-MS:
855 (20, [M Na] ), 833 (100, [M 1] ).
(8R)-1,9,13-Tris[(4-methylphenyl)sulfonyl]-8-undecyl-1,5,9,13-tetraazacycloheptadecan-6-one (34) and
(3R)-3-{[(4-Methylphenyl)sulfonyl]amino}-N-{3-[[(4-methylphenyl)sulfonyl](4-{[(4-methylphenyl)sulfonyl]-
(prop-2-enyl)amino}butyl)amino]propyl}tetradecanamide (35). To a suspension of 32 (1.0 g, 1.20 mmol) and
Cs2CO3 (821 mg, 2.52 mmol) in DMF (300 ml), 1,3-dibromopropane (266 mg, 1.32 mmol) was added dropwise
over ca. 12 h. The mixture was stirred for 20 h at r.t. After evaporation, the residue was dissolved in CHCl3, the
soln. washed with H2O, dried (Na2SO4), and evaporated, and the residue submitted to CC (silica gel, CH2Cl2/
MeOH98 :2): 870 mg (83%) of unseparable 34/35. Colorless oil.
(À)-(8R)-8-Undecyl-1,5,9,13-tetraazacycloheptadecan-6-one (36) and (À)-(3R)-3-Amino-N-(3-{[4-(prop-
2-enylamino)butyl]amino}propyl)tetradecanamide (37). As described for 15, with 34/35. CC (SiO2, CH Cl/
3
MeOH/25% aq. NH3 soln. 15 :4 :1) yielded 152 mg (47%) of 36 and 132 mg (41%) of 37, both as colorless oils.
Data for 36: [a]D À14.2 (c 1.15, CHCl3). IR: 2920, 2850, 1640, 1520. 1H-NMR (CDCl3): 8.48 (br. t, 1 H );
3.49 3.22 (m, 2 H); 2.90 2.80 (m, 1 H); 2.80 2.60 (m, 10 H); 2.36 (dd, J 15.3, 3.4, 1 H); 2.14 (dd, J 15.3,
7.7, 1 H); 1.99 (br. s, 3 H); 1.75 1.40 (m, 8 H); 1.35 1.20 (m, 20 H); 0.88 (t, J 7.0, 3 H). 13C-NMR (CDCl3):
172.3 (s); 55.6 (d); 48.6, 48.3, 48.2, 47.6, 45.9, 40.4, 37.8, 34.1, 31.9, 29.7, 29.6, 29.3, 29.0, 26.8, 25.9, 22.6 (16t, 21
CH2); 14.1 (q). ESI-MS: 411 ([M 1] ).
Data for 37. IR: 2920, 2850, 1640, 1520. 1H-NMR (CDCl3): 7.74 (br. s, 1 H); 5.88 (ddt, J 17.1, 10.2, 6.0,
1 H); 5.18 (ddt, J 17.1, 1.6, 1 H); 5.08 (ddt, J 10.2, 1.6, 1 H); 3.32 (q, J 6.1, 2 H); 3.25 (ddd, J 6.0, 1.3, 2 H);
3.11 3.09 (m, 1 H); 2.69 (t, J 6.5, 2 H); 2.65 2.60 (m, 4 H); 2.31 (dd, J 15.0, 3.3, 1 H); 2.06 (dd, J 15.0,
9.2, 1 H); 1.84 (br. s, 4 H); 1.69 (quint.-like m, 2 H); 1.57 1.52 (m, 4 H); 1.32 1.20 (m, 20 H); 0.88 (t, J 6.5,
3 H ).13C-NMR (CDCl3): 172.0 (s); 136.5 (d); 115.8, 52.2 (2t); 48.7 (d); 49.5, 48.9, 47.6, 43.7, 38.3, 37.7, 31.7, 29.4,
29.2, 29.0, 27.7, 27.6, 25.9, 22.5 (14t, 18 CH2); 13.9 (q). ESI-MS: 41 ([M 1] ).
(À)-(8R)-1,9,13-Trimethyl-8-undecyl-1,5,9,13-tetraazacycloheptadecan-6-one ((À)-(R)-Budmunchiamine
A; 3). To a stirred soln. of 36 (41 mg, 0.1 mmol) in AcOH(5 ml) at 0 8, 37% formalin (1.5 ml) was added, and
stirring was continued for 7 min. Then NaCNBH3 (124 mg, 2 mmol) in MeOH(0.5 ml) was added and stirred
overnight at r.t. The mixture was quenched with aq. 2n HCl and evaporated, the residue taken up in sat. aq.
K2CO3, the mixture extracted with CH2Cl2, the org. phase dried (Na2SO4) and evaporated, and the residue
purified by CC (SiO2, CH C3l/MeOH/25% aq. NH3 soln. 90 :10 :0.7): 40 mg (88%) of 3. Colorless oil. [a]D
À16.3 (c 1.01, CHCl3). IR: 3420, 2920, 2850, 2800, 1640, 1520. 1H-NMR (CDCl3): 8.42 (br. t, 1 H); 3.37 (dt, J
6.7, 6.3, 2 H); 2.92 2.80 (m, 1 H); 2.64 (dt, J 12.0, 7.0, 1 H); 2.50 2.23 (m, 14 H); 2.22 (s, 3 H); 2.21 (s, 3 H );
1.71 1.60 (m, 4 H); 1.56 1.52 (m, 4 H); 1.30 1.25 (m, 20 H); 0.88 (t, J 7.0, 3 H). 13C-NMR (CDCl3): 172.6
(s); 61.2 (d); 56.4, 56.1, 55.5, 54.3, 51.3 (5t, 6 CH2); 42.4, 42.1 (2q); 37.2, 37.4 (2t, 4 CH2); 35.3 (q); 31.7, 29.7, 29.4,
29.1, 27.4, 27.3, 27.1, 25.2, 24.3, 23.2, 22.5 (11t); 13.9 (q). ESI-MS: 453 ([M 1] ).
Ethyl ()-(3S)-3-{[(4-Methylphenyl)sulfonyl]amino}-4-(octylthio)butanoate (39). To a soln. of KOH
(0.41 g, 7.3 mmol) and octane-1-thiol (1.07 g, 1.27 ml, 7.3 mmol) in EtOH(15 ml) a soln. of 2 (2.0 g, 4.9 mmol) in
EtOH(15 ml) was added slowly and dropwise at r.t. Then, the mixture was evaporated and the product
separated by CC (hexane/AcOEt 4 :1): 1.86 g (895) of 39. Colorless oil. [a]D 9.50 (c 1.00, CHCl3). IR:
3330m, 3020w, 2980w, 2950m, 2920s, 2850m, 1720s, 1600m, 1410m, 1375m, 1335m, 1300m, 1180w, 1160s, 1090m,
1060w, 1025m, 960m, 875w. 1H-NMR (CDCl3): 7.76 (d, J 8.3, 2 H); 7.30 (d, J 7.9, 2 H); 5.36 (d, J 7.8, 1 H);
4.13 4.01 (m, 2 H); 3.68 3.60 (m, 1 H); 2.77 (dd, J 4.9, 16.5, 1 H); 2.63 (d, J 4.9, 2 H); 2.51 (dd, J 6.3,
16.5, 1 H); 2.43 (s, 3 H); 2.33 2.24 (m, 2 H); 1.46 1.39 (m, 2 H); 1.33 1.19 (m, t, J 7.1, 13 H); 0.89 (t, J 7.0,
3 H ).13C-NMR (CDCl3): 170.9 (s); 143.4 (s); 137.4 (s); 129.6 (d); 127.1 (d); 60.7 (t); 49.8 (d); 37.4 (t); 36.2 (t);
32.3 (t); 31.7 (t); 29.3 (t); 29.0 (2t); 28.7 (t); 22.5 (t); 21.4 (q); 14.0 (2q). ESI-MS: 452 ([M Na] ).
()-(3S)-N-(4-Aminobutyl)-3-{[(4-methylphenyl)sulfonyl]amino}4-(octylthio)butanamide (40). As de-
scribed for 11, with 39 (1.86 g, 4.4 mmol): 2.03 g (quant.) of 40. Colorless oil. [a]D 7.98 (c 1.10, MeOH).
IR: 3500 3100(br.), 3440m, 3020w, 3000m, 2930m, 2860s, 1660s, 1600w, 1525m, 1470m, 1405m, 1380w, 1330m,
1305w, 1290w, 1220w, 1185w, 1160s, 1120w, 1095s, 1020w, 960m, 880m. 1H-NMR (CDCl3): 7.76 (d, J 8.3, 2 H);
7.30 (d, J 8.0, 2 H); 6.65 (br. t, 1 H); 3.58 3.50 (m, 1 H); 3.23 3.17 (m, 2 H); 2.80 2.44 (m, 8 H); 2.42 2.37
(m, s, 4 H); 2.32 2.20 (m, 2 H); 1.57 1.35 (m, 6 H); 1.33 1.20 (m, 10 H); 0.89 (t, J 7.0, 3 H).13C-NMR
(CDCl3): 170.1 (s); 143.3 (s); 137.4 (s); 129.6 (d); 127.1 (d); 50.5 (d); 41.3 (t); 39.1 (t); 38.5 (t); 36.2 (t); 32.1 (t);
31.7 (t); 30.3 (t); 29.4 (t); 29.0 (2t); 28.7 (t); 26.66 (t); 22.5 (t); 21.4 (q); 13.9 (q). ESI-MS: 494 (18, [M Na] ),
472 (100, [M H] ).
()-(3S)-3-{[(4-Methylphenyl)sulfonyl]amino}-N-(4-{[(4-methylphenyl)sulfonyl]amino}butyl)-4-(octyl-
thio)butanamide (41). As described for 12, with 40 (0.88 g, 1.87 mmol): 1.17 g (quant.) of 41. Colorless oil, which