N. A. Grigorenko et al. / Tetrahedron 63 (2007) 2257–2262
2261
CH2CH2CH2CH2), 1.36 (d, 3H, J 6.6 Hz, CHCH3); 13C
NMR (D2O) d 47.07, 45.41, 44.62, 44.00, 36.67, 30.47,
23.79, 22.83, 17.58, 17.34.
d 3.55–3.46 (m, 2H, MeCH), 3.20 (t, 4H, J 6.8 Hz, NCH2),
3.17–3.11 (m, 4H, NCH2), 2.18–2.09 (m, 2H, CH2CHNH2),
2.04–1.93 (m, 2H, CH2CHNH2), 1.84–1.75 (m, 4H,
CH2CH2CH2CH2), 1.35 (d, 6H, J 6.6 Hz, CHCH3); 13C
NMR (D2O) d 49.86, 48.14, 46.78, 33.27, 25.64, 20.09.
Starting from 7b and following the same procedure 8b was
obtained as colorless crystals (63%); [a]2D0 ꢀ4.5 (c 2.0,
H2O); ee 97%; found, %: C 36.40, H 9.00, N 15.35;
C11H32N4Cl4 calcd, %; C 36.48, H 8.90, N 15.47.
Starting from 9b and following the same procedure 10b was
obtained (92%) as a white solid, mp 224–225 ꢁC (MeOH/
EtOH); Rf 0.13 (BunOH/AcOH/Py/H2O, 4:2:1:2); [a]2D0
ꢀ8.4 (c 3.0, H2O); ee 97%; found, %: C 38.20, H 9.28, N
14.69; C12H34N4Cl4 calcd, %: C 38.31, H 9.11, N 14.89;
1H NMR (D2O) d 3.56–3.47 (m, 2H, MeCH), 3.20 (t, 4H,
J 6.8 Hz, CH2NH), 3.18–3.12 (m, 4H, NCH2), 2.19–2.10
(m, 2H, CH2CHNH2), 2.05–1.94 (m, 2H, CH2CHNH2),
1.84–1.75 (m, 4H, CH2CH2CH2CH2), 1.35 (d, 6H, J
6.6 Hz, CHCH3); 13C NMR (D2O) d 49.86, 48.14, 46.78,
33.27, 25.64, 20.09.
4.1.8. (R,R)-N2,N13-di-(tert-Butyloxycarbonyl)-2,13-di-
amino-5,10-diazatetradecane (9a). A mixture of 3a
(8.95 g, 24 mmol), K2CO3 (11.6 g, 84 mmol), and 1,4-di-
iodobutane (3.72 g, 12 mmol) in dry DMF (50 mL) was
stirred for 24 h at 30 ꢁC before the addition of BnBr
(0.34 mL, 2.9 mmol). The mixture was then stirred for a
further 14 h, PhSH (3.67 mL, 36 mmol) and K2CO3
(4.97 g, 36 mmol) were added followed by stirring for 20 h
at 30 ꢁC. The reaction mixture was evaporated in vacuo to
dryness and the residue was treated with CH2Cl2 (250 mL),
washed with H2O (2ꢂ50 mL), brine (20 mL), and dried
(K2CO3). The solvent was evaporated in vacuo, and the
residue was purified by flash chromatography (SiO2, 1,4-
dioxane/25% NH4OH, 100:2.5) to give 9a (4.7 g, 91%) as
an amorphous colorless solid; Rf 0.28 (1,4-dioxane/25%
NH4OH, 95:5); [a]D20 ꢀ11.6 (c 2.0, CHCl3); 1H NMR
(CDCl3) d 4.91 (br s, 2H, BocNH), 3.76–3.68 (m, 2H,
CH3CH), 2.72–2.55 (m, 8H, NCH2), 1.70–1.62 (m, 2H,
CHCH2), 1.54–1.47 (m, 6H, CH2CH2CH2CH2+CHCH2),
1.44 (s, 18H, CMe3), 1.14 (d, 6H, J 6.6 Hz, CHCH3); 13C
NMR (CDCl3) d 155.22, 78.52, 49.77, 46.44, 44.91, 37.03,
28.45 (6C), 27.78, 21.42.
Starting from 9c and following the same procedure 10c was
obtained (94%) as a white solid, mp 224–225 ꢁC (H2O/
MeOH/EtOH); Rf 0.13 (BunOH/AcOH/Py/H2O, 4:2:1:2);
[a]2D0 0 (c 2.0, H2O); found, %: C 38.13, H 9.20, N 14.86;
C12H34N4Cl4 calcd, %: C 38.31, H 9.11, N 14.89; 1H NMR
(D2O) d 3.55–3.46 (m, 2H, MeCH), 3.21 (t, 4H, J 6.8 Hz,
NCH2), 3.17–3.11 (m, 4H, NCH2), 2.18–2.09 (m, 2H,
CH2CHNH2), 2.04–1.94 (m, 2H, CH2CHNH2), 1.84–1.75
(m, 4H, CH2CH2CH2CH2), 1.35 (d, 6H, J 6.6 Hz, CHCH3);
13C NMR (D2O) d 49.8, 48.14, 46.78, 33.27, 25.64, 20.09.
Acknowledgements
This work was supported by the Russian Foundation for
Basic Research (grant no. 06-04-49638) and by grant from
Academy of Finland (117436). We thank Mrs. Maritta
Salminkoski for technical assistance.
Starting from 3b and following the same procedure 9b was
obtained as amorphous colorless solid (90%); Rf 0.28 (1,4-
dioxane/25% NH4OH, 95:5); [a]2D0 +11.8 (c 2.0, CHCl3);
1H NMR (CDCl3) d 4.90 (br s, 2H, BocNH), 3.75–3.67
(m, 2H, MeCH), 2.72–2.54 (m, 8H, NCH2), 1.71–1.62 (m,
2H, CHCH2), 1.54–1.46 (m, 6H, CH2CH2CH2CH2+
CH3CHCH2), 1.43 (s, 18H, CMe3); 1.13 (d, 6H, J 6.6 Hz,
CHCH3); 13C NMR (CDCl3) d 155.53, 78.82, 49.83,
46.51, 45.08, 37.17, 28.40 (6C), 27.86, 21.36.
References and notes
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