J. H. Jung et al. / Tetrahedron 63 (2007) 7449–7456
7455
–CH–), 3.48–3.43 (m, 1H, –CH–), 3.20–3.16 (m, 4H, –CH–
5.7. Compound 11
and –CH2–), 1.50–1.43 (m, 8H, –CH2–), 1.24 (s, 12H,
–CH2–); MS (FAB): 524 (M+H)+ (calcd MW¼525.25);
elemental analysis calcd (%) for C24H37NO9: C 59.61, H
7.71, N 2.90, O 29.78; found: C 59.28, H 7.17, N 2.23.
Dodecanedioyl dichloride (0.30 g, 1.12 mmol) in dry THF
(8 mL) was cooled to 0 ꢀC, and a solution of 9 (0.5 g,
1.13 mmol) and Et3N (0.12 g, 1.14 mmol) in THF (8 mL)
was added dropwise over a period of 1 h and stirred for fur-
ther 2 h. A solution of N-Boc-1,2-diaminoethane (0.18 g,
1.13 mmol) and Et3N (0.12 g, 1.14 mmol) in THF (5 mL)
was added at once. The mixture was left to reach room tem-
perature slowly and stirred for 18 h. The precipitate formed
was filtered off and the residue obtained after evaporation
of the solvent. The reaction mixture was stirred with
CF3COOH (5 mL) and CH2Cl2 (5 mL) at room temperature
for 5 h. The solvents were evaporated to dryness to yield
a colorless syrup. Yield 50%. 1H NMR (300 MHz, DMSO-
d6): d 9.82 (s, 1H, –NH), 9.65 (s, 1H, –NH), 7.33 (d, 2H,
ArH), 7.08 (d, 2H, J¼8.7, ArH), 5.36 (d, 1H, J¼9.6,
–CH–), 5.04–4.98 (m, 2H, –CH), 4.68 (d, 1H, J¼9,
–CH2–), 4.65 (d, 1H, J¼5.2, –CH–), 4.08–4.02 (m, 2H,
–CH2–), 3.50–3.42 (m, 2H), 3.01–2.92 (m, 2H), 2.30–2.26
(m, 2H, –CH2–), 2.22–2.16 (m, 2H), 2.06 (s, 12H, –CH3),
1.56–1.52 (m, 4H, –CH2–), 1.30 (s, 12H, –CH2–).
5.4. Compound 8
Nitrophenyl-b-D-glucopyranoside 7 (1.0 g, 2.54 mmol) was
dissolved in pyridine (1.0 mL) and acetylacetone (1.0 mL).
The reaction mixture was allowed to stand overnight and
was then evaporated in vacuo to dryness with dry toluene.
The residue was purified by column chromatography on sil-
ica gel with EA/Hx (1:1 v/v, Rf¼0.5). Yield 75%. 1H NMR
(300 MHz, CDCl3): d 7.23 (d, 2H, J¼9.0, ArH), 7.08 (d,
2H, J¼9.0, ArH), 5.27–5.21 (m, 3H), 5.04 (d, 1H, J¼9.0),
4.30–4.14 (m, 2H), 3.90–3.86 (m, 1H), 1.97 (s, 12H); 13C
NMR (75 MHz, CDCl3): 170.5, 158.6, 130.5, 123.1, 115.3,
98.1, 71.4, 68.3, 65.4, 20.8, 19.6 ppm; MS (FAB): 470
(M+H)+ (calcd MW¼469.1); elemental analysis calcd (%)
for C20H23NO12: C 51.18, H 4.94, N 2.98; found: C 51.01,
H 5.24, N 2.86.
5.5. Compound 9
5.8. Compound 12
Compound 8 (1.0 g) was dissolved in MeOH (25 mL). After
5 min of N2 purging, Pd on activated carbon (10 wt %,
100 mg) was added. Under 2 atm of H2, the reaction was al-
lowed to proceed for 3 h. After filtration and evaporation,
pure 9 was obtained as a pale yellow solid (2.48 g, quantita-
tive). EA/Hx (1:1 v/v, Rf¼0.5). Yield 75%. 1H NMR
(300 MHz, CDCl3): d 6.85 (d, 2H, J¼9.0, ArH), 6.64 (d,
2H, J¼9.0, ArH), 5.31–5.13 (m, 3H), 4.96 (d, 1H, J¼9.0),
4.32–4.19 (m, 2H), 3.82–3.77 (m, 1H), 3.48 (s, 2H), 2.05
(s, 12H); 13C NMR (75 MHz, CDCl3): 170.3, 158.9, 130.2,
121.0, 119.3, 97.1, 73.4, 69.1, 64.6, 20.5, 19.1 ppm; MS
(FAB): 438 (M+H)+ (calcd MW¼439.1); elemental analysis
calcd (%) for C20H25NO10: C 54.67, H 5.73, N 3.19; found:
C 54.89, H 6.10, N 3.40.
Dodecanedioyl dichloride (1.21 g, 4.52 mmol) in dry THF
(8 mL) was cooled to 0 ꢀC, and a solution of 9 (0.5 g,
1.14 mmol) and Et3N (0.12 g, 1.22 mmol) in THF (8 mL)
was added dropwise over a period of 1 h and stirred for
further 2 h. A solution of amino-18-crown-6 (0.74 g,
2.26 mmol) and Et3N (0.23 g, 2.29 mmol) in THF (5 mL)
was added at once. The mixture was left to reach room tem-
perature slowly and stirred for 18 h. The precipitate formed
was filtered off and the residue obtained after evaporation of
the solvent purified by column chromatography (CH2Cl2/
MeOH, 10:1 v/v, Rf¼0.5) to yield 7 (0.80 g, 37%) as gray
1
solid. H NMR (300 MHz, CDCl3): d 9.48 (s, 1H, –NH),
7.38 (d, 2H, ArH), 6.98 (d, 2H, J¼8.7, ArH), 5.84 (d, 1H,
J¼9.6, –CH–), 5.04–4.98 (m, 2H, –CH), 4.68 (d, 1H, J¼9,
–CH2–), 4.65 (d, 1H, J¼5.2, –CH–), 4.08–4.02 (m, 2H,
–CH2–), 2.27–2.22 (m, 2H, –CH2–), 2.19–2.15 (m, 2H),
2.06 (s, 12H, –CH3), 1.55–1.50 (m, 4H, –CH2–), 1.28 (s,
12H, –CH2–).
5.6. Compound 10
Dodecanedioyl dichloride (0.62 g, 2.32 mmol) in dry THF
(8 mL) was cooled to 0 ꢀC, and a solution of 9 (1.0 g,
2.28 mmol) and Et3N (0.23 g, 2.28 mmol) in THF (8 mL)
was added dropwise over a period of 1 h and stirred for
further 2 h. A solution of amino-18-crown-6 (0.74 g,
2.26 mmol) and Et3N (0.23 g, 2.29 mmol) in THF (5 mL)
was added at once. The mixture was left to reach room tem-
perature slowly and stirred for 18 h. The precipitate formed
was filtered off and the residue obtained after evaporation of
the solvent purified by column chromatography (CH2Cl2/
MeOH, 10:1 v/v, Rf¼0.4) to yield 10 (0.80 g, 37%) as light
yellow solid. 1H NMR (300 MHz, DMSO-d6): d 9.84 (s, 1H,
–NH), 9.73 (s, 1H, –NH), 7.53 (d, 2H, J¼9, ArH), 7.33 (s,
1H, ArH), 7.08 (d, 1H, J¼8.7, ArH), 6.93 (d, 1H, J¼9,
ArH), 6.86 (d, 2H, J¼9, ArH), 5.44 (d, 1H, J¼8.1, –CH–),
5.37 (d, 1H, J¼9.6, –CH–), 5.05–4.96 (m, 2H, –CH),
4.21 (d, 2H, J¼9, –CH2–), 4.10 (d, 1H, J¼5.2, –CH–),
4.06–4.01 (m, 4H, –CH2–), 3.79–3.73 (m, 4H, –CH2–),
3.62–3.54 (m, 12H, –CH2–), 2.25 (q, 4H, –CH2–), 2.03
(s, 12H, –CH3), 1.61–1.52 (m, 4H, –CH2–), 1.27 (s, 12H,
–CH2–).
Acknowledgements
This work was supported by a Korea Research Foundation
Grant (KRF-2004-015-C00242) and KOSEF (R01-2005-
000-10229-0).
Supplementary data
Supplementary data associated with this article can be found
References and notes
1. van Esch, J.; Feringa, B. L. Angew. Chem., Int. Ed. 2000, 39,
2263–2266.
2. Schoonbeek, F. S.; van Esch, J.; Hulst, R.; Kellogg, R. M.;
Feringa, B. L. Chem.—Eur. J. 2000, 6, 2633–2643.