80.1, 80.0, 68.0, 64.9, 49.1, 48.8, 48.4, 33.7, 29.5, 29.4, 29.3, 29.2,
29.1, 28.9, 28.44, 28.42, 26.0. ESI MS: m/z = 737.2 ([M + Na+]);
calculated exact mass: 714.46. HR ESI MS: m/z = 737.4502 ([M +
Na+]); calculated exact mass for C44H62N2NaO6: 737.4500.
in dry toluene (100 mL) to 140 ◦C for 16 h using a Dean–
Stark apparatus under nitrogen atmosphere. The solvent was
removed under vacuum, and the imine obtained was dissolved
in THF (20 mL) and MeOH (20 mL) to which NaBH4 (0.27 g,
7.3 mmol) was added in portions. After stirring for overnight,
the solvent was removed under vacuum leaving a residue which
was extracted by CHCl3. The organic layer was washed by
brine, dried over anhydrous Na2SO4, and the solvent was then
removed under vacuum leaving a residue which was purified by
column chromatography (silica gel, MeOH/CHCl3 = 1 : 19) to
Compound 17. Using the procedure for synthesizing com-
pound 11, compound 16 (2.48 g, 3.4 mmol) was brominated by
CBr4 (1.72 g, 5.2 mmol) and PPh3 (1.36 g, 5.2 mmol) to give
compound 17 (2.27 g, 86%) after purification by column chro-
matography (silica gel, EA/hexane = 1 : 4). 1H NMR (500 MHz,
CDCl3): d = 7.35 (2 H, d, J = 7.8 Hz, Ar), 7.17 (8 H, br, Ar),
6.87 (2 H, d, J = 8.2 Hz, Ar), 5.81 (1 H, m, C(H) = CH2), 4.97
(2 H, m, CH = C(H2)), 4.47 (2 H, s, CH2), 4.41 (8 H, br, CH2),
3.95 (2 H, t, J = 6.3 Hz, CH2), 2.07 (2 H, m, CH2), 1.81 (2 H, m,
CH2) 1.51 (30 H, br, CH2 & Boc). 13C NMR (125 MHz, CDCl3):
d = 158.3, 155.75, 155.73, 138.9, 138.3, 137.0, 136.6, 129.6, 129.2,
129.1, 128.6, 128.2, 127.9, 127.6, 127.5, 114.3, 114.0, 79.9, 79.7,
67.8, 48.6, 48.3, 33.6, 33.0 29.3, 29.23, 29.19, 29.12, 28.9, 28.7,
28.33, 28.28, 25.9. ESI MS: m/z = 799.0 ([M + Na+]); calculated
exact mass: 776.38. HR ESI MS: m/z = 799.3663 ([M + Na+]);
calculated exact mass for C44H61BrN2NaO5: 799.3656.
1
give compound 20 (1.37 g, 65%). H NMR (500 MHz, CDCl3):
d = 7.21 (4 H, d, J = 8.2 Hz, Ar), 7.16 (4 H, d, J = 8.2 Hz, Ar),
7.08 (9 H, br, Ar), 6.81 (2 H, d, J = 8.8 Hz, Ar), 6.77 (4 H, d, J =
8.2 Hz, Ar), 6.44 (3 H, br, Ar), 5.73 (2 H, m, C(H) = CH2), 4.88
(4 H, m, CH = C(H2)), 4.29 (8 H, br, CH2), 4.05 (8 H, m, CH2),
3.86 (12 H, br, CH2), 3.69 (4 H, s, CH2), 3.65 (4 H, s, CH2), 1.98
(4 H, m, CH2), 1.75 (2 H, br, NH), 1.71 (4 H, m, CH2), 1.41 (42
H, br, CH2 & Boc). 13C NMR (125 MHz, CDCl3): d = 159.9,
158.4, 157.8, 155.9, 139.16, 139.13, 136.7, 132.5, 129.8, 129.3,
128.7, 128.3, 128.0, 127.5, 114.5, 114.4, 114.1, 107.1, 101.8, 79.9,
69.9, 69.8, 67.9, 67.5, 67.4, 52.7, 52.5, 48.5, 48.3, 33.7, 29.4, 29.34,
29.31, 29.2, 29.0, 28.8, 28.4, 25.9. ESI MS: m/z = 1451.4 ([M +
H+]), 726.5 ([M + 2H+]); calculated exact mass: 1450.91. HR
ESI MS: m/z = 1451.9158 ([M + H+]); calculated exact mass for
C90H123N4O12: 1451.9132.
Compound 18. Using the procedure for synthesizing com-
pound 12, compound 17 (0.56 g, 0.72 mmol) was treated with
sodium azide (0.09 g, 1.44 mmol) to give compound 18 (0.47 g,
88%). Chromatographic purification was not done at this stage.
1H NMR (500 MHz, CDCl3): d = 7.28 (2 H, d, J = 7.5 Hz, Ar),
7.15 (8 H, br, Ar), 6.85 (2 H, d, J = 8.2 Hz, Ar), 5.81 (1 H, m,
C(H) = CH2), 4.97 (2 H, m, CH = C(H2)), 4.41 (8 H, br, CH2),
4.33 (2 H, s, CH2), 3.94 (2 H, t, J = 6.95 Hz, CH2), 2.06 (2 H,
m, CH2), 1.80 (2 H, m, CH2), 1.49 (30 H, br, CH2 & Boc). 13C
NMR (125 MHz, CDCl3): d = 158.4, 155.9, 139.2, 136.8, 134.3,
129.7, 129.3, 128.8, 128.4, 128.1, 127.6, 114.5, 114.1, 80.2, 79.9,
68.0, 54.5, 49.0, 48.7, 33.8, 29.5, 29.4, 29.35, 29.27, 29.1, 28.9,
28.5, 28.4, 26.0. ESI MS: m/z = 762.2 ([M + Na+]); calculated
exact mass: 739.47. HR ESI MS: m/z = 762.4581 ([M + Na+]);
calculated exact mass for C44H61N5NaO5: 762.4565.
Compound 21. A mixture of compound 5 (0.1 g, 0.21 mmol)
and compound 19 (0.3 g, 0.42 mmol) in 1 : 2 molar ratio was
◦
heated in dry toluene (70 mL) to 140 C for 16 h using a Dean–
Stark apparatus under nitrogen atmosphere. The solvent was
removed under vacuum, and the imine obtained was dissolved
in THF (6 mL) and MeOH (6 mL) to which NaBH4 (0.04 g,
1.06 mmol) was added in portions. After stirring for overnight,
the solvent was removed under vacuum leaving a residue which
was extracted by CHCl3. The organic layer was washed by
brine, dried over anhydrous Na2SO4, and the solvent was then
removed under vacuum leaving a residue which was purified by
column chromatography (silica gel, MeOH/CHCl3 = 1 : 15) to
Compound 19. Using the procedure for synthesizing com-
pound 13, compound 18 (0.47 g, 0.63 mmol) was reduced by
H2O (0.029 g, 1.58 mmol) and PPh3 (0.34 g, 1.27 mmol) to
give compound 19 (0.32 g, 72%) after purification by column
chromatography (silica gel, MeOH/CHCl3 = 1 : 9). 1H NMR
(500 MHz, CDCl3): d = 7.28 (2 H, d, J = 8.2 Hz, Ar), 7.15 (8 H, br,
Ar), 6.85 (2 H, d, J = 8.2 Hz, Ar), 5.81 (1 H, m, C(H) = CH2), 4.96
(2 H, m, CH = C(H2)), 4.39 (8 H, br, CH2), 3.94 (2 H, t, J = 6.95 Hz,
CH2), 3.87 (2 H, s, CH2), 2.06 (2 H, m, CH2), 1.80 (4 H, br, CH2 &
NH2), 1.50 (30 H, br, CH2 & Boc). 13C NMR (125 MHz, CDCl3):
d = 158.4, 155.96, 155.95, 142.0, 139.2, 137.1, 136.9, 136.6, 129.7,
129.3, 128.72, 128.67, 128.4, 128.1, 127.6, 127.3, 114.5, 114.1, 80.0,
79.9, 68.0, 48.9, 48.7, 48.4, 46.1, 33.8, 29.5, 29.38, 29.35, 29.27,
29.1, 28.9, 28.5, 28.4, 26.0. ESI MS: m/z = 714.1 ([M + H+]);
calculated exact mass: 713.48. HR ESI MS: m/z = 714.4848 ([M +
H+]); calculated exact mass for C44H64N3O5: 714.4840.
1
give compound 21 (0.32 g, 81%). H NMR (500 MHz, CDCl3):
d = 7.32 (4 H, d, J = 7.6 Hz, Ar), 7.26 (4 H, d, J = 8.2 Hz, Ar),
7.18 (17 H, br, Ar), 6.91 (4 H, d, J = 8.8 Hz, Ar), 6.87 (4 H, d,
J = 8.2 Hz, Ar), 6.54 (3 H, br, Ar), 5.82 (2 H, m, C(H) = CH2),
4.97 (4 H, m, CH = C(H2)), 4.42 (16 H, br, CH2), 4.14 (8 H, m,
CH2), 3.95 (4 H, t, J = 6.3 Hz, CH2), 3.92 (8 H, m, CH2), 3.79
(4 H, s, CH2), 3.75 (4 H, s, CH2), 2.08 (4 H, m, CH2), 1.96 (2 H,
br, NH), 1.81 (4 H, m, CH2), 1.52 (60 H, br, CH2 & Boc). 13C
NMR (125 MHz, CDCl3): d = 159.8, 158.3, 157.7, 155.82, 155.79,
139.2, 138.9, 136.9, 136.5, 132.4, 129.7, 129.1, 128.6, 128.3, 128.2,
127.9, 127.5, 114.44, 114.36, 114.0, 107.0, 101.7, 79.9, 79.8, 69.8,
69.7, 67.9, 67.4, 67.3, 52.6, 52.4, 48.8, 48.6, 48.3, 33.6, 29.3, 29.24,
29.21, 29.1, 28.9, 28.8, 28.33, 28.32, 25.9. ESI MS: m/z = 1890.5
([M + H+]), 946.3 ([M + 2H+]); calculated exact mass: 1889.16.
HR ESI MS: m/z = 945.5885 ([M + 2H+]); calculated exact mass
for C116H158N6O16: 945.5862.
Tert-butyl
(4,4¢-(4,4¢-(2,2¢-(2,2¢-(1,3-phenylenebis(oxy))bis-
(ethane-2,1-diyl))bis(oxy)bis(ethane-2,1-diyl))bis(oxy)bis(4,1-phe-
nylene))bis(methylene)bis(azanediyl)bis(methylene)bis(4,1-pheny-
lene))bis(methylene)bis(4-(undec-10-enyloxy)benzylcarbamate)
(20). A mixture of compound 5 (0.71 g, 1.45 mmol) and
compound 13 (1.44 g, 2.9 mmol) in 1 : 2 molar ratio was heated
Compound 1·(PF6)4. Compound 20 (1.3 g, 0.9 mmol) was
dissolved in dry DCM (50 mL) under nitrogen atmosphere.
Trifluoroacetic acid (2.04 g, 17.9 mmol) was added to this solution
and stirred overnight. The solvent was removed in vacuum and the
residue was dissolved in minimum amount of methanol-acetone
This journal is
The Royal Society of Chemistry 2011
Org. Biomol. Chem., 2011, 9, 3504–3515 | 3513
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