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(2CH), 126.7 (CH), 127.7 (CH), 127.9 (CH), 128.8 (CH), 131.8 (C), 133.0
(C), 133.1 (C), 154.7 (2C), 166.5 (C), 192.2 (2C); MS (ESIþ, m/z): 354
[(Mþ62)þ, 50%], 292 [(MþH)þ, 100%]. HRMS (ESI)þ calcd for
C18H13NNaO3 (MþNa)þ: 314.0788; found 314.0776.
(CDCl3, 300.13 MHz): d 0.99e1.12 (m, 8H), 1.55e1.65 (m, 4H),
2.00e2.09 (m, 8H), 3.10e3.63 (br s, 4H, NH), AB system (dA¼3.68
dB¼4.02, 2JHH¼15.5 Hz), AB system (dA¼5.05 dB¼5.09, 2JHH¼11.9 Hz),
5.29 (d, 3JHH (cis)¼10.4 Hz, 2H), 5.79 (d, 3JHH (trans)¼17.6 Hz, 2H), 6.63
(s, 4H), 6.74 (dd, 3JHH (trans)¼17.6 Hz, 3JHH (cis)¼10.4 Hz, 2H), AB sys-
3
4.1.14. Synthesis of 4-(naphthalen-1-ylmethoxy)pyridine-2,6-di-
carboxaldehyde (5d). Over a solution of 10d (200 mg, 0.67 mmol) in
tem (dA¼7.36 dB¼7.44, JHH¼8.0 Hz); 13C NMR (CDCl3, 75.5 MHz):
d 24.5 (CH2), 32.7 (CH2), 51.4 (CH2), 58.9 (CH), 69.5 (CH2), 107.6 (CH),
1,4-dioxane (10 mL) were successively added H2O (75
m
L) and SeO2
126.4 (CH),127.7 (CH),135.1 (C),136.1 (CH),137.6 (C),161.8 (C),165.5
(C); MS (ESIþ, m/z): 699 [(MþH)þ, 100%]. HRMS (ESI)þ calcd for
C44H55N6O2 (MþH)þ: 699.4381; found 699.4373.
(225 mg, 2.0 mmol). The resulting solution was stirred at 100 ꢁC for
4 h, and then the reaction quenched by filtration of the suspended
solid. Solvent was evaporated under reduced pressure, obtaining
a reaction crude that was purified by flash chromatography (20%
EtOAc/hexane). White solid. Yield: 81%; mp 157e161 ꢁC (ethyl ac-
etate/hexane); Rf (20% EtOAc/hexane): 0.26; IR (cmꢀ1) 2975, 1731,
4.1.18. Synthesis of (R,R,R,R)-4-(naphthalen-2-ylmethoxy) dimer
(6c). We used the same procedure as for 6a, but using 5c. White
solid. Yield: 81%; mp 107e109 ꢁC (CH2Cl2); Rf (5% NH3/MeOH): 0.11;
1543, 1422, 1375, 1224; 1H NMR (DMSO-d6, 300.13 MHz):
2H), 7.52e7.75 (m, 4H), 7.87 (s, 2H), 7.96e8.15 (m, 3H), 10.1 (s, 2H);
13C NMR (DMSO-d6, 75.5 MHz):
69.1 (CH2), 112.2 (2CH), 123.6
d
5.87 (s,
[
a
]
20 ꢀ19.5 (c 1, CH2Cl2); IR (cmꢀ1) 3404, 2953, 1645, 1443; 1H NMR
D
(CDCl3, 300.13 MHz):
d 0.96e1.13 (m, 8H), 1.53e1.64 (m, 4H),
d
1.98e2.09 (m, 8H), 3.10e3.63 (br s, 4H, NH), AB system (dA¼3.71
2
(CH), 125.3 (2CH), 126.0 (CH), 126.7 (CH), 128.4 (CH), 128.8 (CH),
131.0 (C), 132.1 (C), 154.6 (2C), 167.1 (C), 192.5 (2C); MS (ESIþ, m/z):
292 [(MþH)þ, 100%]. HRMS (ESI)þ calcd for C18H13NNaO3 (MþNa)þ:
314.0788; found 314.0782.
dB¼4.06, JHH¼15.5 Hz), 3.83e3.87 (br s, 4H, NH), 5.19e5.29 (m,
4H), 6.68 (s, 4H), 7.45e7.51 (m, 6H), 7.81e7.89 (m, 8H); 13C NMR
(CDCl3, 75.5 MHz):
d 24.5 (CH2), 32.5 (CH2), 51.3 (CH2), 58.9 (CH),
69.8 (CH2), 107.7 (CH), 124.9 (CH), 126.1 (CH), 126.2 (CH), 126.4 (CH),
127.6 (CH), 127.8 (CH), 128.4 (CH), 133.0 (2C), 133.1 (C); MS (ESIþ,
m/z): 747 [(MþH)þ, 100%]. HRMS (ESI)þ calcd for C48H55N6O2
(MþH)þ: 747.4381; found 747.4405.
4.1.15. Synthesis of 4-(anthracen-9-ylmethoxy)pyridine-2,6- dicar-
boxaldehyde (5e). Over a solution of 10e (320 mg, 0.9 mmol) in
EtOAc (70 mL) was added IBX (1.5 g, 3.8 mmol). The resulting so-
lution was stirred at 70 ꢁC for 5 h, and then the reaction quenched
by filtration of the precipitated solid. Solvent was evaporated under
reduced pressure, obtaining a reaction crude that was purified by
flash chromatography (20% EtOAc/hexane). Yellowish solid. Yield:
80%; mp 157e161 ꢁC (ethyl acetate/hexane); Rf (20% EtOAc/hex-
ane): 0.24; IR (cmꢀ1) 2972, 1731, 1573, 1442, 1310, 1218; 1H NMR
4.1.19. Synthesis of (R,R,R,R)-4-(naphthalen-1-ylmethoxy) dimer
(6d). We used the same procedure as for 6a, but using 5d. White
solid. Yield: 75%; mp 105e107 ꢁC (CH2Cl2); Rf (5% NH3/MeOH): 0.12;
[a
]
20 ꢀ44.7 (c 0.4, CH2Cl2); IR (cmꢀ1) 3403, 2955, 1625, 1525, 1445;
D
1H NMR (CDCl3, 300.13 MHz):
d 0.96e1.13 (m, 8H), 1.53e1.64 (m,
4H),1.98e2.09 (m, 8H), 3.10e3.63 (br s, 4H, NH), AB system (dA¼3.74
dB¼4.11, 2JHH¼15.5 Hz), 3.83e3.87 (br s, 4H, NH), 5.45e5.59 (m, 4H),
6.73 (s, 4H), 7.47e7.60 (m, 8H), 7.86e8.01 (m, 6H); 13C NMR (CDCl3,
(CDCl3, 300.13 MHz):
d 6.13 (s, 2H), 7.49e7.63 (m, 4H), 7.87 (s, 2H),
8.09 (d, 3JHH¼8.1 Hz, 2H), 8.21 (d, 3JHH¼8.2 Hz, 2H), 8.61 (s, 1H), 10.1
(s, 2H); 13C NMR (CDCl3, 75.5 MHz):
d
63.9 (CH2), 111.7 (2CH), 123.1
75.5 MHz): d 24.5 (CH2), 32.5 (CH2), 51.3 (CH2), 59.0 (CH), 68.3 (CH2),
(2CH), 124.2 (2C), 125.2 (2CH), 127.1 (2CH), 129.3 (2CH), 129.9 (CH),
130.9 (2C), 131.3 (C), 154.9 (2C), 167.0 (C), 192.1 (2C); MS (ESIþ, m/z):
342 [(MþH)þ,100%]. HRMS (ESI)þ calcd for C22H15NNaO3 (MþNa)þ:
364.0944; found 364.0961.
107.7 (CH),123.3 (CH),125.2 (CH),126.0 (CH),126.6 (CH),126.7 (CH),
128.7 (CH), 129.3 (CH), 130.9 (C), 131.3 (C), 133.7 (C), 161.5 (C), 165.7
(C); MS (ESIþ, m/zm/z): 747 [(MþH)þ, 100%]. HRMS (ESI)þ calcd for
C48H55N6O2 (MþH)þ: 747.4381; found 747.4366.
4.1.16. Synthesis of (R,R,R,R)-4-(benzyloxy) dimer (6a). Over a solu-
tion of (1R,2R)-(ꢀ)-cyclohexane-1,2-diamine (45 mg, 0.39 mmol) in
CH2Cl2/MeOH (1:1, 8 mL), was added 5a (94 mg, 0.39 mmol) and
the solution was stirred for 15 min at room temperature. Then BaCl2
(146 mg, 0.60 mmol) was added and the resulting mixture stirred
for additional 14 h. Then the solution was cooled 0 ꢁC, and NaBH4
(64 mg, 1.70 mmol) was carefully added. The resulting white sus-
pension was stirred for 4 h at room temperature, quenching the
reaction with concentrated HCl (0.5 mL). The mixture was basified
with NaOH 4 N (10 mL) and extracted with CH2Cl2 (3ꢄ10 mL), or-
ganic phases were combined, dried over Na2SO4, filtered under
vacuum and evaporated to dryness, isolating 6a. White solid. Yield:
4.1.20. Synthesis of (R,R,R,R)-4-(anthracen-9-ylmethoxy) dimer
(6e). We used the same procedure as for 6a, but using 5e. Yellowish
solid. Yield: 83%; mp 127e129 ꢁC (CH2Cl2); Rf (5% NH3/MeOH):
0.12; [
a
]
D
20 ꢀ20.1 (c 0.25, CH2Cl2); IR (cmꢀ1) 3410, 3401, 2975, 1634,
1501, 1440; 1H NMR (CDCl3, 300.13 MHz):
d 0.98e1.13 (m, 8H),
1.55e1.63 (m, 4H), 1.99e2.09 (m, 8H), 3.50e4.101 (br s, 4H, NH), AB
system (dA¼3.80 dB¼4.15, 2JHH¼15.8 Hz), 5.86e5.94 (m, 4H), 6.81 (s,
3
4H), 7.49e7.58 (m, 8H), 8.08 (d, JHH¼8.2 Hz, 4H), 8.19 (d,
2JHH¼8.1 Hz, 4H), 8.55 (s, 2H); 13C NMR (CDCl3, 75.5 MHz):
d 24.3
(CH2), 31.6 (CH2), 50.9 (CH2), 59.1 (CH), 62.5 (CH2), 108.0 (CH), 123.9
(CH), 124.1 (C), 125.3 (CH), 127.1 (CH), 129.4 (CH), 129.7 (CH), 130.9
(C), 131.3 (C), 160.4 (C), 161.7 (C); MS (ESIþ, m/z): 847 [(MþH)þ,
100%]. HRMS (ESI)þ calcd for C56H59N6O2 (MþH)þ: 847.4694; found
847.4668.
79%; mp 99e101 ꢁC (CH2Cl2); Rf (5% NH3/MeOH): 0.12; [
a]
20 ꢀ38.5
D
(c 0.5, CH2Cl2); IR (cmꢀ1) 3400, 2950, 1600, 1435; 1H NMR (CDCl3,
300.13 MHz): d 0.98e1.13 (m, 8H), 1.55e1.63 (m, 4H), 1.99e2.09 (m,
8H), 3.10e3.63 (br s, 4H, NH), AB system (dA¼3.72 dB¼4.07,
4.1.21. Study of the 4-position effect on the templated step. Over
2JHH¼15.8 Hz, 8H), 5.01e5.11 (m, 4H), 6.66 (s, 4H), 7.31e7.43 (m,
a
solution of (1R,2R)-(ꢀ)-cyclohexane-1,2-diamine (61 mg,
10H); 13C NMR (CDCl3, 75.5 MHz):
d
24.5 (CH2), 32.4 (CH2), 51.2
0.50 mmol) in CH2Cl2/MeOH (1:1, 10 mL), were added 2 (34 mg,
0.25 mmol) and 5b (67 mg, 0.25 mmol) and the solution was stirred
for 15 min at room temperature. Then BaCl2 (195 mg, 0.80 mmol)
was added and the resulting mixture stirred for additional 14 h.
Then the solution was cooled down to 0 ꢁC, and NaBH4 (80 mg,
2.13 mmol) was carefully added. The resulting white suspension
was stirred for 4 h at room temperature, quenching the reaction
with concentrated HCl (1.0 mL). The mixture was basified with
NaOH 4 N (15 mL) and extracted with CH2Cl2 (3ꢄ10 mL), organic
phases were combined, dried over Na2SO4, filtered under vacuum
(CH2), 59.0 (CH), 69.8 (CH2), 107.8 (CH), 127.5 (CH), 128.3 (CH), 128.6
(CH), 135.6 (C), 161.4 (C), 165.4 (C); MS (ESIþ, m/z): 647 [(MþH)þ,
100%]. HRMS (ESI)þ calcd for C40H51N6O2 (MþH)þ: 647.4068; found
647.4083.
4.1.17. Synthesis of (R,R,R,R)-4-[(4-ethenylbenzyl)oxy] dimer (6b).
We used the same procedure as for 6a, but using 5b. White solid.
20
Yield: 85%; mp 105e106 ꢁC (CH2Cl2); Rf (5% NH3/MeOH): 0.12; [
a]
D
ꢀ27.5 (c 1.0, CH2Cl2); IR (cmꢀ1) 3400, 2950, 1600, 1435; 1H NMR