Synthesis of [2]catenanes by template-directed clipping approach

Article abstract of DOI:10.1021/jo3012804

A series of [2]catenanes were efficiently synthesized in high yields by a template-directed clipping approach with the formation of one macrocycle around another macrocycle containing a dialkylammonium recognition site. Their structures were identified by the NMR spectra and ESI mass spectrometry, and their geometries were investigated by the theoretical calculation.

Full text of DOI:10.1021/jo3012804

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Synthesis of [2]Catenanes by Template-Directed Clipping Approach
Ziyong Li, Wenju Liu, Jishan Wu, Sheng Hua Liu, and Jun Yin
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/jo3012804 • Publication Date (Web): 27 Jul 2012
Downloaded from http://pubs.acs.org on August 4, 2012
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Synthesis of [2]Catenanes by Template-Directed Clipping
Approach
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Ziyong Li,† Wenju Liu,† Jishan Wu,‡ Sheng Hua Liu† and Jun Yin*†
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†Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central
China Normal University, Wuhan 430079, PR China.
‡Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543.
* E-mail: yinj@mail.ccnu.edu.cn
ABSTRACT: A series of [2]catenanes were efficiently synthesized in high yields by a template-directed
clipping approach with the formation of one macrocycle around another macrocycle containing a
dialkylammonium recognition site. Their structures were identified by the NMR spectra and ESI mass
spectrometry and their geometry were investigated by the theoretical calculation.
In the field of molecular devices and machines, studies on the mechanically interlocked molecular
architectures such as rotaxanes, catenanes and knots have become the focus of research.1 The efficient
synthesis of mechanically interlocked molecules is crucial for their successful applications. Catenanes,
topologically unique structures possessing two or more mechanically interlocked rings, have been known
for nearly half a century.2 In recent years, the rapid development of catenanes has promoted the
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understanding of design strategies and self-assembling structures of synthetic supramolecular systems.
Current synthetic approaches mainly rely on supramolecular preorganization of the macrocyclic precursors
utilizing non-covalent interactions such as hydrogen bonding, metal coordination, hydrophobic forces,
electronic effects and π-π stacking.3 This "template-directed" approach can efficiently promote formation
of the desired catenanes upon the final ring-closing reaction. For instance, Stoddart and co-worker utilized
the π-π stacking and donor-acceptor interactions to develop numerous functional catenanes.4 Metal
template based on the coordination was also used to synthesize mechanically interlocked catenanes.5,6 Beer
et al utilized anions as hydrogen-bond acceptor and developed an efficient synthetic method of catenanes.7
Recently, Leigh et al reported the synthetic strategy of [2]catenanes by the active metal templated click
chemistry.8 Olefine metathesis reaction as the classical cyclization was usually used for the synthesis of
catenane molecules after the formation of pseudorotaxanes by threading.9
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The dynamic clipping protocol for the synthesis of rotaxanes has been widely reported, which took
advantage of noncovalent bonding interactions to control the formation of ring by templation.10 Recently,
Liu reported a π-templated dynamic clipping reaction to construct [2]catenanes from dialdehyde, diamine
and bipyridyl tetracationic cyclophane.11 The template-directed clipping reaction based on
2,6-pyridinedicarboxaldehyde and tetra(ethylene glycol) bis(2-aminophenyl)ether can efficiently form
dynamic macrocycles around the dialkylammonium recognition sites.10,12 However, few reports
investigated the clipping efficiency of the macrocyclic alkylammonium sites. It was worth mentioning that
the clipping reaction based on 2,6-pyridinedicarboxaldehyde and tetra(ethylene glycol)
bis(2-aminophenyl)ether could form catenanes having different geometry due to the configuration of
N-hetero crown ether component, which promoted us to explore the application of clipping reaction in the
synthesis of catenanes and steric configuration of catenanes. Herein, we designed and synthesized two
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macrocycles having alkylammonium site, which were used to successfully prepare a series of [2]catenanes
in high yields by template-directed clipping reactions, as shown in Scheme 1.
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Scheme 1: Schematic representation of the template-directed clipping approach for the synthesis of [2]catenanes.
The stepwise synthesis of macrocyclic alkylammonium salts 1a-b was shown in Scheme 2. The
4-(aminomethyl)phenol (5) as starting material was treated with 4-hydroxybenzaldehyde (4a) and
4-hydroxy-3-methoxybenzaldehyde (4b) to afford the corresponding dynamic imine 6a and 6b in the
presence of anhydrous magnesium sulfate, respectively, which were then reduced by NaBH4 in the solution
of THF and MeOH to give the kinetically stable amine 7a and 7b, respectively, in 63-85% yields for two
steps. The cyclization was performed by the condensation of the amines 7a-b with the pseudo crown ether
8 in the condition of Cs2CO3, in which the Cs+ was also served as the template of cyclization simultaneity.
Compound 8 was synthesized according to the previous literature.13 In view of convenient purification, the
NH of free amines was protected by the Boc2O before purification. Subsequently, the Boc-protected
macrocyclic alkylamines 9a and 9b were obtained in 23-26% yields for two steps. Their Boc protective
groups were removed with excess trifluoroacetic acid (TFA) in dry dichloromethane, and the as-formed
amines were simultaneously protonated. Subsequent counterion exchange with saturated NH4PF6 afforded
the macrocyclic alkylammonium salts 1a and 1b in 91-93% yields. The key intermediates were well
characterized by the standard spectroscopic techniques such as NMR spectroscopy, mass spectrometry and
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elemental analysis. Additionally, for comparison, N-hetero crown ethers 2a and 2b as the one of
components of catenanes were also synthesized in 43-75% yields by the condensation of
2,6-pyridinedicarboxaldehyde (10a), 1,3-benzenedialdehyde (10b) and tetra(ethylene glycol)
bis(2-aminophenyl)ether (11), respectively, reduction with BH3·THF under the effect of
dibenzylammonium 12,12c which was outlined in Scheme 2. The chemical structures of all new compounds
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were well-confirmed by standard spectroscopic characterizations such as H NMR, 13C NMR, elemental
analyses and mass spectrometry (see supporting information).
Scheme 2
Figure 1. Partial 1H NMR spectra (400 MHz, CD3CN, 298 K) of 2a (A); 3a (B), 1a (C), 3b (D) and 2b (E).
The clipping reaction was firstly investigated for the symmetrical macrocyclic alkylammonium salt 1a
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by mixing together equimolar amounts of 10a and 11 in CD3CN, and a light yellow solution was observed
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due to the formation of Schiff bases. Subsequently, the clipping process was followed by H NMR
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spectroscopy. A complicated mixture containing imine oligomer was observed after one day by NMR.
Simultaneously, a broad singlet at 9.71 ppm for ammonium NH2+ protons was observed, which was well in
agreement with the chemical shift of ammonium reported in the previous literature.12 The results suggested
the existance of a dynamic [2]catenane. And then, the mixture was treated with BH3·THF to reduce the
dynamic imine bond into the kinetically stable C-NH bonds, and then the [2]catenane 3a was separated by
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column chromatography in 63% yield. In the H NMR spectra (Figure 1), the resonance of ammonium
NH2+ proton in the kinetically stable [2]catenane 3a showed an obvious upfield shift (singlet at 8.46 ppm)
compared with the dynamic [2]catenane, as shown in Figure 1(B). Furthermore, the resonance of the
protons on the adjacent benzene rings (He and Hf) showed obvious upfield shifts according to the 1H NMR
spectra of macrocycle 1a in the Figure 1(C). The results indicated the hetero crown ether encircled onto the
template-site of macrocyclic ammonium salt. Therefore, we demonstrated that the template-directed
clipping reaction was applied for efficient synthesis of [2]catenanes. Further proof was performed by the
electrospray ionization mass spectrometry (ESI-MS) in acetonitrile. As can be seen from Figure 2(C), the
- +
peak at m/z 1047.5 can be assigned to the [M-PF6 ] species, in which M was the [2]catenane 3a.
Figure 2. ESI mass spectra of compounds 1a (A), 1b (B), 3a (C), 3b (D), 3c (E) and 3d (F).
Stoddart et al found that the 1,3-benzenedialdehyde (10b) could also replace the
2,6-pyridinedicarboxaldehyde (10a) to perform the clipping reaction.12b Then we investigated the clipping
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reaction of 1,3-benzenedialdehyde (10b) and tetra(ethylene glycol) bis(2--aminophenyl)ether (11) with
macrocyclic ammonium salt 1a in CH3CN. After stirring for 2 weeks and reducing with BH3·THF, the pure
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[2]catenane 3b was successfully obtained by column chromatography in 51% yield. In the H NMR
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spectrum, the resonance of the protons on the adjacent benzene rings (He and Hf) showed obvious upfield
shifts compared with the macrocyclic ammonium salt 1a, which indicated that the hetero crown ether
encircled onto the macrocyclic ammonium salt. Furthermore, in comparison to [2]catenane 3a, a downfield
shift (He and Hf) was observed in the 1H NMR spectrum of 3b possibly due to the weaker
deficient-electron of the benzene ring in 2b than pyridine ring in 2a. In addition, the ESI-MS in Figure 2(D)
(peak at m/z 1046.4) further confirmed the existence of [2]catenane 3b. Subsequently, we investigated the
performance of unsymmetric macrocyclic ammonium 1b with the methoxy group in the clipping reaction.
The clipping reaction was performed in CH3CN. The results exhibited that the macrocyclic ammonium 1b
can also work well in the clipping reactions based on 2,6-pyridinedicarboxaldehyde (10a),
1,3-benzenedialdehyde (10b) with tetra(ethylene glycol) bis(2--aminophenyl)ether (11), respectively. And
the pure [2]catenanes 3c and 3d were obtained after column chromatography in high yields. Similarly, the
resonance of the protons on the adjacent benzene rings (He, Hf, Hh, Hi and Hk) of [2]catenanes 3c and 3d
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showed obvious upfield shifts compared with the H NMR spectra of unsymmetrical macrocyclic
alkylammonium salt 1b, which were well in agreement with the [2]catenanes 3a and 3b (see supporting
information: Figure S1). Moreover, the formation of catenanes was further confirmed by ESI mass
spectrometry in Figure 2. These results indicated that the introduction of substituted group on the
macrocyclic ammonium displayed little effect.
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Figure 3. The energy-minimized structures of [2]catenanes 3a-d based on density functional theory (DFT) calculations at the
B3LYP/6-31G* level by using Gaussian 09 programs.
Despite the template-directed clipping reaction has been confirmed to be efficient for the construction
of [2]catenane according to the above experiment, the steric configuration of [2]catenane was not defined.
In this respect, the steric configuration of [2]catenane 3 included two possible types: 1) the pyridine or
benzene unit (which contained H1 and H2 hydrogen atoms) of 2 was wrapped by the ammonium-based
crown ether 1 and located within the center of 1; and 2) the pyridine or benzene unit was situated at the
1
periphery of 1. For this case, we investigated their H-1H ROESY spectra (See supporting information:
Figure S2-S6), however no evident relevant signals of protons were observed between the pyridine or
benzene units (H1, H2 and H8) and macrocyclic ammonium salt 1. As a result, it was possible that the
pyridine or benzene (which contained H1 and H2 hydrogen atoms) unit was situated at the periphery of 1.
To clarifying that, we sought for theoretical calculations. Based on the density functional theory (DFT)
calculation at B3LYP/6-31G* level was performed by using Gaussian 09 programs. By comparison, we
found that these configurations possessed the minimized energy when the pyridine or benzene unit was
situated at the periphery of 1, as shown in Figure 3 (See supporting information: Table S1).
Scheme 3
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H4-7
H2
H3
CH2
(A)
(B)
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18
H1
NH
CH=N
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NH2
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H4-7
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(C)
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Ha-d
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He
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ppm
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7.0
6.0
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Figure 4. Partial 1H NMR spectra (400 MHz, CD3CN, 298 K) of 2a (A); 3c (B), 1b (C), 3d (D) and 2b (E).
Figure 5. The energy-minimized structure of [2]catenane 19 based on density functional theory (DFT) calculation at the
B3LYP/6-31G* level by using Gaussian 09 programs.
Based on the above theoretical calculations, if the bigger substituted group was introduced to the
4-site of 2,6-pyridinedicarboxaldehyde (10a) such as compound 16, it would also replace 10 to perform the
clipping reaction. In order to prove this hypothesis, firstly, we needed to prepare compound 16. According
to Scheme 3, compound 13 was used as starting materials to prepare compound 14 in an 89% yield, which
was reduced with NaBH4 to give diol 15 in an 83% yield. The oxidation based on diol 15 afforded the
4-site alkoxyl-substituted 2,6-pyridinedicarboxaldehyde16, which was cyclized with 11 in the presence of
template 12 to get N-hetero crown ether 17 in a high yield. Subsequently, the clipping reaction based on 11,
16 with 1a was investigated. As recorded by 1H NMR spectra in Figure 4, an obvious imine signal at 8.28
ppm and a broad resonance signal for ammonium NH2+ at 9.74 ppm were observed, and the chemical shift
of ammonium was similar to previous reports.12 The results suggested the formation of dynamic
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[2]catenane 18 and further confirmed the pyridine or benzene unit was situated at the periphery of
macrocycles. Subsequently, the mixture was treated with BH3·THF to give the kinetically stable
[2]catenane 19 in 65% yield. It is worth mentioning that the ammonium of [2]catenane 19 revealed very
evident downfield shift compared with the dynamic [2]catenane. Simultaneously, some similar changes of
1H NMR spectra were also found in Figure 4 as same as 3a and 3c. Additionally, we also utilized Gaussian
09 programs to optimize and obtain the energy-minimized structure via density functional theory (DFT)
calculations at the B3LYP/6-31G* level, as shown in Figure 5.
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In conclusion, five [2]catenanes were efficiently synthesized in high yields by a template-directed
clipping approach. This research further confirmed that the template-directed clipping reaction could be
also utilized as an efficient approach to synthesize catenanes. Such approach could also be used for the
synthesis of more complicated catenanes and molecular necklaces.
 EXPERIMENTAL SECTION
General Methods. All manipulations were carried out under an argon atmosphere by using standard Schlenk techniques,
unless otherwise stated. THF was distilled under nitrogen from sodium-benzophenone. EtOH and MeOH were distilled
under drying pipe from magnesium-iodine. DMF was dried with magnesum sulfate then distilled under vacuum. 1H and 13
C
NMR spectra were collected with either a 400 or 600 MHz spectrometer. Mass spectra were measured in the ESI mode.
Elemental analyses were performed by investigation of C, H, N.
Synthesis of Compound 6b ((E)-4-(((4-hydroxybenzyl)imino)methyl)-2-methoxyphenol): To
a
solution of
4-hydroxy-3-methoxybenzaldehyde 4b (0.61 g, 4.0 mmol) in anhydrous EtOH (80 mL) was added 4-(aminomethyl)phenol 5
(0.49 g, 4.0 mmol) with anhydrous magnesium sulfate acting as drying agent under a argon atmosphere. The mixture was
refluxed for 24 h. The formed precipitate was collected and the crude product was washed with EtOH to give a yellow solid
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6b. Yield: 0.92 g, 89%. mp 205-207 ℃. Compound 6b: 1H NMR (400 MHz, DMSO-d6): δ ppm = 3.78 (s, 3H, OCH3), 4.58
(s, 2H, CH2), 6.75 (d, J = 7.6 Hz, 2H, Ar), 6.84 (d, J = 7.6 Hz, 1H, Ar), 7.12 (t, J = 13.2 Hz, 3H, Ar), 7.36 (s, 1H, Ar), 8.27 (s,
1H, CH=N). 13C NMR (100 MHz, DMSO-d6): δ ppm = 56.2 (s, OCH3), 63.6 (s, CH2), 109.9, 115.2, 123.0, 127.8, 129.3,
130.1, 148.0, 149.6, 156.3, 160.7 (s, Ar and CH=N). Anal. Calcd for C15H15NO3: C, 70.02; H, 5.88; N, 5.44. Found: C, 70.23;
H, 5.80; N, 5.32.
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Synthesis of Compound 7a (4,4'-(azanediylbis(methylene))diphenol): To a solution of 4-hydroxybenzaldehyde 4a (0.49 g,
4.0 mmol) in anhydrous EtOH (80 mL) was added 4-(aminomethyl)phenol 5 (0.49 g, 4.0 mmol) with anhydrous magnesium
sulfate acting as drying agent under a argon atmosphere. The mixture was refluxed for 24 h. The solvent was removed under
vacuum and the residue was dissolved in THF (60 mL) and MeOH (60 mL), and then NaBH4 (0.61 g, 16.0 mmol) was added
slowly in ten portions. After stirring for overnight, the reaction was quenched with the saturated ammonium chloride (aq).
The solvents were removed under vacuum, and the residue was extracted by absolute ethyl ether, and then dried over
anhydrous sodium sulfate. Unon removed of solvent under reduced pressure and purified on a silica gel column using
petroleum ether/ethyl acetate (1:9) as the eluent to obtain the target compound 7a as a brown solid. Yield: 0.58 g, 63%. mp
141-142 ℃. Compound 7a: 1H NMR (400 MHz, DMSO-d6): δ ppm = 3.52 (s, 4H, CH2), 6.70 (d, J = 8.0 Hz, 4H, Ar), 7.11
(d, J = 8.0 Hz, 4H, Ar), 9.27 (s, 2H, OH). 13C NMR (100 MHz, DMSO-d6): δ ppm = 51.7 (s, CH2), 114.9, 129.1, 131.0,
156.0 (s, Ar). EI MS: m/z = 229.1 [M]+; calculated exact mass: 229.1. Anal. Calcd for C14H15NO2: C, 73.34; H, 6.59; N, 6.11.
Found: C, 73.22; H, 6.72; N, 6.03.
Synthesis of Compound 7b (4-(((4-hydroxybenzyl)amino)methyl)-2-methoxyphenol): The Schiff base 6b (1.00 g, 4.0
mmol) was dissolved in THF (60 mL) and MeOH (60 mL), and then NaBH4 (0.61 g, 16.0 mmol) was added slowly in ten
portions. After stirring for overnight, the reaction was quenched with the saturated ammonium chloride (aq). The solvents
were removed under vacuum, and the residue was extracted by absolute ethyl ether, and then dried over anhydrous sodium
sulfate. Upon removed of solvent under reduced pressure and purified on a silica gel column using petroleum ether/ethyl
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acetate (1:9) as the eluent to obtain the target compound as a brown solid Yield: 0.88 g, 85%. mp 146-147 ℃. Compound
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1
7b: H NMR (400 MHz, DMSO-d6): δ ppm = 3.56 (s, 4H, CH2), 3.75 (s, 3H, OCH3), 6.72 (d, J = 8.0 Hz, 4H, Ar), 6.92 (s,
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1H, Ar), 7.13 (d, J = 8.4 Hz, 2H, Ar). 13C NMR (100 MHz, DMSO-d6): δ ppm = 51.6 (s, CH2), 51.9 (s, CH2), 55.5 (s, OCH3),
112.2, 115.0, 115.1, 120.5, 129.3, 130.7, 131.4. 145.2, 147.5, 156.1 (s, Ar). EI MS: m/z = 259.1 [M]+; calculated exact mass:
259.1. Anal. Calcd for: C15H17NO3: C, 69.48; H, 6.61; N, 5.40. Found: C, 69.25; H, 6.76; N, 5.48.
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Synthesis of Compound 9a: A mixture of 8 (0.34 g, 0.5 mmol) and 7a (0.12 g, 0.5 mmol) in dry DMF (150 mL) was added
dropwise over a period of 12 h to a stirred suspension of Cs2CO3 (0.65 g, 2.0 mmol) at 80℃ under a dry N2 atmosphere.
After the addition was completed, the mixture was stirred at 80℃ for a further 3 d. The resulting mixture was allowed to
cool to room temperature, and filtered. After that, the solvent were removed under vacuum, and the residue was extracted by
ethyl ether, and then dried over anhydrous sodium sulfate. Upon removed of solvent under reduced pressure and dried. The
unpurified product was dissolved in dry chloroform (20 mL) and then Boc2O (0.30 g, 1.4 mmol) and triethylamine (0.24 mL)
were added. The mixture was stirred at room temperature for 24 h. Upon removed of solvent under reduced pressure and
purified on a silica gel column using petroleum ether/ethyl acetate (1:1) as the eluent to obtain the Boc-protected macrocycle
9a as a light yellow liquid. Yield: 0.09 g, 26%. Compound 9a: 1H NMR (400 MHz, CDCl3): δ ppm = 1.47 (s, 9H, Boc),
3.70-3.76 (m, 8H, CH2), 3.80 (t, J = 4.0 Hz, 4H, CH2), 3.87 (t, J = 4.0 Hz, 4H, CH2), 4.05 (t, J = 4.0 Hz, 4H, CH2), 4.15 (t, J
= 4.0 Hz, 4H, CH2), 4.32 (s, 2H, CH2), 4.41 (s, 2H, CH2), 6.66 (t, J = 8.0 Hz, 4H, Ar), 6.77 (d, J = 8.0 Hz, 2H, Ar), 6.87-6.95
(m, 6H, Ar). 13C NMR (100 MHz, CDCl3): δ ppm = 28.3, 51.1, 67.4, 68.8, 69.6, 69.75, 70.8, 79.7, 114.3, 114.7, 121.5, 128.8,
129.7, 130.5, 130.8, 148.8, 155.8, 157.4. EI MS: m/z = 667.4 [M]+; calculated exact mass: 667.3. Anal. Calcd for
C37H49NO10: C, 66.55; H, 7.40; N, 2.10. Found: C, 66.43; H, 7.25; N, 2.24.
Synthesis of Compound 9b: Compound 9b was prepared by an analogous method similar to that used for to 9a and was
obtained as a light yellow liquid. Yield: 0.08 g, 23%. Compound 9b: 1H NMR (400 MHz, CDCl3): δ ppm = 1.47 (s, 9H, Boc),
3.64-3.75 (m, 12H, OCH3 and CH2), 3.81 (d, J = 4.4 Hz, 4H, CH2), 3.87 (t, J = 4.8 Hz, 4H, CH2), 4.06 (t, J = 4.4 Hz, 2H,
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CH2), 4.13-4.41 (m, 9H, CH2), 6.40-6.99 (m, 11H, Ar). 13C NMR (100 MHz, CDCl3): δ ppm = 28.3, 51.0, 51.4, 55.5, 60.2,
67. 5, 68.8, 69.6, 69.7, 69.7, 70.7, 77.2, 79.7, 111.1, 112.0, 113.7, 114.3, 114.6, 120.0, 120.8, 121.4, 128.9, 129.8, 130.7,
131.5, 131.9, 147.0, 148.8, 149.3, 155.6, 157.6 (d). ESI MS: m/z = 720.2 [M + Na+], 736.1 [M + K+]; calculated exact mass:
697.3. Anal. Calcd for C38H51NO11: C, 65.41; H, 7.37; N, 2.01. Found: C, 65.26; H, 7.46; N, 2.09.
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Synthesis of Compound 1a: To a solution of the Boc-protected amine 9a (0.13 g, 0.19 mmol) in dry DCM (10 mL), TFA
(0.06 mL, 0.95 mmol) was added at room temperature. After stirring for 2 h under nitrogen atmosphere, the solvent was
removed under vacuum. The residue was dissolved in MeOH (1.0 mL), and then saturated NH4PF6 (2.0 mL, aq) was added
to yield a brown precipitate. After filtering, washing with H2O and dry under vacuum, the title compound was obtained as
the light yellow gum. Yield: 0.12 g, 91%. Compound 1a: 1H NMR (400 MHz, CD3CN): δ ppm = 3.60-3.65 (m, 8H, CH2),
3.72-3.74 (m, 4H, CH2), 3.76-3.78 (m, 4H, CH2), 4.05-4.07 (m, 4H, CH2), 4.13 (s, 4H, CH2), 4.15-4.17 (m, 4H, CH2), 6.86
(d, J = 8.8 Hz, 4H, Ar), 6.89-6.95 (m, 4H, Ar), 7.14 (d, J = 8.8 Hz, 4H, Ar). 13C NMR (150 MHz, CD3CN): δ ppm = 51.9,
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69.1, 69.4, 70.6, 70.6, 71.4, 71.7, 115.4, 116.5, 118.7, 122.9, 124.1, 132.8, 149.6, 160.9. ESI MS: m/z = 568.3 [M-PF6 ];
calculated exact mass: 713.3. Anal. Calcd for C32H42F6NO8P: C, 53.86; H, 5.93; N, 1.96. Found: C, 53.93; H, 6.03; N, 1.81.
Synthesis of Compound 1b: Compound 1b was prepared by an analogous method similar to that used for to 1a and was
obtained as a light yellow liquid. Yield: 0.13 g, 93%. Compound 1b: 1H NMR (600 MHz, CD3CN): δ ppm = 3.57-3.61 (m,
8H, CH2), 3.69 (t, J = 3.6 Hz, 4H, CH2), 3.73-3.75 (m, 8H, CH2), 4.01-4.03 (m, 4H, CH2), 4.10 (d, J = 7.8 Hz, 4H, CH2),
4.15 (s, 3H, OCH3), 6.78-6.93 (m, 9H, Ar), 7.18 (d, J = 8.4 Hz, 2H, Ar). 13C NMR (150 MHz, CD3CN): δ ppm = 50.0, 55.0,
67.8, 68.1, 69.0, 69.9, 70.0, 105.1, 114.0, 114.8, 116.2, 121.0, 122.4, 131.2, 148.2, 148.8, 149.2, 159.4. ESI MS: m/z = 598.3
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[M-PF6 ]; calculated exact mass: 743.3. Anal. Calcd for C33H44F6NO9P: C, 53.30; H, 5.96; N, 1.88. Found: C, 53.19; H, 6.08;
N, 1.92.
Synthesis
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Compound
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10b
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2,2'-((((oxybis(ethane-2,1-diyl))bis(oxy))bis(ethane-2,1-diyl))bis(oxy))dianiline 11 (0.38 g, 1.0 mmol), and
dibenzylammonium hexafluorophosphate 12 (0.34 g, 1.0 mmol) in acetonitrile (50 mL) was stirred at room temperature
overnight. BH3·THF (1.0 M in THF, 5 mL, 5.0 mmol) was added to the mixture, which was left stirring at rt for 4 h. The
excess of solvent was removed under vacuum and the residue was partitioned between 2 M aqueous NaOH solution and
CHCl3. The residue was extracted with DCM and the organic layer was washed with water, dried over anhydrous sodium
sulfate, and then purified by column chromatography (silica gel, CH2Cl2) to give compounds 2b as the light yellow gum.
Yield: 0.21 g, 43%. Compound 2b: 1H NMR (400 MHz, CDCl3): δ 3.54 – 3.46 (m, 4H), 3.62-3.55 (m, 4H), 3.75 (d, J = 4.2
Hz, 4H), 4.11-4.03 (m, 4H), 4.29 (d, J = 5.2 Hz, 4H), 5.07 (s, 2H), 6.56 (dd, J = 15.0, 7.7 Hz, 4H), 6.86-6.74 (m, 4H), 7.33
(dd, J = 11.9, 6.6 Hz, 3H), 7.45 (s, 1H), 13C NMR (100 MHz, CDCl3) δ 47.9, 70.0, 70.2, 70.9, 71.0, 110.8, 113.6, 116.9, 122.
7, 126.4, 127.3, 129.1, 139.9, 141.4, 146.5. ESI MS: m/z = 478.9 [M]+; calculated exact mass: 478.2. Anal. Calcd for:
C28H34N2O5: C, 70.27; H, 7.16; N, 5.85. Found: C, 70.46; H, 7.32; N, 5.67.
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Synthesis of Compound 3a-d: A mixture of macrocyclic dialkylammonium 1a-b (71.3 mg or 74.3 mg, 0.1 mmol),
tetraethyleneglycol bis(2-aminophenyl) ether 11 (37.6 mg, 0.1 mmol) and dicarboxaldehyde 10a-b (13.5 mg or 13.4 mg, 0.1
mmol) were stirred for 10 d in dry CH3CN (10 mL) under nitrogen atmosphere at room temperature. Then BH3·THF solution
(0.8 mL) was added and the mixture was further stirred overnight. The solvents were removed under vacuum and the residue
was purified by column chromatography (silica gel, DCM / MeCN / MeOH = 100:0:0 ~ 75:25:1) to give the [2]catenane.
Compound 3a: The white solid. Yield: 75.1 mg, 63%. mp > 300 ℃. 1H NMR (400 MHz, CD3CN): δ ppm = 3.41-3.43 (m,
3H, CH2), 3.48-3.51 (m, 3H, CH2), 3.53-3.70 (m, 17H, CH2), 3.74-3.77 (m, 5H, CH2), 3.87-3.89 (m, 3H, CH2), 3.97-4.03 (m,
5H, CH2), 4.11-3.18 (m, 8H, CH2), 4.37-4.40 (m, 4H, CH2), 6.41-6.43 (m, 2H, Ar), 6.57 (d, J = 8.0 Hz, 3H, Ar), 6.75-6.77
(m, 8H, Ar), 6.86-6.94 (m, 7H, Ar), 7.18-7.20 (m, 1H, Ar), 7.34 (d, J = 8.0 Hz, 1H, Ar), 7.79 (t, J = 8.0 Hz, 1H, Ar), 8.47 (s,
2H, NH2 ). The 13C NMR spectrum was not collected due to the poor solubility of 3a. ESI MS: m/z = 1047.5 [M-PF6 ];
+
-
calculated exact mass: 1192.5. Anal. Calcd for C59H75F6N4O13P: C, 59.39; H, 6.34; N, 4.70. Found: C, 59.51; H, 6.28; N,
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Compound 3b: The white solid. Yield: 60.8 mg, 51%. mp > 300 ℃.1H NMR (400 MHz, CD3CN): δ ppm = 3.57-3.65 (m,
15H, CH2), 3.67-3.70 (m, 3H, CH2), 3.72-3.81 (m, 9H, CH2), 4.01-4.06 (m, 3H, CH2), 4.07-4.12 (m, 7H, CH2), 4.16-4.18 (m,
2H, CH2), 4.30-4.35 (m, 2H, CH2), 4.55 (d, J = 12.0 Hz, 5H, CH2), 4.79-4.82 (m, 2H, CH2), 6.48-6.91 (m, 17H, Ar),
7.18-7.33 (m, 7H, Ar). The 13C NMR spectrum was not collected due to the poor solubility of 3b. ESI MS: m/z = 1046.4
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[M-PF6 ]; calculated exact mass: 1191.5. Anal. Calcd for C60H76F6N3O13P: C, 60.45; H, 6.43; N, 3.52. Found: C, 60.53; H,
6.29; N, 3.63.
Compound 3c: The white solid. Yield: 88.0 mg, 72%. mp > 300 ℃. 1H NMR (400 MHz, CD3CN): δ ppm = 3.23 (s, 1H,
CH2), 3.40-3.79 (m, 24H, CH2), 3.84-3.97 (m, 4H, CH2), 4.04-4.15 (m, 8H, CH2), 4.40-4.47 (m, 4H, CH2), 4.75 (s, 8H, CH2),
5.03 (s, 2H, CH2), 6.35 (s, 1H, Ar), 6.41 (d, J = 4.0 Hz, 1H, Ar), 6.52-6.93 (m, 17H, Ar), 7.19-7.23 (m, 2H, Ar), 7.38 (d, J =
+
4.0 Hz, 1H, Ar), 7.81 (t, J = 4.0 Hz, 1H, Ar), 8.40 (s, 2H, NH2 ). The 13C NMR spectrum was not collected due to the poor
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solubility of 3c. ESI MS: m/z = 1077.3 [M-PF6 ]; calculated exact mass: 1222.5. Anal. Calcd for C60H77F6N4O14P: C, 58.91;
H, 6.34; N, 4.58. Found: C, 59.02; H, 6.18; N, 4.52.
Compound 3d: The white solid. Yield: 81.8 mg, 67%. mp > 300 ℃.1H NMR (400 MHz, CD3CN): δ ppm = 3.51-3.67 (m,
16H, CH2), 3.70-3.82 (m, 12H, CH2), 4.04-4.13 (m, 11H, CH2), 4.15-4.18 (m, 2H, CH2), 4.30 (s, 2H, CH2), 4.36 (s, 2H,
CH2), 4.58 (s, 4H, CH2), 4.80-4.91 (m, 2H, CH2), 6.51-6.93 (m, 15H, Ar), 7.19-7.47 (m, 9H, Ar). The 13C NMR spectrum
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was not collected due to the poor solubility of 3d. ESI MS: m/z = 1076.4 [M–PF6 ]; calculated exact mass: 1221.5. Anal.
Calcd for C61H78F6N3O14P: C, 59.94; H, 6.43; N, 3.44. Found: C, 59.88; H, 6.36; N, 3.56.
Synthesis of Compound 14 (dimethyl 4-(tetradecyloxy)pyridine-2,6-dicarboxylate): A mixture of compound dimethyl
4-hydroxypyridine-2,6-dicarboxylate 13 (2.10 g, 10 mmol), 1-bromotetradecane (2.80 g, 10 mmol), K2CO3 (2.80 g, 20 mmol)
in dry DMF (100 mL) was heated to 50 ℃ under argon atmosphere for 24 h. The solvent was removed under vacuum, and
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the residue was extracted with ethyl ether. The organic layer was washed with water, dried over anhydrous sodium sulfate,
and the excess of solvent was then removed under vacuum. The residue was purified by recrystallization in methanol to give
compound 14 as the yellow solid. Yield: 3.62 g, 89%. mp 78-79 ℃.1H NMR (400 MHz, CDCl3): δ 0.88 (t, J = 6.4 Hz, 3H,
CH3), 1.26 (br, 20H, CH2), 1.35-1.47 (m, 2H, CH2), 1.77-1.86 (m, 2H, CH2), 3.55 (s, 6H, COOMe), 4.13 (t, J = 6.4 Hz, 2H,
OCH2), 7.81 (s, 2H, Ar). 13C NMR (100 MHz, CDCl3): δ 14.1, 22.7, 23.0, 23.2, 25.8, 28.7, 29.2, 29.3, 29.5, 29.6, 30.0, 31.9,
41.9, 53.2, 65.2, 69.1, 114.5, 149.6, 165.2, 167.1. EI MS: m/z =407.4 [M]+; calculated exact mass:407.3. Anal. Calcd for:
C23H37NO5: C, 67.78; H, 9.15; N, 3.44. Found: C, 67.64; H, 9.46; N, 3.23.
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Synthesis of Compound 15 ((4-(tetradecyloxy)pyridine-2,6-diyl)dimethanol): Compound 14 (1.80 g, 5.2 mmol) was
dissolved in a mixture of solvents of MeOH (50 mL) and THF (50 mL), powder of NaBH4 (0.70 g) was then added in
portions. The mixture was stirred at room temperature for 24 h and the excess of solvent was removed under vacuum. The
residue was extracted with ethyl ether and the organic layer was washed with water The organic layer was washed with water,
dried over anhydrous sodium sulfate. The residue was purified by recrystallization in DCM / hexane to give compound 15 as
the white solid. Yield: 1.52 g, 83%. mp 90-91 ℃. 1H NMR (400 MHz, CDCl3): δ 0.88 (t, J = 6.4 Hz, 3H, CH3), 1.26 (br,
20H, CH2), 1.35-1.47 (m, 2H, CH2), 1.75-1.80 (m, 2H, CH2), 4.01 (t, J = 6.4 Hz, 2H, OMe), 4.69 (s, 4H, CH2), 6.69 (s, 2H,
Ar). 13C NMR (100 MHz, CDCl3): δ 14.1, 22.7, 25.9, 28.8, 29.3, 29.3, 29.5, 29.6, 29.6, 31.9, 64.4, 68.2, 105.6, 160.3, 166.6.
EI MS: m/z = 351.5 [M]+; calculated exact mass: 351.3. Anal. Calcd for: C21H37NO3: C, 71.75; H, 10.61; N, 3.98. Found: C,
71.64; H, 10.78; N, 3.77.
Synthesis of Compound 16 (4-(tetradecyloxy)pyridine-2,6-dicarbaldehyde): A mixture of 15 (0.79 g, 2.3 mmol) and SeO2
(0.50 g, 4.6 mmol) in dioxane (10 mL) was heated to 90 ℃under argon atmosphere for 16 h. After cooling, the mixture was
filtered and washed with more dioxane. The excess of solvent in the filtrate was removed under vacuum and the residue was
purified by column chromatography (silica gel, CH2Cl2) to give compound 16 as the light brown solid. mp 61-62 ℃. Yield:
1
0.59 g, 75%. H NMR (400 MHz, CDCl3): δ 0.88 (t, J = 6.4 Hz, 3H, CH3), 1.26 (br, 20H, CH2), 1.45-1.47 (m, 2H, CH2),
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1.81-1.86 (m, 2H, CH2), 4.14 (t, J = 6.4 Hz, 2H, OCH2), 7.63 (s, 2H, Ar), 10.12 (s, 2H, CHO). 13C NMR (100 MHz, CDCl3):
δ 14.1, 22.7, 25.8, 28.6, 29.2, 29.3, 29.5, 29.5, 29.6, 31.9, 69.3, 111.5, 154.7, 167.1, 192.4. EI MS: m/z =347.4 [M]+;
calculated exact mass: 347.2. Anal. Calcd for: C21H33NO3: C, 72.58; H, 9.57; N, 4.03. Found: C, 72.64; H, 9.45; N, 3.89.
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Synthesis of Compound 17: A solution of 16 (0.35 g, 1.0 mmol), 11 (0.38 g, 1.0 mmol), and dibenzylammonium
hexafluorophosphate 12 (0.34 g, 1.0 mmol) in acetonitrile (50 mL) was stirred at room temperature overnight. BH3·THF (1.0
M in THF, 5 mL, 5.0 mmol) was added to the mixture, which was left stirring at rt for 4 h. The excess of solvent was
removed under vacuum and the residue was partitioned between 2 M aqueous NaOH solution and CHCl3. The residue was
extracted with DCM and the organic layer was washed with water, dried over anhydrous sodium sulfate, and then purified by
1
column chromatography (silica gel, CH2Cl2) to give compound 17 as the light yellow gum. Yield: 0.52 g, 75%. H NMR
(400 MHz, CDCl3): δ 0.88 (t, J = 6.4 Hz, 3H, CH3), 1.26 (br, 20H, CH2), 1.38 (br, 2H, CH2), 1.69-1.73 (m, 2H, CH2), 3.56 (t,
J = 4.4 Hz, 4H, CH2), 3.74 (t, J = 4.4 Hz, 4H, CH2), 3.84 (s, 4H, CH2), 3.92 (t, J = 6.4 Hz, 2H, CH2), 4.15 (s, 4H, CH2), 4.43
(s, 4H, CH2), 5.73 (s, 2H), 6.60-6.66 (m, 4H, Ar), 6.74 (s, 2H, Ar), 6.85 (d, J = 7.6 Hz, 2H, Ar), 6.91 (t, J = 7.6 Hz, 2H, Ar).
13C NMR (100 MHz, CDCl3): δ 14.1, 22.7, 25.9, 28.9, 29.3, 29.3, 29.5, 29.6, 29.6, 31.9, 49.3, 68.0, 70.0, 70.3, 70.7, 70.8,
106.3, 110.6, 114.3, 116.4, 122.9, 140.0, 146.1, 160.0, 166.5. ESI MS: m/z = 691.0 [M]+; calculated exact mass: 691.5. Anal.
Calcd for: C41H61N3O6: C, 71.17; H, 8.89; N, 6.07. Found: C, 71.34; H, 9.01; N, 5.89.
Synthesis of Compound 19: Catenane 19 was prepared by an analogous method similar to that of 3 and was obtained as
1
light yellow gum. Yield: 91.3 mg, 65%. H NMR (400 MHz, CDCl3): δ 0.88 (d, J = 6.7 Hz, 3H), 1.28 (br, 20H), 1.39 (br,
2H), 1.73 (dd, J = 13.7, 6.6 Hz, 2H), 3.44 (dd, J = 11.5, 6.6 Hz, 5H), 3.51 (dd, J = 10.3, 5.3 Hz, 9H), 3.71-3.57 (m, 12H),
3.92 (t, J = 8.2 Hz, 5H), 3.97 (t, J = 5.4 Hz, 2H), 4.10 (dd, J = 15.5, 5.3 Hz, 11H), 4.36 (d, J = 4.2 Hz, 6H), 6.49-6.41 (m,
2H), 6.57 (d, J = 8.5 Hz, 4H), 6.76 (t, J = 13.9 Hz, 8H), 6.89-6.82 (m, 4H), 6.96-6.90 (m, 4H), 8.62 (s, 2H). 13C NMR (100
MHz, CD3CN): δ ppm = 14.0, 23.0, 26.2, 29.3, 29.7, 29.9, 30.0, 32.3, 50.4, 52.1, 65.2, 68.1, 68.4, 69.0, 69.8, 70.1, 70.9, 71.5,
71.9, 108.9, 110.9, 113.1, 114.8, 115.3, 116.0, 120.1, 122.0, 124.9, 131.3, 138.0, 147.4, 149.2, 159.9, 161.0, 167.2. ESI MS:
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m/z = 1259.6 [M-PF6 ]; calculated exact mass: 1404.7. Anal. Calcd for C73H103F6N4O14P: C, 62.38; H, 7.39; N, 3.99. Found:
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 ACKNOWLEDGMENT
The authors acknowledge financial support from National Natural Science Foundation of China (Nos. 20931006, 21072070)
and Program for Changjiang Scholars and Innovative Research Team in University (No. IRT0953) and self-determined
research funds of CCNU from the colleges’ basic research and operation of MOE.
 SUPPORTING INFORMATION
Details on the synthesis, characterization, NMR, MS spectra of interminates and [2]catenanes are available in the Supporting
Information. This material is available free of charge via the Internet at http://pubs.acs.org.

REFERENCES
(1) Balzani, V.; Credi, A.; Venturi, M. Molecular Devices and Machines: Concepts and Perspectives for the Nanoworld,
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