Construction of hetero[n]rotaxanes by use of polyfunctional rotaxane frameworks

Article abstract of DOI:10.1021/jo402166y

Heterorotaxanes, one class of topological organic structures, have attracted increasing interesting during the past two decades. In general, two types of heterorotaxane structures exist, one in which two or more different macrocycles are threaded onto one dumbbell-shaped molecule and the other where one macrocycle is threaded onto two or more different dumbbell-shaped molecules. In comparison to these traditional types, another family of topologically interesting heterorotaxanes can be envisaged as arising from polyfunctional molecules that possess both host (crown ether) and guest (ammonium templates). In the present investigation, we have explored the construction of selected members of this new heterorotaxane family, which possess crown ether moieties that are wrapped around a dumbbell-shaped molecule. These structures are prepared by routes in which "stitching" processes, involving template-directed clipping reaction or olefin metathesis reactions, are used to install crown ether ring systems encircling ammonium cation centers. This is then followed by implementation of a threading-followed-by-stoppering sequence to install a second encircling crown ether ring. The results show that the polyfunctional building blocks assemble with high efficiencies. Finally, this investigation provides a foundation for future studies aimed at constructing more complicated heterorotaxane architectures, such as switchable systems, self-assembling polymers, and functional molecular machines.

Full text of DOI:10.1021/jo402166y

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Article
Construction of Hetero[n]rotaxanes Using
Polyfunctional Rotaxane Frameworks
Ziyong Li, Guoxing Liu, Wen Xue, Di Wu, Ying-Wei Yang,
Jishan Wu, Sheng Hua Liu, Juyoung Yoon, and Jun Yin
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/jo402166y • Publication Date (Web): 14 Oct 2013
Downloaded from http://pubs.acs.org on October 17, 2013
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Construction of Hetero[n]rotaxanes Using Polyfunctional
Rotaxane Frameworks
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Ziyong Li,† Guoxing Liu,† Wen Xue,† Di Wu,† Ying-Wei Yang,§ Jishan Wu,ǁ Sheng Hua
Liu,†* Juyoung Yoon,‡* 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, P. R. China.
‡Department of Chemistry and Nano Science, Global Top 5 Program, Ewha Womans University, Seoul
120-750, Korea.
§State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University,
Changchun, 130012, P. R. China.
ǁDepartment of Chemistry, National University of Singapore, 3 Science Drive 3, 117543, Singapore.
* E-mail: yinj@mail.ccnu.edu.cn; chshliu@mail.ccnu.edu.cn; jyoon@ewha.ac.kr
ABSTRACT: Heterorotaxanes, one class of topological organic structures, have attracted increasing
interesting during the past two decades. In general, two types of heterorotaxane structures exist, one in
which two or more different macrocycles are threaded onto one dumbbell-shaped molecule and the other
where one macrocycle is threaded onto two or more different dumbbell-shaped molecules. In comparison
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to these traditional types, another family of topologically interesting heterorotaxanes can be envisaged as
arising from polyfunctional molecules that possess both host (crown ether) and guest (ammonium
templates). In the current investigation, we have explored the construction of selected members of this
new heterorotaxane family, which possess crown ether moieties that are wrapped dumbbell-shaped
molecule. These structures are prepared by routes in which “stitching” processes, involving
template-directed clipping reaction or olefin metathesis reactions, are used to install crown ether ring
systems encircling ammonium cation centers. This is then followed by implementation of a
threading-followed-by-stoppering sequence to install a second encircling crown ether ring. The results
show that the polyfunctional building blocks assemble with high efficiencies. Finally, this investigation
provides a foundation of future studies aimed at constructing more complicated heterorotaxane
architectures, such as switchable systems, self-assembling polymers and functional molecular machines.
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n INTRODUCTION
Construction of the novel topological structures has been one of the major goals of research efforts in
the areas of supramolecular chemistry and self-assembly. Much attention has been given to the design and
synthesis of molecular representations of mathematical topologies, and to the structural analysis of these
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topologically interesting chemical motifs. As one type of classic topological structures, mechanically
interlocked molecules (MIMs), such as rotaxanes, catenanes, knots, and links, have unique structural
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features that enable their application in various fields, including molecular devices, molecular switches
and machines, 3 nanotechnology, 4 biological technology, 5 drug delivery 4a, 5b and polymer materials. 6 As a
consequence, the creation of MIMs that have novel configurations is an important aim of supramolecular
self-assembly and systems chemistry.
In recent years, the focus of studies of rotaxanes has shifted from single and simple structures to those
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that possess functionalized and complicated structures.
Recently, heterorotaxanes have attracted
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increasing interest owing to the fact that interactions between the cyclic and linear components of these
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systems can lead to different chemical structures with interesting functionalities.
Based on a
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consideration of binding affinities between different host and guest components, a self-sorting strategy was
developed for the efficient construction of heterorotaxanes, which have topological configurations that are
similar to those of dumbbell-shaped molecules wrapped by different types of macrocyclic hosts. 9 For
example, in 1996 Stoddart and his coworkers took advantage of the different binding affinities of
dibenzo[24]crown-8 and bis(p-phenylene-34-crown-10) towards secondary dialkylammonium and
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bipyridinium ions to synthesize a novel hetero[3]pseudorotaxane.
Schalley et al. used the different
binding behaviors of [24]crown-8 and [21]-crown-7 towards dialkylammonium ions to construct
hetero[3]rotaxanes. 11 12 Chiu et. al also described the use of another self-sorting method to construct a
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hetero[3]rotaxane.
Recently, a new twin-axial hetero[7]rotaxane derived from benzo-21-crown-7 and
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bis(p-phenylene-34-crown-10) was prepared by Liu and co-workers. In addition to crown ethers, other
macrocyclic hosts such as cucurbiturils, 15 cyclodextrins, 16 and others 17, 18 have been utilized to construct
heterorotaxanes. For example, in 2010 Wu and our group independently reported a hetero[4]rotaxane that
is generated from a crown ether and cucurbituril by employing a threading-followed-by-clipping approach.
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Another family of heterorotaxanes contain members that are composed of macrocycles in which
different dumbbell-shaped molecules are threaded. In 2006, Anderson et al. described a hetero[3]rotaxane
containing one stilbene and one cyanine dye moiety threaded through the center of a γ–cyclodextrin
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molecule. Schalley’s group also constructed a series of heterorotaxanes by employing self-assembly of
hosts containing 21-crown-7 and 24-crown-8 units onto different ammonium templates. 21
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In the effort described below, we have designed, synthesized and investigated several new
hetero[n]rotaxanes (n = 3, 4) and hetero[5]pseudorotaxane that have unique topological structures that are
different from those of the two traditional types described above. The new types of dual functional
molecules are comprised of crown ether and ammonium building blocks that play the roles of respective
hosts and guests. The crown ether groups in these dual functional molecules are designed to have the
ability to wrap dumbbell-shaped molecules while the ammonium components play the roles of guest
templates that thread the crown ethers. The dual-functional molecules highly efficiently assemble to form
novel topological hetero[n]rotaxanes.
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n RESULTS AND DISCUSSION
Design of new heterorotaxanes. The general strategy we have developed for the preparation of novel
hetero[n[rotaxane is depicted pictorially in Scheme 1. In general, the heterorotaxanes are comprised of two
simple rotaxanes A and B, which are formed from polyfunctional host-guest building blocks. It should be
noted that previous efforts have shown that dual functional molecules of this type undergo intermolecular
self-assembly to form daisy-shaped molecules and polymers. 22 Consequently, in our approach a stopper is
introduced in order to avoid daisy-shaped polymer formation. The building block C, contains a stopper
group along with both a crown ether and an ammonium cation group. In this approach, hetero[n]rotaxane
construction take place through a two-step self-assembly strategy in which the ammonium unit serves as a
template for incorporating an encircling macrocyclic ring by using either template-directed clipping
reaction or olefin metathesis reactions. 23 These processes afford intermediate D, which is then subjected to
a threading-followed-by-stoppering sequence to install a second encircling crown ether ring as part of the
new heterorotaxane.
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Scheme 1. A schematic representation of the route for heterorotaxane formation.
Synthesis of building blocks. One group of substances needed to aid spectroscopic analysis of the
processes involved in heterorotaxane formation following the strategy described above, include the
azacrown and normal crown ethers 4 and 9 (Scheme 2). The synthesis 4 is accomplished using
dibenzylammonium ion 3 as a template and aldimine forming condensation reaction of the
4-alkoxyl-substituted 2,6-pyridinedicarboxaldehyde 1 with tetra(ethylene glycol) bis(2-aminophenyl)ether
2 followed by BH3·THF promoted reduction. The preparation of crown ether 9 is carried out using olefin
metathesis reaction (41%) of the bis-olefin containing pseudo-crown ether 8, which is generated by
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substitution reaction between naphthalene-diol 5 and mono-tosylate 6 followed by O-allylation reaction
of the resulting diol 7.
Scheme 2. Synthesis of macrocycles 4 and 9.
The substance selected to aid spectroscopic analysis of the stopper region in the heterorotaxane forming
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process is the dumbbell-shaped ammonium ester 16 (Scheme 3). The route employed to prepare 16 begins
with. Reductive amination reaction between 3,5-dihydroxybenzaldehyde (12) and 5-aminopentan-1-ol (13)
which generates amine 14 (83%). Protonation of the amine group in 14 using excess trifluoroacetic acid
followed by counterion exchange with saturated aqueous NH4PF6 affords the corresponding ammonium
salt 15. Finally, treatment of 15 with 3,5-dimethoxybenzoic anhydride (11), produce from the
corresponding acid 10, and catalytic tributylphosphane leads to formation of the dumbbell-shaped
ammonium salt 16 in a yield of 55%. The final products and intermediates in the synthetic pathways
shown in Schemes 2 and 3 as well in all of the Schemes that follow were fully characterized by using
standard spectroscopic techniques (see the Supporting Information).
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Scheme 3. Synthesis of the dumbbell-shaped ammonium 16.
With models 4, 9 and 16 in hand, we set out to synthesize the dual functional structural components of
the heterorotaxanes. One key substance 24, containing a crown ether and an ammonium structural unit,
was synthesized utilizing the route shown in Scheme 4. Treatment of 3,5-dihydroxybenzaldehyde 20 with
25
the pseudo crown ether 19, formed by a route starting with bis-phenol 17 and mono-tosylate 6, in the
presence of Cs2CO3 produces the aldehyde-substituted crown ether 21 in 46% yield. Reductive amination
of 21 with 3,5-dimethoxybenzylamine (22) gives the precursor of the Boc-protected amino crown ether 23,
produced for the purpose of convenient purification. The Boc-deprotection with trifluoroacetic acid (TFA)
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in dry dichloromethane followed by counterion exchange with saturated aqueous NH4PF6 gives the target
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ammonium tethered bis(m-phenylene)-26-crown-8 24.
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Scheme 4. Synthesis of the dual functional crown ether 24.
A similar synthetic strategy was employed to prepare the dual functional crown ether 30, which contains
two ammonium groups and one crown ether host unit (Scheme 5). The sequence was initiated by treatment
of 3,5-dihydroxybenzaldehyde (25) with the bis-tosylate 27, generated from 25. This process produces
crown ether 28 (54%), which then undergoes reductive amination with 3,5-dimethoxybenzylamine 22
followed by N-protection using Boc2O to form the bis-substituted crown ether 29 (69% three steps).
Subsequent deprotection and counterion exchange affords the bis-ammonium tethered crown ether 30. A
single crystal of 30 suitable for crystallographic analysis was obtained by diffusion of isopropyl ether into
an acetonitrile solution at room temperature (Figure S1). X-ray crystallographic analysis of 30 shows that
it exists in a highly ordered packed structure in the solid state (Table S1).
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Scheme 5. Synthesis of the dual functional crown ether 30.
Scheme 6. Synthesis of dual functional crown ether 34.
The triangular shaped tris-ammonium tethered crown ether 34 was prepared employing the pathway
outlined in Scheme 6. The route begins with Cs+ template controlled reaction of
3,5-dihydroxybenzaldehyde 25 with bis-tosylate 31, which forms the key tris-aldehyde intermediate 32
(43%). Reductive amination of 32 with amine 22 followed by Boc-protection (for the purpose of
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purification), deprotection and ion exchange then gives 34.
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Hetero[n]rotaxanes assembly. A reductive amination based stitching process was employed to affix a
macrocyclic ring on the side chain ammonium residue in the dual functional substrate 24. This process was
accomplished by mixing 24 with dialdehyde 1 and bis-aniline derivative 2 in CD3CN (pictorially
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+
represented in Scheme 7). The observation of a broad singlet at 9.76 ppm for ammonium NH2 protons
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as well as a singlet at 8.24 ppm for imine (CH=N) protons in H NMR spectra of the crude reactions
mixture shows that macrocyclic bis-imine formation has taken place in a reversible manner (Figure S2).
Reduction of the imine moieties in this substance with BH3·THF followed by chromatographic purification
then generates the kinetically stable [2]rotaxane-1 (78%).
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The resonance for ammonium protons in the H NMR spectrum of [2]rotaxane-1 is upfield shifted
(singlet at 8.31 ppm) compared to those of its bis-imine containing precursor. In addition, resonance of
protons on the stopper units (H2 and H3, H6 and H7) of [2]rotaxane-1 (Figure 1C, see Scheme 4 for proton
numbering) also display upfield shifts in comparison to those in the dual functional molecule 24 (Figure
1B) as a result of shielding effects associated with the encircling crown ether macrocyclic ring. In contrast,
the resonances for the methylene protons (H4 and H5) adjacent to the ammonium nitrogen are downfield
shifted. In addition, a downfield shift of the proton (Hb) on the hetero-crown ether ring in [2]rotaxane-1 is
downfield shifted relative to the related proton in the model 4 (Figure 1A). The observed shifts in proton
resonances, which are in good agreement with those noted in previous studies, 19, 26 suggest that the newly
installed crown ether ring system in [2]rotaxane-1 encircles the ammonium moiety of the dual functional
molecule. Additional evidence supporting this conclusion comes from analysis of the electrospray
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ionization mass spectum (ESI-MS), which contains a peak at m/z 1320.3 that corresponds to the -PF6 salt
of [2]rotaxane-1 (see the supporting information).
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Scheme 7. Synthesis of hetero[3]rotaxanes-1 and hetero[3]rotaxanes-2.
In order to construct the topologically novel hetero[3]rotaxane-1, [2]rotaxane-1 was treated with the
ammonium salt 15 and the resulting threaded complex was subjected to a tributylphosphine catalyzed
endcapping reaction with 3,5-dimethylbenzoic anhydride (11). Evidence for the formation of
hetero[3]rotaxane-1 in this process comes from analysis of its 1H NMR spectrum. As shown in Figure 1D,
an obvious downfield shift of the resonance for the ammonium protons and upfield shifts for benzene ring
protons (HB and HC) in the comparative spectra of [2]rotaxane-1 and hetero[3]rotaxane-1 show that the
crown ether unit in the former substance is threaded by the ammonium template (modeled by 16) (Figure
1E). The results of two-dimensional ROESY experiment enabled the identification of the changes
occurring in resonances associated with dual functional and hetero crown ether and dumbbell-shaped
components upon formation of hetero[3]rotaxane-1. For example, the benzene ring prtotons of the dual
functional molecular component are strongly shielded by the hetero crown ether component in
hetero[3]rotaxane-1. In addition, obvious correlations exist between the benzene ring (H3 and H6) and
methylene (Hb) protons and between protons in the dumbbell-shaped and dual functional molecular
components of hetero[3]rotaxane-1 (Figure S3). Finally, inspection of the MALDI-MS spectrum (Figure
2A) shows the presence of a peak at m/z 1736.84 that is assigned to [M-PF6 -HPF6]+ of
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hetero[3]rotaxane-1 (Figure 2A).
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Figure 1. Partial 1H NMR spectra (400 MHz, CD3CN, 298 K) of 4 (A); 24 (B); [2]rotaxane-1 (C); hetero[3]rotaxane-1 (D)
and 16 (E).
Figure 2. MALDI-TOF mass spectra of hetero[3]rotaxane-1 (A), hetero[3]rotaxane-2 (B), hetero[4]rotaxane-3 (C),
hetero[4]rotaxane-4 (D).
Another method used to generate a heterorotaxane from 24 involves the use of an olefin metathesis
process. In this approach, the complex formed by treatment of 24 with the bis-olefin containing crown
ether 8 was reacted using the Grubbs’ catalyst to form [2]rotaxane-2 (67%) (Scheme 7). Subsequent
threading of [2]rotaxane-2 by the ammonium ion 15 followed by endcapping reaction with
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3,5-dimethylbenzoic anhydride (11) produced hetero[3]rotaxane-2 in a 51% yield. In the H NMR
spectrum, protons in the two side methylene groups (H4 and H5) adjacent to the ammonium residue in
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[2]rotaxane-2 display similar downfield shifts as seen in the spectrum of [2]rotaxane-1 while the
corresponding benzene ring protons (H2, H3 and H6, H7) display similar upfield shifts owing to the
shielding effect of the encircling naphthalene-based crown ether ring system (Figure 3B and 3C). In the 1H
NMR spectrum of hetero[3]rotaxane-2, the resonance associated with the ammonium protons on the
dumbbell component are shifted downfield relative to those in the model 16, suggesting that that this
moiety is encircled by a crown ether group of the dual functional component. In addition, resonances of
protons HB and HC also display upfield shifts in a manner that is similar to the corresponding protons in the
spectrum of hetero[3]rotaxane-1 (Figures 3D and 3E).
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Figure 3. Partial 1H NMR spectra (400 MHz, CD3CN, 298 K) of 9 (A); 24 (B); [2]rotaxane-2 (C); hetero[3]rotaxane-2 (D)
and 16 (E).
The results of ESI MALDI-TOF mass spectrometric analysis support the assigned structures of
[2]rotaxane-2 and hetero[3]rotaxane-1. Specifically, the peak at m/z 1105.1 in the spectrum of
- +
[2]rotaxane-2 is assigned to the [M-PF6 ] species while the spectrum of hetero[3]rotaxane-2 contains a
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peak at m/z 1521.72 for the [M-PF6 -HPF6]+ species (Figure 2B and SI). Finally, the two-dimensional
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ROESY spectrum of hetero[3]rotaxane-2 contains significant cross peaks associated with the existence of
interactions between the host and guest components (Figure S4).
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An investigation was conducted to determine if hetero[4]rotaxanes can be generated by using
appropriate polyfunctional substrates. The crown ether 30 was selected for this purpose because, in
addition to a host component, it contains two ammonium units that can serve as templates for stitching
processes that introduce crown ether rings. Template-directed clipping reaction of 30 and two equivalents
of dialdehyde 1 and diamine 2 in CH3CN was employed to generate a bis-imine, which upon treatment
with BH3·THF produced [3]rotaxane-3 in a high yield (Scheme 8). In addition, the analogous
[3]rotaxane-4 was prepared from 30 by using olefin metathesis reaction of diene 8. Both [3]rotaxanes
were then subjected to threading with 15 and endcapping reactions with anhydride 15. The overall
sequences afforded hetero[4]rotaxane-3 and hetero[4]rotaxane-4 in high yields.
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Scheme 8. Synthesis of hetero[4]rotaxane-3 and hetero[4]rotaxane-4.
1
The steps in these assembly sequences were followed by using H NMR spectroscopy. As can be seen
by inspection of Figures 4 and S5, the resonance of protons (H2’, H3’ and H6’, H7’) on the benzene rings of
30 are downfield shifted in [3]rotaxane-3 and [3]rotaxane-4 while two side methylenes (H4’ and H5’)
adjacent to the ammonium nitrogens are also downfield shifted. The results clearly show that the
template-directed clipping reaction leads to incorporation of crown ether components wrapped around the
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ammonium ion centers. In contrast to those of the dumbbell-shaped molecule 16, the ammonium protons
of hetero[4]rotaxane-3 and hetero[4]rotaxane-4 are also downfield shifted while the resonance of
benzene ring protons are upfield shifted relative to those in 16. Morover, the 2D ROESY spectra of both
hetero[4]rotaxanes display some important correlations expected for their assigned structures (Figure S6
and S7). Finally, the mass spectra of both substances contain peaks at expected m/z ratios (as shown in SI
and Figures 2C and 2D).
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Figure 4. Partial 1H NMR spectra (400 MHz, CD3CN, 298 K) of 4 (A); 30 (B); [3]rotaxane-3 (C); hetero[4]rotaxane-3 (D)
and 16 (E).
Scheme 9. Synthesis of [4]rotaxane-5 and hetero[5]pseudorotaxane-5.
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The final phase of this effort focused on the star-shaped dual functional crown ether 34, bearing three
ammonium units linked to a central crown ether core (Scheme 9). Treatment of 34 with three equivalents
of dialdehyde 1, and diamine 2 in CH3CN led to formation of [4]rotaxane-5 in 62% yield. The structure of
this substance was assigned by using 1H NMR spectroscopy and mass spectrometry (Figure 5A and SI). In
addition, further studies revealed that [4]rotaxane-5 reacts to form hetero[5]pseudorotaxane when
treated with the rod-type, phenanthroline based ammonium ion 35. As can be seen by viewing the 1H NMR
spectra contained in Figures 5B and 5D, obvious shifts in key resonance of protons take place in this
process. For instance, the aromatic protons (HB’, HC’, HD’, HE’) display obvious upfield shifts and protons
in the nitrogen bonded methylene groups display downfield shifts upon the addition of one equivalent
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ammonium 35 to [4]rotaxane-5. These changes are in agreement with those made in previous studies.
Addition of five equivalents of 35 to [4]rotaxane-5 led to formation of more hetero[5]pseudorotaxane
Based on an analysis of the 35 concentration dependence of this process, an association constants for the
equilibrium reaction of [4]rotaxane-5 with 35 to form hetero[5]pseudorotaxane is estimated to be 2.42 ×
102 M-1.
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Figure 5. Partial H NMR spectra (400 MHz, CD3CN, 298 K) of 34 (A); [4]rotaxane-5 (B); [4]rotaxane-5/35 = 1:1 (C);
[4]rotaxane-5/35 = 1:5 (D) and phenanthroline-based ammonium 35 (E). Complexed and uncomplexed species are denoted
by “c” and “uc” in the parentheses, respectively.
n CONCLUSION
In the study describe above, three polyfunctional building blocks, possessing crown ether host and
ammonium guest components were synthesized and used to construct new types of topologically novel
hetero[n]rotaxanes. In the routes for preparation of the target hetero[n]rotaxanes, the guest ammonium
units serve as templates to direct construction of encircling crown ether ring systems using
template-directed clipping reaction or olefin metathesis reactions as key stitching processes. In these
processes, the host crown ether units guide introduction of dumbbell-shaped molecules by use of a
threading-followed-by stoppering strategy. The results of this effort demonstrate the feasibility of the
self-assembly strategy relying on the use of polyfunctional substrates. In addition, by using this approach a
number of topologically unique heterorotaxane structures have been prepared. Finally, this investigation
provides a foundation of future studies aimed at constructing more complicated heterorotaxane
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architectures, such as switchable systems, self-assembling polymers and functional molecular machines.
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n EXPERIMENTAL SECTION
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General Methods. All reactions and assembly processes 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. Oxybis(ethane-2,1-diyl) bis(4-methylbenzenesulfonate) 31, 24 the 3,5-dimethoxybenzoic
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anhydride (11),
and the phenanthroline-based ammonium 35
were prepared by using literature methods or
modifications therof. All other starting materials were obtained commercially as analytical-grade and used without
further purification. 1H and 13C NMR spectra were collected with either a 400 or 600 MHz spectrometer. Mass spectra
were measured in the ESI or MALDI mode.
Synthesis of 8: A mixture of 5 (1.60 g, 10.0 mmol), 6 (6.10 g, 20 mmol) and K2CO3 (4.20 g, 30.0 mmol) in
anhydrous DMF (50 mL) was stirred for 24 h at 50℃. The resulting mixture was cooled to room temperature and
concentrated in vacuo giving a residue that waswas extracted by ethyl acetate. The organic layer was then dried over
anhydrous sodium sulfate and concentrated in vacuo giving a residue was dissolved in dry THF (40 mL). To the
solution was added NaH (4.00 g, 0.1 mol, 60% dispersion in mineral oil). After stirring for 2 h, allyl bromide (2.42 g,
20.0 mmol) was added and the mixture was stirred for 36 h, quenched by addition of saturated ammonium chloride
(aq). Concentration in vacuo gave a residue was extracted with CH2Cl2. The organic layer was dried over anhydrous
sodium sulfate and concentrated in vacuo giving a residue that was subjected to silica gel column using petroleum
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ether/ethyl acetate (1:1) as the eluent to form 8 as a brown liquid. Yield: 3.38 g, 67%. H NMR (400 MHz, CDCl3) δ
7.66 (dd, J = 5.7, 3.2 Hz, 2H), 7.32 (dd, J = 5.9, 3.1 Hz, 2H), 7.15 (s, 2H), 5.90 (ddd, J = 16.2, 10.7, 5.4 Hz, 2H), 5.22
(dd, J = 38.3, 13.7 Hz, 4H), 4.28 (t, J = 4.9 Hz, 4H), 4.01 (d, J = 5.4 Hz, 4H), 3.95 (t, J = 4.9 Hz, 4H), 3.83 – 3.74 (m,
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4H), 3.74 – 3.64 (m, 8H), 3.64 – 3.54 (m, 4H). 13C NMR (100 MHz, CDCl3): δ 148.9, 134.7, 129.3, 126.3, 124.2,
117.1, 108.5, 72.2, 70.9, 70.7, 70.6, 69.5, 69.4, 68.3. ESI MS: m/z = 527.3 [M + Na+], 543.3 [M + K+]; calculated
exact mass: 504.27. Anal. Calcd for: C28H40O8: C, 66.65; H, 7.99. Found: C, 66.72; H, 7.91.
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Synthesis of 9: To a solution of 8 (505 mg, 1.0 mmol) in dry DCM (20 mL) was added Grubbs catalyst (2nd
generation) (85 mg, 0.1 mmol). After stirring at reflux for 48 h, the mixture was diluted with ethyl vinyl ether.
Concentration in vacuo gave a residue that was subjected to silica gel column using petroleum ether/ethyl acetate (1:1)
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as the eluent to obtain macrocycle 9 as a brown viscous liquid. Yield: 197 mg, 41%. H NMR (400 MHz, CD3CN): δ
7.71 (dd, J = 5.9, 3.3 Hz, 2H), 7.33 (dd, J = 6.1, 3.2 Hz, 2H), 7.27 (s, 2H), 5.79 (s, 2H), 4.28 – 4.19 (m, 4H), 3.97 (s,
4H), 3.92 – 3.83 (m, 4H), 3.73 – 3.65 (m, 4H), 3.66 – 3.56 (m, 8H), 3.54 (d, J = 5.2 Hz, 4H). 13C NMR (100 MHz,
CD3CN): δ 149.6, 130.0, 129.8, 126.9, 124.8, 108.6, 71.3, 71.1, 71.0, 70.9, 70.0, 69.0. ESI MS: m/z = 499.3 [M +
Na+], 515.3 [M + K+]; calculated exact mass: 476.24. Anal. Calcd for: C26H36O8: C, 65.53; H, 7.61. Found: C, 65.60;
H, 7.67.
Synthesis of 14: A solution of 12 (830 mg, 5.0 mmol) and 13 (520 mg, 5.0 mmol) was stirred at reflux for 24 h in
MeOH (40 mL) under an argon atmosphere. After the reaction mixture was cooled to ambient temperature, NaBH4
(3.40 g, 90.0 mmol) was added portionwise to the stirring solution. After stirring for overnight, the mixture was
diluted with the saturated ammonium chloride (aq). Concentration in vacuo gave a residue that was extracted by ethyl
acetate. The organic layer was dried over anhydrous sodium sulfate and concentrated in vacuo giving a residue that
was subjected to silica gel column using ethyl acetate as the eluent to give 14 as a viscous liquid. Yield: 1.05 g, 83%.
1H NMR (600 MHz, CDCl3): δ 6.49 (s, 2H), 6.36 (s, 1H), 3.79 (s, 6H), 3.73 (s, 2H), 3.62 (t, J = 5.7 Hz, 2H), 2.64 (t, J
= 6.5 Hz, 2H), 2.12 (s, 2H), 1.58-1.52 (m, 4H), 1.45-1.36 (m, 2H). 13C NMR (100 MHz, CDCl3): δ 160.7, 142.2,
105.9, 98.9, 62.2, 55.2, 53.9, 48.9, 32.3, 29.4, 23.3. ESI MS: m/z = 254.2 [M + H+]; calculated exact mass: 253.17.
Anal. Calcd for: C14H23NO3: C, 66.37; H, 9.15; N, 5.53. Found: C, 66.43; H, 9.08, N, 5.49.
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Synthesis of 15: To a solution of 14 (253 mg, 1.0 mmol) in dry DCM (20 mL), TFA (0.32 mL, 5.0 mmol) was
added at room temperature. After stirring for 2 h, the solution was concentrated in vacuo giving a residue that was
dissolved in MeOH (2 mL). To this solution was added saturated NH4PF6 (4 mL, aq) to yield a white precipitate,
which was collected by filtration, washed with H2O and dried under vacuum to give 15. Yield: 363 mg, 91%. 1H NMR
(400 MHz, CDCl3) δ 6.76 (s, 2H), 6.56 (d, J = 6.2 Hz, 2H), 6.47 (s, 1H), 4.31 (t, J = 6.4 Hz, 2H), 4.14 (s, 2H), 3.77 (s,
6H), 3.02 (s, 2H), 2.18 (s, 2H), 1.75 (s, 4H), 1.49 – 1.38 (m, 2H). 13C NMR (100 MHz, CDCl3): δ 161.6, 130.9, 107.3,
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102.3, 67.4, 55.4, 52.5, 47.2, 27.3, 25.2, 22.2. ESI MS: m/z = 252.8 [M - PF6 ]; calculated exact mass: 399.14. Anal.
Calcd for: C14H24F6NO3P: C, 42.11; H, 6.06; N, 3.51. Found: C, 42.05; H, 5.99; N, 3.60.
Synthesis of 16: To a solution of 15 (800 mg, 2.0 mmol) in acetone (5 mL) was added 11 (1.00 g, 3.0 mmol) and
tributylphosphine (75 µL , 0.3 mmol). The mixture was stirred for 12 h. Conentration in vacuo gave a residue that was
subjected to silica gel column using dichloromethane as the eluent to give 16 as a viscous solid. Yield: 620 mg, 55%.
1H NMR (400 MHz, CD3CN): δ 7.14 (s, 1H), 6.73 (s, 1H), 6.58 (d, J = 12.0 Hz, 4H), 4.38 (t, J = 6.1 Hz, 2H), 4.07 (s,
2H), 3.81 (d, J = 5.1 Hz, 12H), 3.03 (d, J = 7.2 Hz, 2H), 1.81 – 1.66 (m, 4H), 1.45 (d, J = 7.3 Hz, 2H). 13C NMR (100
MHz, CD3CN): δ 161.8, 161.6, 161.2, 132.8, 108.2, 108.0, 107.4, 105.4, 101.4, 68.3, 55.7, 55.5, 51.7, 47.9, 27.3, 25.2,
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22.4. ESI MS: m/z = 418.4 [M - PF6 ]; calculated exact mass: 563.19. Anal. Calcd for: C23H32F6NO6P: C, 49.03; H,
5.72; N, 2.49. Found: C, 49.11; H, 5.81; N, 2.41.
Synthesis of 21: A mixture of 19 (680 mg, 1.0 mmol) and 20 (140 mg, 1.0 mmol) in dry DMF (400 mL) was added
dropwise over a period of 24 h to a stirred suspension of Cs2CO3 (1300 mg, 4.0 mmol) in DMF (200 mL) at 80℃. The
mixture was stirred for 48 h, cooled to room temperature and filtered. The filtrate was concentrated in vacuo giving a
residue that was extracted by ethyl acetate. The organic layer was dried over anhydrous sodium sulfate. Concentration
in vacuo gave a residue that was subjected to silica gel column using DCM/ethyl acetate (5:1) as the eluent to give 21
as a white solid. Yield: 219 mg, 46%. 1H NMR (400 MHz, CDCl3): δ 9.84 (s, 1H), 7.10 (d, J = 7.7 Hz, 1H), 6.99 (d, J =
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1.8 Hz, 2H), 6.76 (s, 1H), 6.48 (d, J = 7.1 Hz, 3H), 4.17 – 4.09 (m, 4H), 4.10 – 4.01 (m, 4H), 3.85 (dd, J = 10.8, 6.4
Hz, 8H), 3.78 – 3.69 (m, 8H). 13C NMR (100 MHz, CDCl3): δ 191.7, 160.3, 159.8, 138.1, 129.6, 108.3, 107.8, 106.8,
101.8, 70.8, 69.5, 69.3, 67.6, 67.2. ESI MS: m/z = 499.3 [M + Na+], 515.3 [M + K+]; calculated exact mass: 476.2.
Anal. Calcd for: C25H32O9: C, 63.01; H, 6.77. Found: C, 63.09; H, 6.69.
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Synthesis of 23: To a solution of 21 (480 mg, 1.0 mmol) in anhydrous (EtOH 20 mL) was added 22 (170 mg, 1.0
mmol) with anhydrous magnesium sulfate acting as drying agent. The mixture was stirred at reflux for 24 h.
Concentration in vacuo gave a residue that was dissolved in THF (15 mL) and MeOH (15 mL). To this solution was
added NaBH4 (150 mg, 4.0 mmol) slowly in ten portions. After stirring overnight, the mixture was diluted with
saturated ammonium chloride (aq). Concentration in vacuo gave a residue that was extracted with absolute ethyl ether.
The organic layer was dried over anhydrous sodium sulfat and concentrated in vacuo giving a residue that was
dissolved in dry chloroform (20 mL). To this solution was added Boc2O (440 mg, 2.0 mmol) and triethylamine (0.43
mL). The mixture was stirred for 24 h at room temperature and concentrated in vacuo giving a residue that was
subjected to silica gel column using petroleum ether/ethyl acetate (1:2) as the eluent to give the Boc-protected 23 as a
white solid. Yield: 546 mg, 75%. 1H NMR (400 MHz, CDCl3): δ 7.13 (t, J = 8.1 Hz, 1H), 6.50 (d, J = 8.4 Hz, 3H), 6.40
(d, J = 11.6 Hz, 3H), 6.34 (d, J = 8.7 Hz, 3H), 4.33 (s, 2H), 4.25 (s, 2H), 4.18 – 4.07 (m, 4H), 4.05 (s, 4H), 3.95 – 3.79
(m, 8H), 3.78 (d, J = 10.3 Hz, 6H), 3.72 (d, J = 14.3 Hz, 8H), 1.49 (s, 9H). 13C NMR (100 MHz, CDCl3): δ 162.5,
160.8, 159.9, 140.5, 140.2, 129.6, 106.9, 106.8, 106.1, 105.3, 101.8, 100.3, 98.9, 80.0, 70.8, 69.5, 69.5, 67.2, 63.5,
55.2, 49.4, 36.4, 28.4. ESI MS: m/z =750.5 [M + Na+], 766.4 [M + K+]; calculated exact mass: 727.36. Anal. Calcd
for: C39H53NO12: C, 64.36; H, 7.34; N, 1.92. Found: C, 64.42; H, 7.28; N, 1.98.
Synthesis of 24: To a solution of 23 (730 mg, 1.0 mmol) in dry DCM (30 mL), TFA (0.32 mL, 5.0 mmol) was
added at room temperature. After stirring for 2 h, the mixture was concentrated in vacuo giving a residue that was
dissolved in MeOH (5 mL). To this solution was added saturated NH4PF6 (10 mL, aq) to give a white precipitate,
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which was isolated by filtration, washed with H2O and dried under vacuum to give 24. Yield: 665 mg, 86%. H NMR
(400 MHz, CD3CN): δ 7.18 (t, J = 8.2 Hz, 1H), 6.62 (m, 4H), 6.52 (m, 4H), 6.43 (s, 1H), 4.13 – 4.03 (m, 12H), 3.82 –
3.73 (m, 14H), 3.64 (s, 8H). 13C NMR (100 MHz, CD3CN): δ 161.7, 160.6, 160.4, 133.6, 130.8, 108.3, 106.4, 102.9,
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C34H46F6NO10P: C, 52.78; H, 5.99; N, 1.81. Found: C, 52.69; H, 6.06; N, 1.73.
Synthesis of 27: A mixture of 25 (138 mg, 1.0 mmol), 6 (610 mg, 2.0 mmol) and K2CO3 (420 mg, 3.0 mmol) in
anhydrous DMF (50 mL) was stirred for 24 h at 50 ℃. The resulting mixture was cooled to room temperature and
concentrated in vacuo giving a residue that was extracted with ethyl acetate. The organic layer was dried over
anhydrous sodium sulfate and concentrated in vacuo giving a residue that was dissolved in dry DCM (20 mL) To
this solution at 0 ℃ was sequentially added Et3N (1.5 mL) and p-tosyl chloride (950 mg, 5.0 mmol) in dry DCM (30
mL) . After the mixture was stirred atambient temperature overnight, 5N HCl (4 mL) was tadded. The separated
organic phase was washed with saturated brine (30 mL) and dried over MgSO4 giving a residue that was
concentrated in vacuo giving a residue that was subjected to silica gel column using petroleum ether/ethyl acetate (1:1)
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as the eluent to give 27 as a brown liquid. Yield: 455 mg, 64%. H NMR (400 MHz, CDCl3): δ 9.88 (s, 1H), 7.79 (d, J
= 7.9 Hz, 4H), 7.34 (d, J = 7.9 Hz, 4H), 7.02 (s, 2H), 6.76 (s, 1H), 4.15 (s, 8H), 3.86 (d, J = 15.6 Hz, 4H), 3.73 – 3.61
(m, 12H), 2.43 (s, 6H). 13C NMR (100 MHz, CDCl3): δ 191.9, 160.2, 144.8, 138.1, 132.7, 129.7, 127.8, 108.0, 107.8,
70.6, 69.4, 69.2, 68.6, 67.6, 21.5. ESI MS: m/z = 733.3 [M + Na+], 749.3 [M + K+]; calculated exact mass: 710.21.
Anal. Calcd for: C33H42O13S2: C, 55.76; H, 5.96. Found: C, 55.71; H, 6.04.
Synthesis of 28: Compound 28 was prepared via an analogous method similar to that used for 21. Yield: 272 mg,
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54%. H NMR (400 MHz, CDCl3): δ 9.84 (s, 2H), 6.98 (d, J = 1.8 Hz, 4H), 6.74 (s, 2H), 4.27 – 4.06 (m, 8H),
4.00–3.81 (m, 8H), 3.75 (s, 8H). 13C NMR (100 MHz, CDCl3): δ 191.9, 160.2, 138.1, 108.4, 107.7, 70.8, 69.4, 67.6.
ESI MS: m/z = 527.3 [M + Na+], 543.2 [M + K+]; calculated exact mass: 504.20. Anal. Calcd for: C26H32O10: C, 61.90;
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Synthesis of 29: Compound 29 was prepared by an analogous method similar to that used for 23. Yield: 694 mg,
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69%. H NMR (400 MHz, CDCl3): δ 6.42 (s, 4H), 6.38 (s, 2H), 6.35 (d, J = 7.0 Hz, 6H), 4.34 (s, 4H), 4.26 (s, 4H),
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4.07 (s, 8H), 3.85 (s, 8H), 3.76 (s, 12H), 3.74 (s, 8H), 1.49 (s, 18H). 13C NMR (100 MHz, CDCl3): δ 160.8, 160.0,
155.8, 140.3, 106.5, 105.7, 105.1, 100.4, 98.9, 80.0, 70.8, 69.5, 67.2, 55.2, 49.4, 49.0, 28.4. ESI MS: m/z = 1029.6 [M
+ Na+], 1045.9 [M + K+]; calculated exact mass: 1006.50. Anal. Calcd for: C54H74N2O16: C, 64.40; H, 7.41; N, 2.78.
Found: C, 64.46; H, 7.35; N, 2.73.
Synthesis of 30: Compound 30 was prepared by an analogous method similar to that used for 24. Yield: 505 mg,
92%. 1H NMR (400 MHz, CDCl3): δ 6.60 (d, J = 4.6 Hz, 8H), 6.54 (s, 2H), 6.51 (s, 2H), 4.12 (s, 8H), 4.08 (s, 8H),
3.79 (s, 12H), 3.77 (s, 8H), 3.63 (s, 8H). 13C NMR (100 MHz, CDCl3): δ 161.8, 160.9, 133.2, 108.5, 108.4, 103.6,
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101.6, 70.9, 69.6, 68.2, 55.8, 51.9, 51.8. ESI MS: m/z = 404.8 [M - 2PF6 ]2+, 808.8 [M - PF6 - HPF6], 845.7 [M - 2PF6
+ K+]; calculated exact mass: 1098.34. Anal. Calcd for: C44H60F12N2O12P2: C, 48.09; H, 5.50; N, 2.55. Found: C, 48.03;
H, 5.59; N, 2.62.
Synthesis of 32: A solution of 25 (138 mg, 1.0 mmol) and Cs2CO3 (1.30 g, 4.0 mmol) in dry DMF (50 mL) was
stirred for 1 h at 50℃ under an argon atmosphere. And then 31 (420 mg, 1.0 mmol) in DMF (50 mL) was added
dropwise over 1 h to a stirred solution. After further stirring for 24 h, 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 acetate, and then dried over anhydrous sodium sulfate. Removal of solvent under reduced pressure and
purification on a silica gel column using petroleum ether/ethyl acetate (1:2) as the eluent obtained 32 as a white solid.
Yield: 268 mg, 43%. 1H NMR (600 MHz, CDCl3): δ 9.85 (s, 3H), 6.99 (s, 6H), 6.73 (s, 3H), 4.19 - 4.09 (m, 12H), 3.91
(s, 12H). 13C NMR (100 MHz, CDCl3): δ 191.9, 160.2, 108.8, 107.8, 69.5, 67.8. ESI MS: m/z = 647.5 [M + Na+],
663.5 [M + K+]; calculated exact mass: 624.22. Anal. Calcd for: C33H36O12: C, 63.45; H, 5.81. Found: C, 63.52; H,
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Synthesis of 33: Compound 33 was prepared by an analogous method similar to that used for 23. Yield: 496 mg,
72%. 1H NMR (400 MHz, CDCl3): δ 6.48 (s, 3H), 6.40 (d, J = 8.5 Hz, 6H), 6.34 (d, J = 8.3 Hz, 9H), 4.34 (s, 6H), 4.26
(s, 6H), 4.11 (s, 12H), 3.88 (s, 12H), 3.75 (s, 18H), 1.51 (s, 27H). 13C NMR (100 MHz, CDCl3): δ 160.8, 159.9, 155.9,
140.3, 106.5, 105.9, 105.7, 105.2, 100.8, 99.0, 80.0, 69.6, 67.4, 55.2, 49.4, 49.0, 28.4. ESI MS: m/z =1400.8 [M +
Na+], 1416.8 [M + K+]; calculated exact mass: 1377.68. Anal. Calcd for: C75H99N3O21: C, 65.34; H, 7.24; N, 3.05.
Found: C, 65.41; H, 7.32, N, 2.94.
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Synthesis of 34: Compound 34 was prepared by an analogous method similar to that used for 24. Yield: 667 mg,
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88%. H NMR (400 MHz, CD3CN): δ 6.57 (d, J = 2.4 Hz, 12H), 6.54 (s, 3H), 6.50 (s, 3H), 4.09 (s, 24H), 3.81 (s,
12H), 3.78 (s, 18H). 13C NMR (100 MHz, CD3CN): δ 161.9, 160.9, 133.5, 133.4, 108.8, 108.4, 103.4, 101.5, 69.8,
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68.4, 55.8, 51.8. ESI MS: m/z = 1078.46 [M - PF6 - 2HPF6], 1090.46 [M - 3HPF6 + Na+]; calculated exact mass:
1515.44. Anal. Calcd for: C60H78F18N3O15P3: C, 47.53; H, 5.19; N, 2.77. Found: C, 47.60; H, 5.24, N, 2.68.
Synthesis of [2]rotaxane-1: A solution of 24 (77 mg, 0.1 mmol), 1 (35 mg, 0.1 mmol) and 2 (38 mg, 0.1 mmol) in
dry CH3CN (10 mL) was stirred for 5 days at room temperature under an argon atmosphere. Then BH3·THF (0.8 mL)
was added and the solution was further stirred for 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 obtain
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[2]rotaxane-1 as a light brown solid. Yield: 114 mg, 78%. H NMR (400 MHz, CD3CN): δ 8.79 (s, 2H), 7.16 (t, J =
8.2 Hz, 1H), 6.94 (s, 2H), 6.73 – 6.60 (m, 6H), 6.50 (d, J = 2.4 Hz, 1H), 6.48 (d, J = 2.4 Hz, 1H), 6.46 – 6.38 (m, 3H),
6.29 (t, J = 2.2 Hz, 1H), 6.22 (d, J = 2.1 Hz, 1H), 6.16 (d, J = 2.2 Hz, 2H), 6.12 (d, J = 2.2 Hz, 2H), 4.54 (s, 4H), 4.39
(s, 2H), 4.14 (t, J = 6.6 Hz, 2H), 4.08 – 4.01 (m, 8H), 3.96 – 3.90 (m, 4H), 3.82 (s, 4H), 3.80 – 3.72 (m, 12H), 3.64 –
3.57 (m, 12H), 3.55 (d, J = 5.3 Hz, 4H), 3.46 – 3.39 (m, 6H), 1.88 – 1.77 (m, 2H), 1.49 (m, 2H), 1.30 (br, 20H), 0.89
(t, J = 6.8 Hz, 3H). 13C NMR (100 MHz, CD3CN): δ 161.8, 160.9, 160.7, 147.4, 137.8, 134.3, 134.2, 130.9, 122.7,
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120.4, 115.9, 113.3, 112.0, 111.1, 108.0, 107.9, 107.0, 103.3, 102.8, 101.6, 71.5, 71.3, 71.1, 70.0, 69.9, 69.1, 68.5,
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68.2, 56.0, 53.4, 32.4, 30.1, 29.8, 29.7, 29.1, 26.2, 23.1, 14.1. ESI MS: m/z = 1320.3 [M - PF6 ]; calculated exact mass:
1463.72. Anal. Calcd for: C75H106F6N4O16P: C, 61.50; H, 7.29; N, 3.83. Found: C, 61.33; H, 7.35; N, 3.76.
Synthesis of [2]rotaxane-2: 24 (193 mg, 0.25 mmol) and 8 (126 mg, 0.25 mmol) were dissolved in anhydrous
CH2Cl2 (50 mL) and stirred for 2 h at room temperature under an argon atmosphere. Then Grubbs catalyst (2nd
generation) (9 mg, 0.01 mmol) was added and the resulting mixture was refluxed for 48 h. The reaction was allowed
to cool to room temperature and quenched by addition of ethyl vinyl ether. The reaction was stirred for an additional 1
h. The excess solvent was removed in vacuum and purified on a silica gel column using DCM / MeOH = 100:0 ~ 50:1
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as the eluent to obtain the [2]rotaxane-2 as a brown solid. Yield: 209 mg, 67%. H NMR (400 MHz, CD3CN): δ 7.70
(dd, J = 6.0, 3.3 Hz, 4H), 7.36 (dd, J = 6.0, 3.1 Hz, 2H), 7.18 (t, J = 8.3 Hz, 1H), 7.13 (s, 2H), 6.60 (s, 4H), 6.50 (d, J
= 8.2 Hz, 2H), 6.39 (s, 1H), 6.25 (d, J = 14.9 Hz, 2H), 5.77 (s, 2H), 4.42 (s, 4H), 4.13 (s, 4H), 4.02 (d, J = 4.2 Hz, 4H),
3.88 (s, 8H), 3.72 (d, J = 3.1 Hz, 8H), 3.60 (t, J = 6.6 Hz, 16H), 3.61 - 3.51 (m, 18H). 13C NMR (100 MHz, CD3CN):
δ 161.5, 160.6, 160.5, 148.8, 147.7, 134.0, 139.0, 130.7, 129.8, 129.6, 126.9, 125.1, 124.9, 108.6, 108.4, 108.2, 107.9,
106.7, 103.0, 102.6, 100.9, 71.4, 71.1, 70.8, 70.6, 70.4, 70.4, 70.0, 69.8, 69.7, 69.5, 68.9, 68.5, 68.0, 67.9, 55.6. ESI
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MS: m/z = 1105.1 [M - PF6 ]; calculated exact mass: 1249.52. Anal. Calcd for: C60H82F6NO18P: C, 57.64; H, 6.61; N,
1.12. Found: C, 57.71; H, 6.52; N, 1.18.
Synthesis of hetero[3]rotaxane-1: To a solution of [2]rotaxane-1 (146 mg, 0.1 mmol) and 15 (40 mg, 0.1 mmol)
in dichloromethane (3 mL) was added 11 (52 mg, 0.15 mmol) and tributylphosphine (7.0 µL, 0.03 mmol). After the
reaction mixture was stirred for 48 h at room temperature under an argon atmosphere, water was added and the
reaction mixture was stirred for additional 1 h. After filtration, the filtrate was washed with 5 % sodium carbonate
solution and then saturated ammonium hexafluorophosphate solution, and dried over anhydrous magnesium sulfate.
The solvents were removed under vacuum and the residue was purified by column chromatography (silica gel,
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DCM/MeOH = 100:0 ~ 50:1) to obtain the hetero[3]rotaxane-1 as a viscous solid. Yield: 126 mg, 62%. 1H NMR (600
MHz, CD3CN): δ 8.79 (s, 4H), 7.14 -7.18 (m, 2H), 6.95 (s, 2H), 6.72 – 6.70 (t, J = 6.0 Hz, 2H), 6.66 – 6.61 (m, 6H),
6.53 (s, 2H), 6.50 – 6.48 (m, 2H), 6.43 (d, J = 12 Hz, 2H), 6.40 (s, 1H), 6.29 (s, 1H), 6.21 (s, 1H), 6.15 (s, 2H), 6.11 (s,
2H), 4.54 (s, 4H), 4.40 (s, 2H), 4.14 (t, J = 6.0 Hz, 2H), 4.08 – 4.02 (m, 10H), 3.92 (t, J = 6.0 Hz, 4H), 3.81 (t, J = 6.0
Hz, 6H), 3.80 – 3.76 (m, 10H), 3.75 (d, J = 6.0 Hz, 4H), 3.72 (t, J = 6.0 Hz, 4H), 3.63 – 3.58 (m, 12H), 3.53 (d, J =
6.0 Hz, 4H), 3.49 (t, J = 6.0 Hz, 4H), 3.42 (s, 6H), 3.00 (t, J = 12 Hz, 2H), 1.84 – 1.81 (m, 2H), 1.72 – 1.67 (m, 2H),
1.50 – 1.47 (m, 4H), 1.42 – 1.37 (m, 2H), 1.29 (br, 20H), 0.89 (t, J = 6.0 Hz, 3H). 13C NMR (100 MHz, CD3CN): δ
167.3, 161.9, 161.8, 161.6, 161.4, 160.9, 160.7, 160.9, 147.2, 137.5, 135.5, 134.9, 130.7, 129.2, 122.0, 120.0, 112.8,
110.7, 109.3, 108.3, 108.1, 107.6, 107.5, 107.0, 106.3, 105.7, 104.0, 103.4, 103.0, 102.7, 101.6, 101.2, 71.9, 71.8, 71.0,
69.8, 69.6, 69.1, 68.1, 61.7, 55.9, 55.8, 55.6, 53.2, 51.8, 50.4, 48.1, 32.3, 30.0, 29.7, 29.2, 26.3, 26.0, 24.1, 23.0, 14.0,
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13.5. MALDI-TOF MS: m/z = 1736.84 [M - PF6 - HPF6], m/z = 1882.76 [M - PF6 ]; calculated exact mass: 2027.92.
Anal. Calcd for: C98H139F12N5O22P2: C, 58.01; H, 6.90; N, 3.45. Found: C, 58.11; H, 6.83; N, 3.52.
Synthesis of hetero[3]rotaxane-2: Hetero[3]rotaxane-2 was prepared by an analogous method similar to that
used for hetero[3]rotaxane-1. Yield: 92 mg, 51%. 1H NMR (600 MHz, CD3CN): δ 7.71 (s, 4H), 7.37 (s, 2H), 7.19 (t, J
= 12.0 Hz, 2H), 7.14 (s, 2H), 6.61 (br, 6H), 6.55 (s, 1H), 6.52 (d, J = 6.0 Hz, 3H), 6.41 (s, 2H), 6.27 (s, 1H), 6.24 (s,
1H), 5.78 (s, 2H), 4.43 (s, 4H), 4.24 (s, 2H), 4.15 – 4.10 (m, 6H), 4.07 – 4.04 (m, 6H), 3.88 (br, 8H), 3.83 (br, , 8H),
3.73 (s, 8H), 3.64 – 3.51 (m, 36H), 3.03 (t, J = 6.0 Hz, 2H), 1.51 – 1.30 (m, 6H), 0.95 – 0.91 (m, 2H). 13C NMR (100
MHz, CD3CN): δ 161.9, 161.6, 161.0, 160.7, 160.7, 147.9, 134.1, 134.0, 133.4, 130.7, 129.9, 126.9, 125.1, 124.9,
108.6, 108.4, 108.3, 108.0, 107.7, 107.0, 103.1, 102.7, 101.6, 101.0, 71.2, 70.9, 70.5, 70.1, 70.0, 69.8, 69.6, 69.0, 68.2,
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68.0, 61.7, 55.8, 55.8, 55.6, 53.2, 51.8, 48.2, 32.0, 25.9, 23.0, 13.0. MALDI-TOF MS: m/z = 1521.72 [M - PF6
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HPF6]; calculated exact mass: 1812.70. Anal. Calcd for: C83H114F12N2O24P2: C, 54.96; H, 6.34; N, 1.54. Found: C,
54.89; H, 6.39; N, 1.61.
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Synthesis of [3]rotaxane-3: [3]Rotaxane-3 was prepared by an analogous method similar to that used for
[2]rotaxane-1. Yield: 178 mg, 71%. 1H NMR (400 MHz, CD3CN): δ 8.73 (s, 4H), 6.93 (s, 4H), 6.69 (t, J = 7.1 Hz, 4H),
6.64-6.58 (m, 8H), 6.40 (d, J = 7.5 Hz, 4H), 6.29 (s, 2H), 6.15 (d, J = 6.0 Hz, 6H), 6.08 (s, 4H), 4.53 (s, 8H), 4.34 (s,
4H), 4.14 (t, J = 6.3 Hz, 4H), 4.01 (s, 8H), 3.91 (s, 8H), 3.79 - 3.76 (m, 24H), 3.56 (s, 16H), 3.50 (s, 8H), 3.43 (s,
12H), 1.86 - 1.79 (m, 4H), 1.53 - 1.48 (m, 4H), 1.30 (s, 40H), 0.89 (t, J = 8.0 Hz, 6H). 13C NMR (100 MHz, CD3CN):
δ 167.4, 161.6, 160.6, 147.2, 137.5, 135.0, 134.9, 122.1, 120.0, 112.7, 110.7, 109.4, 107.5, 103.0, 101.5, 72.0, 71.8,
71.0, 69.6, 69.2, 68.1, 68.0, 55.6, 53.4, 50.5, 32.3, 30.1, 29.8, 26.4, 23.1, 14.1. MALDI-TOF MS: m/z = 2191.73 [M -
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PF6 - HPF6]; calculated exact mass: 2481.26. Anal. Calcd for: C126H182F12N8O24P2: C, 60.95; H, 7.39; N, 4.51. Found:
C, 61.04; H, 7.25; N, 4.66.
Synthesis of [3]rotaxane-4: [3]Rotaxane-4 was prepared by an analogous method similar to that used for
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[2]rotaxane-2. Yield: 112 mg, 54%. H NMR (600 MHz, CD3CN): δ 7.71 (s, 8H), 7.37 (s, 4H), 7.17 (s, 1H), 7.13 (s,
2H), 7.08 (s, 1H), 6.63 (s, 2H), 6.59 (d, J = 9.6 Hz, 6H), 6.28 - 6.14 (m, 4H), 6.04 (s, 2H), 5.77 (s, 2H), 4.50 (s, 4H),
4.43 (s, 4H), 4.24 (s, 4H), 4.15 (s, 4H), 4.10 (s, 2H), 4.07 (s, 4H), 4.03 (s, 4H), 3.89 (s, 4H), 3.83 (s, 6H), 3.80 (s, 6H),
3.75 (s, 6H), 3.71 - 3.55 (m, 36H), 3.53 (s, 12H). 13C NMR (100 MHz, CDCl3): δ 161.1, 160.9, 160.1, 147.1, 147.0,
132.9, 129.1, 126.5, 124.7, 108.0, 107.5, 107.2, 102.4, 70.7, 70.4, 70.2, 70.0, 69.4, 69.1, 68.6, 68.4, 67.4, 55.5, 55.2,
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52.6. MALDI-TOF MS: m/z = 1760.41 [M - PF6 - HPF6]; calculated exact mass: 2050.83. Anal. Calcd for:
C96H132F12N2O28P2: C, 56.19; H, 6.48; N, 1.37. Found: C, 56.26; H, 6.55; N, 1.32.
Synthesis of hetero[4]rotaxane-3: Hetero[4]rotaxane-3 was prepared by an analogous method similar to that
used for hetero[3]rotaxane-1. Yield: 170 mg, 56%. 1H NMR (400 MHz, CD3CN): δ 8.65 (s, 1H), 7.15 – 6.99 (m, 4H),
6.73 – 6.67 (m, 8H), 6.60 (br, 8H), 6.58 – 6.55 (m, 2H), 6.51 - 6.44 (m, 4H), 6.34 (br, 4H), 6.20 (br, 8H), 4.49 (s, 8H),
4.38 (t, J = 6.4 Hz, 2H), 4.29 (s, 2H), 4.18 (s, 4H), 4.12 (d, J = 4.0 Hz, 4H), 4.10 – 4.07 (m, 12H), 3.92 (s, 8H), 3.82 –
3.79 (m, 18H), 3.77 – 3.71 (m, 12H), 3.64 – 3.58 (m, 28H), 3.51 – 3.49 (m , 6H), 3.02 (t, J = 8.0 Hz, 2H), 1.83 –
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1.85 (m, 4H), 1.79 – 1.69 (m, 4H), 1.50 – 1.47 (m, 6H), 1.29 (br, 40H), 0.90 (t, J = 8.0 Hz,6H). The spectrum of 13C
NMR was not collected due to the poor solubility of hetero[4]rotaxane-3. MALDI-TOF MS: m/z = 1377.48 [M -
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Synthesis of hetero[4]rotaxane-4: Hetero[4]rotaxane-4 was prepared by an analogous method similar to that
used for hetero[3]rotaxane-1. Yield: 128 mg, 49%. 1H NMR (600 MHz, CD3CN): δ 7.75 – 7.70 (m, 8H), 7.37 (dd, J =
6.1, 3.2 Hz, 4H), 7.31 (s, 4H), 7.16 – 7.14 (m, 2H), 6.89 (s, 4H), 6.63 – 6.60 (m, 12H), 6.58 – 6.56 (m, 2H), 6.52 (d, J
= 2.0 Hz, 2H), 6.27 (d, J = 2.2 Hz, 2H), 5.77 (s, 2H), 4.45 – 4.43 (m, 4H), 4.39 (t, J = 6.0 Hz, 2H), 4.32 – 4.28 (m,
4H), 4.13 (s, 8H), 4.10 – 4.06 (m, 8H), 3.92 – 3.89 (m, 8H), 3.83 (s, 4H), 3.82 (s, 8H), 3.80 (s, 12H), 3.78 – 3.76 (dd,
J = 5.4, 3.4 Hz, 8H), 3.72 – 3.70 (m, 6H), 3.66 – 3.63 (m, 12H), 3.62 – 3.60 (m , 12H), 3.58 (br, 12H), 3.54 (br, 8H),
3.04 (s, 2H), 1.75 – 1.70 (m, 6H). The spectrum of 13C NMR was not collected due to the poor solubility of
hetero[4]rotaxane-4. MALDI-TOF MS: m/z = 1162.05 [M - PF6 ]2+; calculated exact mass: 2614.01. Anal. Calcd for:
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C119H164F18N3O34P3: C, 54.65; H, 6.32; N, 1.61. Found: C, 54.60; H, 6.26; N, 1.66.
Synthesis of [4]rotaxane-5: [4]Rotaxane-5 was prepared by an analogous method similar to that used for
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[2]rotaxane-1. Yield: 223 mg, 62%. H NMR (400 MHz, CD3CN): δ 8.74 (s, 6H), 6.89 (s, 6H), 6.70 - 6.57 (m, 18H),
6.39 (s, 6H), 6.30 (s, 3H), 6.15 (s, 9H), 6.09 (s, 6H), 4.53 (s, 12H), 4.33 (s, 6H), 4.11 (s, 6H), 3.99 (s, 12H), 3.89 (s,
12H), 3.75 (s, 36H), 3.56 (s, 12H), 3.50 (s, 6H), 3.43 (s, 18H), 1.81 (s, 6H), 1.45 (s, 6H), 1.28 (s, 60H), 0.89 (s, 9H).
13C NMR (100 MHz, CD3CN): δ 167.3, 161.7, 161.5, 160.6, 147.2, 137.5, 134.9, 122.0, 120.0, 112.8, 110.7, 109.3,
107.5, 107.0, 103.6, 101.5, 72.0, 71.8, 71.1, 69.8, 69.2, 68.1, 55.7, 53.3, 50.5, 32.4, 30.1, 29.8, 29.3, 26.4, 23.1, 14.2.
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MALDI-TOF MS: m/z = 3152.89 [M - PF6 - 2HPF6]; calculated exact mass: 3152.90. Anal. Calcd for:
C183H261F18N12O33P3: C, 61.19; H, 7.32; N, 4.68. Found: C, 61.33; H, 7.15; N, 4.76.
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The authors acknowledge financial support from National Natural Science Foundation of China (Nos. 20931006, 21072070,
21272088) and the Program for Academic Leader in Wuhan Municipality (No.201271130441). This work was also
supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIP)
(No.2012R1A3A2048814 for J.Y.). The work was also supported by the Scientific Research Foundation for the Returned
Overseas Chinese Scholars, Ministry of Education.
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n SUPPORTING INFORMATION
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Crystal structure and data of compound 30; H NMR, 13C NMR, ROESY, and MS spectra of all the new interminates,
[n]rotaxanes and hetero[n]rotaxanes are available in the Supporting Information. This material is available free of charge via
the Internet at http://pubs.acs.org.
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