Directed synthesis of [2]Catenanes incorporating naphthalenediimide and crown ethers by associated interactions of templates

Article abstract of DOI:10.1021/jo201068y

In this paper, we introduce a simple one-step method to synthesize [2]catenanes incorporating naphthalenediimide and crown ethers by associated interactions of templates. In this functional supermolecular system, the combined hydrogen-bond and π-donor/π-a

Full text of DOI:10.1021/jo201068y

ARTICLE
pubs.acs.org/joc
Directed Synthesis of [2]Catenanes Incorporating
Naphthalenediimide and Crown Ethers by Associated
Interactions of Templates
Wenlong Yang,†,‡ Yongjun Li,† Jianhong Zhang,†,‡ Nan Chen,†,‡ Songhua Chen,†,‡ Huibiao Liu,† and
Yuliang Li*,†
†Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Organic Solids, Institute of Chemistry,
Chinese Academy of Sciences, Beijing 100190, P.R. China
‡Graduate University of Chinese Academy of Sciences, Beijing 100080, P.R. China
S Supporting Information
b
ABSTRACT: In this paper, we introduce a simple one-step
method to synthesize [2]catenanes incorporating naphthalene-
diimide and crown ethers by associated interactions of tem-
plates. In this functional supermolecular system, the combined
hydrogen-bond and π-donor/π-acceptor interactions led pro-
duction of the [2]catenanes which exhibit reversible moving of
the crown ether macrocycle on the big ring between two
stations via de/reprotonation. This movement on the big ring
can change the electron interaction, resulting in strong quench-
ing of the emission of naphthalene diimide.
’ INTRODUCTION
The [2]catenanes synthesized by associated interaction of
hydrogen-bond and π-donor/π-acceptor have not been re-
ported. Herein, we propose a one-step hydrogen-bond and π-
donor/π-acceptor template-directed self-assembly procedure for
the preparation of [2]catenanes by “CuAAC click” reaction.
The efficient preparation of mechanically interlocked struc-
tures, such as rotaxanes and catenanes, is vital for their successful
applications in fabricating molecular machines, sensors, and nano
materials.1 Catenanes, topologically nontrivial molecules posses-
sing two or more mechanically interlocked rings, have been
known for nearly half a century2 and have attracted considerable
attention as synthetic targets3 and more recently as proposed and
realized components of functional molecular devices, such as
switches,4 unidirectional motors,5 and electronic displays.6 The
synthesis of catenanes has been one of the topics where
supramolecular chemistry has obtained numerous successes.
The rapid development of this new area of chemistry has
promoted the understanding of the concepts of design and
strategies of self-assembly of structures based on inter- and
intramolecular interactions to result in synthetic supramolecular
systems of catenanes. The self-assembly processes guided by
noncovalent forces facilitates the preorganization of the molec-
ular components prior to the cyclization reactions, in generally
via π-donor/π-acceptor complexes,7 hydrogen bond interac-
tion,8 anion templation,9 or metal complexation,10 these strate-
gies have been utilized frequently to construct higher order
[n]catenanes by n interlocked macrocycles.11 Recently ever more
diverse methods were reported to synthesize bistable catenanes,
the challenge that remains for these bistable molecules is their
incorporation into an integrated functional supramolecular sys-
tem, design of higher performance supramolecules and under-
standing the structureꢀfunction relationships that relate
specifically to [2]catenanes.
’ RESULTS AND DISCUSSION
Scheme 1 outlines the preparation of the two [2]catenanes 4A
and 4B from the secondary dialkylammonium axle 1, the
naphthalenediimide (NDI) 2, and crown ethers dinaphtho-24-
crown-8 (DN24C8) 3A and dibenzo-24-crown-8 (DB24C8) 3B.
A dilute equimolar amount of 2 was added dropwise to a highly
dilute mixture containing an equimolar amount of compound 1,
3, and catalyst [Cu(MeCN)4]PF6 in dichloromethane at room
temperature for 24 h. The target [2]catenanes 4A and 4B were
obtained in 42% and 35% yield, respectively. The MALDI-TOF
spectra of 4A and 4B gave sharp peaks at m/z 1398.7 [M ꢀ PF6]+
and 1498.5 [M ꢀ PF6]+ (see the Supporting Information),
respectively, which revealed the features of an interlocked
molecule. A product of [3]catenane 7 (MALDI-TOF m/z
2798.2) was obtained in 2% yield in the presence of 3B.
However, [3]catenane was not isolated when the reaction was
carried out in the presence of 3A instead. The result was similar
to the Loeb12 group’s report that a series of [3]catananes was
obtained using different crown ethers as the guest, which
Received: June 1, 2011
Published: August 12, 2011
r
2011 American Chemical Society
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indicated formation of products with DB24C8 was 2ꢀ3 times
more favorable than that with other crown ethers. Remarkably, in
the same way in the absence of crown ethers 3, the naked NDI big
ring 6 (blue cycle, Scheme 1) was not observed. This is due to the
electron-deficient properties of the secondary dialkylammonium
axle 1 and the NDI 2 units, which enabled them to get together.
Regioselective methylation of the [2]catenanes 4 was carried out
in iodomethane at 40 °C overnight to afford the two-station
[2]catenanes 5 by anion exchange (Scheme 1). The electrospray
ionization (ESI) mass spectra of [2]catenanes 5A and 5B reveal
triply charged peaks at m/z 476.6 and 509.9 (see the Supporting
Information), respectively.
did not move toward the triazole station upon addition of a slight
molar excess of DIEA to the solution of 4. The crown ethers can
move toward the N-methyltriazolium station upon addition of
DIEA to the [2]catenane 5 (Scheme 2) because of the strong
interaction between the electron-rich crown ethers ring and the
electron-deficient N-methyltriazolium station.13 In the 1H NMR
spectra of the [2]catenane 5A, the chemical shifts of the
complexed crown ether hydrogens HC and HD are not split,
indicating that they are facing a symmetrical system and the
DN24C8 resides around the dialkylammonium station. Before
deprotonation, the 1H NMR spectra is relatively simple
(Figure 2b). Upon addition of base, deprotonation of the
secondary dialkylammonium moiety resulted in the moving of
DN24C8 toward the N-methyltriazolium station, which led the
[2]catenane to be a wholly nonsymmetrical system. The obvious
changes can be observed from the 1H NMR spectra (Figure 2c).
Nearly all chemical shifts of the crown ether hydrogens are split;
The proposed mechanism for the template-directed synthesis
of the [2]catenanes 4 is shown in Figure 1, which relies on (i) the
combination of N+ꢀH O and CꢀH O hydrogen bonds
3 3 3
3 3 3
and πꢀπ stacking interactions between the dialkylammonium
and the 24-crown-8 (24C8)13and (ii) π-donor/π-acceptor inter-
action between the electron-rich 24C8 and the electron-deficient
NDI. The first step in this reaction is the self-assembly of 24C8 3
with the nonstoppered secondary dialkylammonium axle 1
through hydrogen-bond interaction to form a [2]pseudorotax-
ane [1 ⊂ 3], which is dragged close to the NDI unit 2 by the
π-donor/π-acceptor interaction between the electron-rich 24C8
and the electron-deficient NDI. Then closure of the ring
happened by the click reaction in the presence of catalyst
[Cu(MeCN)4]PF6 to afford the [2]catenanes 4. The result
indicated that the crown ethers play dual roles, not only act as
the hydrogen-bond receptors for the secondary dialkylammo-
nium but also as the essential link for the secondary dialkylam-
monium axle 1 and the NDI 2.
0
the peaks for the N-methyltriazolium CꢀH protons Hf and Hf
are separated into two parts and both shifted downfield, one of
which was evidently shifted downfield due to the CꢀH
O
3 3 3
hydrogen-bond interaction. Obviously, an upfield shift was also
observed for the signals Ha and the peak changed from singlet to
multiplet, which can be attributed to the weak πꢀπ-stacking
interactions between the aromatic ring of DN24C8 and the
naphthalene ring of NDI. All these changes indicated that the
DN24C8 located at one of the N-methyltriazolium stations.
Furthermore, upon addition of trifluoroacetic acid (TFA) to
the deprotonated [2]catenane 5A, the protons Ha appear at δ =
8.65 ppm as well as the signal for the N-methyltriazolium ring
proton Hf which resonates at δ = 8.5 ppm, suggesting that the
DN24C8 was back to the original NH2+ recognition site follow-
ing reprotonation (Figure 2d). The signal changes of the protons
Ha and Hf showed the fact that the pH-controlled switching
Diisopropylethylamine (DIEA) is strong enough to deproto-
nate the NH2+ center.14 However, due to the weak interaction
between the crown ether and the triazole unit, the crown ethers
Scheme 1. Synthesis of [2]Catenanes 5 and [3]Catenane 7
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Scheme 1. Continued
process is reversible. Similar phenomena (Figure S1, Supporting
Information) could also be observed when base and acid were
added to the [2]catenane 5B.
[2]catenane 5A, the color of the solution changed from colorless
to slightly yellow and a new CT band at about 420ꢀ450 nm was
the generated. This was the result of the strong CT between the
naphthalene ring of DN24C8 and the NDI unit, which indicated
that DN24C8 moved toward the N-methyltriazolium station and
was close to NDI unit. Upon addition of 4 equiv of TFA into the
above system, the slightly yellow solution of 5A turned colorless
and the absorption band around 420ꢀ450 nm decreased,
indicating that the CT process was restricted and the DN24C8
was back to the NH2+ station. Similar to the [2]catenane 5A, an
unobvious CT band around 390ꢀ400 nm was observed for
[2]catenane 5B when DIEA was added (Figure S2 Supporting
Information) and the color change was hardly observed, which
can be attributed to the weak CT process between the benzene
ring of DB24C8 and the NDI unit and indicated that the
The present [2]rotaxanes 4 and 5 both display an intramole-
cular charge-transfer (CT) process controlled by the spacial
distance between the aromatic moiety of the crown ethers and
the NDI unit. UVꢀvis absorption spectroscopy experiments
were first performed to demonstate the CT behavior. There is a
CT band at about 420 nm for [2]catenane 4A as shown in
Figure 3, indicating that the CT process occurs between the
naphthalene ring on DN24C8 and the NDI unit. For
[2]catenane 5A, however, the CT band decreased because of
the interaction between the naphthalene ring of DN24C8 and
the electron-deficient N-methyltriazolium unit in the ground
state. When 2 equiv of DIEA was added to the solution of
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Figure 1. Proposed mechanism for synthesis of the [2]catenanes 4.
with the 1H NMR spectra, which all indicated that the
[2]catenanes 5 exhibit fully reversible switching of its crown
ether between two stations via de/reprotonation (Scheme 2).
Scheme 2. Movement Process of [2]Catenanes 5 under
AcidꢀBase Stimuli
’ CONCLUSION
We demonstrated that the concepts of design and strategies of
self-assembly of a [2]catenane structure based on associated
interactions of hydrogen-bond and π-donor/π-acceptor can
result in a reversible pH-controlled movement of two bistable
[2]catenanes. The results demonstrate the fact that the crown
ethers canfunctionnot only as an efficient hydrogen-bondacceptor
for the secondary dialkylammonium but also as the essential link for
the secondary dialkylammonium axle to the NDI by the π-donor/
π-acceptor interaction. Such chemical reactivity of the supramole-
cular species expands the functionality of the system and provides a
means to control the photophysical properties.
’ EXPERIMENTAL SECTION
Compound S-1. A solution of 1-(bromomethyl)-4-(prop-2-yn-1-
yloxy)benzene (2.24 g, 10 mmol) and 4-hydroxybenzaldehyde (1.22 g,
10 mmol) in acetone (100 mL) was heated under reflux in the presence
of K2CO3 (2.76 g, 20 mmol) under nitrogen. The reaction was
monitored by TLC until it was complete. The mixture was filtered,
and the solvent was removed under vacuum. The crude product was
dissolved in CH2Cl2 and washed with water three times (3 ꢁ 50 mL).
The organic layer was dried over anhydrous Na2SO4, concentrated, and
purified by column chromatography with CH2Cl2/hexane (1/1, v/v).
The white solid product compound (S-1), 2.26 g, was obtained with a
1
yield of 86%. H NMR (CDCl3, 400 MHz): δ = 9.88 (s, 1 H), 7.83
(m, 2 H), 7.37 (m, 2 H), 7.0ꢀ7.06 (m, 4 H), 5.07 (s, 2H), 4.70 (s, 2 H),
2.53 ppm (s, 1 H). 13C NMR (CDCl3, 100 MHz): δ = 190.9, 163.9,
157.8, 132.1, 130.2, 129.3, 129.1, 115.3, 78.5, 75.8, 70.1, 55.9 ppm.
HRMS (EI) calcd: m/z 266.0943 for C17H14O3. Found: m/z 266.0946.
Compound S-3. A solution of 1-(bromomethyl)-4-(prop-2-yn-1-
yloxy)benzene (2.24 g, 10 mmol) and 4-hydroxybenzonitrile (1.19 g,
10 mmol) in acetone (150 mL) was heated under reflux in the presence
of K2CO3 (2.76 g, 20 mmol) under nitrogen. The reaction was
monitored by TLC until it was completed. The mixture was filtered,
and the solvent was removed under vacuum. The crude product was
dissolved in CH2Cl2 and washed with water three times (3 ꢁ 50 mL).
The organic layer was dried over anhydrous Na2SO4 and filtered. The
filtrate was reduced in volume to obtain a white solid, which was used for
the next reaction without further purification. The crude product was
dissolved in anhydrous THF (100 mL) and cooled in an ice bath. Excess
LiAlH4 (1.9 g, 50 mmol) was added in a nitrogen atmosphere. The
reaction mixture was stirred overnight at ambient temperature. The
reaction mixture was cooled to 0 °C, and 5 mL of water was added
dropwise. After filtration, the solution was concentrated under reduced
pressure to afford the crude product. Purification was accomplished by
column chromatography on silica with CH2Cl2/MeOH (100/1, v/v) to
DB24C8 located at the N-methyltriazolium station. The CT
band around 390ꢀ400 nm also decreased after TFA was added,
suggesting that the CT process was restricted and the DB24C8
was back to the NH2+ site following reprotonation.
As shown in Figure 4, [2]catenanes 5A and 5B both exhibited
strong emission at 386 nm. After addition of 2 equiv of DIEA, the
emission intensity was quenched obviously, which was attributed
to the CT from the electron-rich 24C8 system to the electron-
deficient NDI unit and also indicated that the 24C8 moved
toward the NDI unit and localized at the N-methyltriazolium
station. The intensity can be completely recovered by addition of
+
TFA, suggesting that the 24C8 component was back to the NH2
recognition site. It is obvious that the [2]catenane 5A showed
weaker fluorescence intensity than the [2]catenane 5B when
they adopt the same conformation; this is due to the fact that
DN24C8 exhibits a stronger electron-donor ability than
DB24C8. The results obtained from the UVꢀvis absorption
and fluorescence spectroscopy experiments were in accordance
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Figure 2. 1H NMR spectra (400 MHz, CD3CN, 298 K) of (a) DN24C8, (b) the original spectrum of 5A, (c) 5A after addition of 2 equiv of DIEA, and
(d) 5A further addition of 4 equiv of TFA.
under reduced pressure after the reaction was cooled to room tempera-
ture. The residue was dissolved in THF (50 mL); then NaBH4 (0.4 g,
10.5 mmol) was added cautiously at 0 °C. The mixture was stirred at
room temperature for a further 4 h. Water was added to quench the
excess NaBH4. The THF was evaporated off, and the remaining aqueous
mixture was extracted with CH2Cl2 (3 ꢁ 100 mL). The combined
organic layers were dried over Na2SO4. After being concentrated in
vacuo, the crude product was purified by chromatography (SiO2:
CH2Cl2/MeOH, 30:1) to afford compound S-4 as a slightly yellow
solid (3.3 g, 64%): mp = 138ꢀ139 °C. 1H NMR (CD3CN, 400 MHz):
δ = 7.36 (d, 4 H, J = 8.4 Hz), 7.25 (d, 4 H, J = 7.1 Hz), 6.98 (d, 4 H, J = 8.5
Hz), 6.92 (d, 4 H, J = 6.7 Hz), 4.98 (s, 4H), 4.69 (d, 4 H, J = 2.2 Hz), 3.72
(s, 4 H), 2.52 ppm (t, 2 H, J = 1.9, 2.2 Hz). 13C NMR (CD3CN,
100 MHz): δ = 158.6, 158.2, 134.3, 131.4, 130.3, 130.2, 79.7, 76.8, 70.2,
Figure 3. Absorption spectra of (a) [2]catenane 4A (1 ꢁ 10ꢀ4 M), (b)
56.5, 53.6 ppm. HRMS (EI) calcd: m/z 517.2253 for C34H31NO4.
Found: m/z 517.2259.
Compound 1. TFA (1 mL) was added to the solution of compound
S-4 (2 g, 3.9 mmol) in acetone, which was stirred at room temperature
[2]catenane 5A (1 ꢁ 10ꢀ4 M), (c) 5A (1 ꢁ 10ꢀ4 M) + DIEA (2 equiv),
and (d) 5A (1 ꢁ 10ꢀ4 M) + DIEA (2 equiv) then TFA (4 equiv) in
CH3CN.
for 30 min. The solvent was evaporated off, and the residue was then
1
dissolved in acetone, followed by addition of excess NH4PF6 (0.82 g, 5
mmol) aqueous solution. The acetone was then removed, and the
aqueous solution was extracted with CH2Cl2 three times (50 mL ꢁ 3).
The organic extracts were dried (Na2SO4), and the solvent was
concentrated to dryness to yield compound 1 (2.46 g, 95%), which is
used for making rotaxane without further purification. 1H NMR
(CD3CN, 400 MHz): δ = 7.38 (m, 8 H), 7.27 (m, 2 H), 7.00 (m, 8
H), 5.03 (s, 4 H), 4.73 (s, 4 H), 4.13 (s, 4 H), 2.8 ppm (s, 2 H). 13C NMR
(CD3CN, 100 MHz): δ = 160.7, 158.4, 132.8, 130.9, 130.5, 123.7, 116.2,
give compound S-3 (1.82 g, 68%, two steps). H NMR (CDCl3, 400
MHz): δ = 7.36 (m, 2 H), 7.22 (m, 2 H), 6.92ꢀ6.98 (m, 4 H), 4.98 (s,
2H), 4.69 (s, 2 H), 3.79 (s, 2 H), 2.52 (s, 1 H), 1.56 ppm (s, 2 H). 13C
NMR (CDCl3, 100 MHz): δ = 157.9, 157.5, 135.9, 130.2, 129.2, 128.4,
115.1, 115.0, 78.6, 75.7, 69.8, 55.9, 46.0 ppm. HRMS (EI) calcd: m/z
267.1259 for C17H17NO2. Found: m/z 267.1263.
Compound S-4. A solution of S-1 (2.67 g, 10 mmol) and S-3
(2.67 g, 10 mmol) in toluene (100 mL) was heated under reflux
overnight using a DeanꢀStark apparatus. The solvent was removed
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Calcd for C86H84F6N9O16P: C, 62.81; H, 5.15; N, 7.67. Found: C,
62.52; H, 4.96; N, 7.71.
Compound 5A. [2]Catenane 4A (20 mg, 0.012 mmol) was
dissolved in iodomethane (2 mL), and the mixture was stirred for 24
h at 40 °C. Then iodomethane was evaporated, and the solid was washed
with Et2O to give a red solid. Then, to a suspension of the previous solid
in H2O (10 mL) were added NH4PF6 (6.5 mg, 0.04 mmol) and CH2Cl2
(15 mL). The resulting bilayer solution was vigorously stirred for 3 h.
After separation, the aqueous layer was extracted with CH2Cl2 (ꢁ3).
The organic layers were combined, dried over Na2SO4, and concen-
trated to obtain quantitatively the [2]catenane 5A (23 mg, 98%) as an
orange solid: mp = 148ꢀ149 °C. 1H NMR (CD3CN, 400 MHz): δ =
8.65 (s, 2 H), 8.44 (s, 1 H), 7.55 (m, 2 H), 7.18ꢀ7.22 (m, 8 H),
6.96ꢀ6.99 (m, 4 H), 6.51 (d, 2 H, J = 8.5 Hz), 5.29 (s, 2 H), 4.58ꢀ4.64
(m, 6 H), 4.16ꢀ4.20 (m, 5 H), 4.08 (m, 4 H), 3.77 (m, 4 H), 3.60 (s, 4
H), 2.42 ppm (m, 2H). 13C NMR (CDCl3, 100 MHz): δ = 163.5, 158.7,
156.7, 147.8, 139.8, 131.3, 131.0, 130.8, 129.9, 129.5, 129.2, 126.9, 126.7,
126.3, 124.5, 124.4, 115.2, 115.1, 107.7, 70.8, 70.1, 68.5, 68.2, 58.4, 52.1,
51.8, 38.6, 37.1, 27.7 ppm. MS (ESI-MS): m/z 509.9 [calcd for M3+
509.5]. Anal. Calcd for C88H90F18N9O16P3: C, 53.8; H, 4.62; N, 6.42.
Found: C, 53.58; H, 4.55; N, 6.51.
Compound 4B. A dilute mixture of 1 (50 mg, 0.075 mmol), 3B (36
mg, 0.08 mmol), and [Cu(MeCN)4]PF6 (37 mg, 0.1 mmol) was stirred
in dry CH2Cl2 (400 mL) at room temperature under nitrogen for 0.5 h.
A highly dilute solution of compound 2 (32 mg, 0.075 mmol) in CH2Cl2
(100 mL) was added to the solution slowly over 8 h and stirred for
another 24 h under nitrogen. After removal of the solvent, the crude
product was purified by column chromatography (CH2Cl2/MeOH
30:1) to afford [2]catenane 4B (40 mg, 35%): mp = 145ꢀ146 °C. 1H
NMR (CD3CN, 400 MHz): δ = 8.57 (s, 2 H), 7.76 (s, 1 H), 7.27
(m, 2 H), 7.14 (m, 2 H), 6.83ꢀ6.88 (m, 4 H), 6.77ꢀ6.8 (m, 2 H), 6.72
(m, 2 H), 4.98 (s, 2 H), 4.85 (s, 2 H), 4.42ꢀ4.46 (m, 4 H), 4.19 (m, 2 H),
3.95 (m, 4 H), 3.56 (m, 4 H), 3.28 (s, 4 H), 2.36 ppm (m, 2H). 13C NMR
(CDCl3, 100 MHz): δ = 163.6, 159.2, 158.3, 148.2, 131.5, 131.3, 129.8,
127.3, 127.0, 124.4, 122.5, 116.3, 115.5, 113.7, 70.9, 70.5, 69.8, 69.2, 54.1,
52.5, 38.7, 28.9 ppm. MS (MALDI-TOF): m/z 1398.7 [calcd for M+
1398.6]. Anal. Calcd for C78H80F6N9O16P: C, 60.66; H, 5.22; N, 8.16.
Found: C, 60.47; H, 5.14; N, 8.25.
Figure 4. Fluorescence spectra of [2]catenanes 5A and 5B (λexc
=
356 nm, 1 ꢁ 10ꢀ5 M, 298 K) in CH3CN before deprotonation (black),
after deprotonation with 2 equiv of DIEA (red), and reprotonation with
4 equiv of trifluoroacetic acid (TFA, blue).
115.9, 79.7, 76.9, 70.3, 56.6, 51.7 ppm. HRMS (EI) calcd: m/z 518.2326
+
for C34H32NO4 . Found: m/z 518.2318.
Compound 2. A solution of S-5 (1.34 g, 5 mmol) and 3-azidopro-
pan-1-amine (1 g, 10 mmol) in DMF (50 mL) was heated at 70 °C for 8
h. The product precipitated from the cooled filtrate was collected by
filtration, washed with water, and dried in a vacuum, and the mixture was
purified by column chromatography on silica with CH2Cl2/petrol (1/2,
v/v) to give 2 as a pink solid (1.82 g, 84%): mp = 187ꢀ188 °C. 1H NMR
(CDCl3, 400 MHz): δ = 8.78 (s, 4 H), 4.32 (t, 4 H, J = 7.0, 7.1 Hz), 3.47
(t, 4 H, J = 6.6, 6.7 Hz), 2.06 ppm (m, 4 H). 13C NMR (CDCl3, 100
MHz): δ = 163.0, 131.3, 126.9, 126.7, 49.6, 38.7, 27.7 ppm. EI-MS: m/z
404 [M-N2]. Anal. Calcd for C20H16N8O4: C, 55.55; H, 3.73; N, 25.91.
Found: C, 55.27; H, 3.65; N, 26.13.
Compound 5B. [2]Catenane 4B (20 mg, 0.013 mmol) was
dissolved in iodomethane (2 mL), and the mixture was stirred for 24
h at 40 °C. Then iodomethane was evaporated, and the solid was washed
with Et2O to give a red solid. To a suspension of the previous solid in
H2O (10 mL) were added NH4PF6 (6.5 mg, 0.04 mmol) and CH2Cl2
(15 mL). Then the resulting bilayer solution was vigorously stirred for 3
h. After separation, the aqueous layer was extracted with CH2Cl2 (3 ꢁ
50 mL). The organic layers were combined, dried over Na2SO4, and
concentrated to obtain quantitatively the [2]catenane 5B (23.5 mg,
1
97%) as a yellow solid: mp = 141ꢀ142 °C. H NMR (CD3CN, 400
MHz): δ = 8.69 (s, 2 H), 8.50 (s, 1 H), 7.38 (d, 2 H, J = 8.5 Hz), 7.18 (d,
2 H, J = 8.6 Hz), 7.04 (d, 2 H, J = 8.6 Hz), 6.80ꢀ6.83 (m, 2 H),
6.72ꢀ6.75 (m, 2 H), 6.68 (d, 2 H, J = 8.5 Hz), 5.32 (s, 2 H), 4.98 (s, 2 H),
4.62 (m, 2 H), 4.53 (m, 2 H), 4.22 (s, 3 H), 4.18 (m, 2 H), 3.97 (m, 4 H),
3.66 (m, 4 H), 3.45 (s, 4 H), 2.43 ppm (m, 2H). 13C NMR (CDCl3, 100
MHz): δ = 164.3, 159.5, 157.7, 148.4, 140.6, 132.1, 131.9, 131.6, 130.8,
130.4, 127.7, 127.6, 125.3, 122.1, 116.0, 115.9, 113.4, 71.4, 70.9, 69.6,
68.9, 59.2, 52.9, 52.5, 39.4, 37.9, 28.4 ppm. MS (ESI-MS): m/z 476.6
[calcd for M3+ 476.2]. Anal. Calcd for C80H86F18N9O16P3: C, 51.53; H,
4.65; N, 6.76. Found: C, 51.41; H, 4.59; N, 6.82.
Compound 4A. A dilute mixture of 1 (50 mg, 0.075 mmol), 3A (44
mg, 0.08 mmol), and [Cu(MeCN)4]PF6 (37 mg, 0.1 mmol) was stirred
in dry CH2Cl2 (400 mL) at room temperature under nitrogen for 0.5 h.
A highly dilute solution of compound 2 (32 mg, 0.075 mmol) in CH2Cl2
(100 mL) was added to the solution slowly over 8 h and stirred for
another 24 h under nitrogen. After removal of the solvent, the crude
product was purified by column chromatography (CH2Cl2/MeOH
30:1) to afford [2]catenane 4A (52 mg, 42%): mp = 142ꢀ143 °C. 1H
NMR (CD3CN, 400 MHz): δ = 8.54 (s, 2 H), 7.76 (s, 1 H), 7.62 (m, 2
H), 7.27 (m, 2 H), 7.11ꢀ7.16 (m, 4 H), 7.07 (s, 2 H), 6.83 (d, 2 H, J = 8.6
Hz), 6.55 (d, 2 H, J = 8.6 Hz), 4.87 (s, 2 H), 4.65 (s, 2 H), 4.55 (m, 2 H),
4.53 (t, 2 H, J = 6.5, 6.7 Hz), 4.19 (t, 2 H, J = 6.7, 6.5 Hz), 4.06 (m, 4 H),
3.67 (m, 4 H), 3.44 (s, 4 H), 2.38 ppm (m, 2H). 13C NMR (CDCl3, 100
MHz): δ = 163.1, 158.7, 147.7, 131.0, 130.6, 129.3, 129.2, 126.8, 126.5,
126.4, 124.9, 123.7, 115.8, 115.1, 108.4, 70.6, 69.9, 69.1, 68.7, 52.1, 42.1,
38.3 ppm. MS (MALDI-TOF): m/z 1498.5 [calcd for M+ 1498.6]. Anal.
Compound 7. In the preparation of compound 4B, compound 7
1
was isolated (2.3 mg, 2%). H NMR (CD3CN, 400 MHz): δ = 8.50
(s, 2 H), 7.84 (s, 1 H), 7.26 (m, 3 H), 7.14 (m, 2 H), 6.92 (m, 2 H), 6.83
(m, 2 H), 6.75 (m, 2 H), 6.68 (m, 2 H), 4.96 (s, 2 H), 4.90 (s, 2 H), 4.44
(m, 5 H), 4.15 (t, 2 H, J = 2.6, 3.04 Hz) 3.96 (m, 4 H), 3.63 (m, 4 H), 3.41
(s, 4 H), 2.14 ppm (m, 2H). 13C NMR (CDCl3, 100 MHz): δ = 162.9,
7755
dx.doi.org/10.1021/jo201068y |J. Org. Chem. 2011, 76, 7750–7756

The Journal of Organic Chemistry
ARTICLE
158.3, 156.8, 147.5, 142.4, 130.9, 130.4, 129.3, 126.5, 121.2, 115.1, 114.8,
112.5, 70.5, 70.0, 68.9, 67.9, 61.5, 51.6, 48.1, 38.0, 27.9 ppm. MS
(MALDI-TOF): m/z 2798.2 [calcd for M+ 2797.1], 1399.6 [calcd for
M2+ 1398.6]. Anal. Calcd for C156H160F12N18O32P2: C, 60.66; H, 5.22;
N, 8.16. Found: C, 60.37; H, 5.13; N, 8.25.
Goddard, W. A.; Stoddart, J. F. Chem. Asian J. 2007, 2, 76–93. (c)
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’ ASSOCIATED CONTENT
S
Supporting Information. Full experimental details per-
b
taining to the preparation and characterization of all compounds
including NMR and MS spectra; COSY-NMR spectra of
[2]catenanes 5A and 5B; absorption spectra of [2]catenanes 4B
and 5B. This material is available free of charge via the Internet at
http://pubs.acs.org.
’ AUTHOR INFORMATION
(8) (a) Johnston, A. G.; Leigh, D. A.; Pritchard, R. J.; Deegan, M. D.
Angew. Chem., Int. Ed. 1995, 34, 1209–1212. (b) Jager, R.; Vogtle, F.
Angew. Chem., Int. Ed. 1997, 36, 930–944. (c) Fustin, C. A.; Bailly, C.;
Clarkson, G. J.; De Groote, P.; Galow, T. H.; Leigh, D. A.; Robertson, D.;
Slawin, A. M. Z.; Wong, J. K. Y. J. Am. Chem. Soc. 2003, 125, 2200–2207.
(d) Leigh, D. A.; Venturini, A.; Wilson, A. J.; Wong, J. K. Y.; Zerbetto, F.
Chem.—Eur. J. 2004, 10, 4960–4969.
(9) (a) Ng, K. -Y.; Cowley, A. R.; Beer, P. D. Chem. Commun.
2006, 3676–3678. (b) Lankshear, M. D.; Evans, N. H.; Bayly, S. R.; Beer,
P. D. Chem.—Eur. J. 2007, 13, 3861–3870. (c) Zhao, Y. J.; Li, Y. L.; Li,
Y. J.; Zheng, H. Y.; Yin, X. D.; Liu, H. B. Chem. Commun. 2010,
46, 5698–5700.
Corresponding Author
*E-mail: ylli@iccas.ac.cn
’ ACKNOWLEDGMENT
We are grateful for financial support from the National Nature
Science Foundation of China (21031006, 20831160507,
20721061, 20971127), the NSFC-DFG joint fund (TRR 61),
and the National Basic Research 973 Program of China.
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