Cryptands with 1,3,5-Tris(1′,3′-dioxan-2′-yl)-benzene units: Synthesis and structural investigations

Article abstract of DOI:10.1021/jo401432y

Various cryptands based on 1,3-dioxane decorated 1,3,5-trisubstituted- benzene building blocks, connected by different chains (exhibiting ester, ether, or triazol groups) to several units with C₃ symmetry, are reported. The structure of the com

Full text of DOI:10.1021/jo401432y

Subscriber access provided by Otterbein University
Article
Cryptands with 1,3,5-Tris(1',3'-Dioxan-2'-yl)-Benzene
Units: Synthesis and Structural Investigations
Monica Circu, Albert Soran, Niculina Daniela Hadade, Monica Rednic, Anamaria Terec, and Ion Grosu
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/jo401432y • Publication Date (Web): 07 Aug 2013
Downloaded from http://pubs.acs.org on August 14, 2013
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts
appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered
to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just
Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
The Journal of Organic Chemistry is published by the American Chemical Society.
1155 Sixteenth Street N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 22
The Journal of Organic Chemistry
1
2
3
4
5
Cryptands with 1,3,5-Tris(1’,3’-Dioxan-2’-yl)-Benzene Units:
Synthesis and Structural Investigations
6
7
8
9
Monica Cîrcu, Albert Soran, Niculina Daniela Hădade, Monica Rednic, Anamaria Terec*
and Ion Grosu*
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
BabeꢀꢁBolyai University, Center of Supramolecular Organic and Organometallic Chemistry
(CSOOMC), ClujꢁNapoca, 11 Arany Janos str., 400028, ClujꢁNapoca, România;
Eꢁmails: asuciu@chem.ubbcluj.ro; igrosu@chem.ubbcluj.ro
Table of Contents Graphic
Abstract: Various cryptands based on 1,3ꢁdioxane decorated 1,3,5ꢁtrisubstitutedꢁbenzene
building blocks, connected by different chains (exhibiting ester, ether or triazol groups) to
several units with C3 symmetry, are reported. The structure of the compounds was
investigated by single crystal Xꢁray diffraction, NMR and MS. The role of the 1,3ꢁdioxane
units was targeted to ensure the preorganization of the substrate for the macrocyclization
reactions on one side, and for easier NMR assignment of the structure of the cryptands, on
the other side.
1
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 2 of 22
1
2
3
4
5
Introduction
6
7
8
9
Building blocks exhibiting 1,3ꢁdioxane units were successfully used in the synthesis of
macrocycles and cyclophanes.1 Many 1,3ꢁdioxane derivatives were extensively
investigated and the main aspects of their stereochemistry were elucidated.2 The NMR
spectra of 1,3ꢁdioxane derivatives are very sensitive to structural alterations and the
changes in NMR spectra of the dioxacyclohexane units were successfully used to monitor
the rotameric behavior of the aromatic groups in some cyclophanes with conformational
equilibria suggesting the work of rudders or wringers,1b in the elucidation of the mechanism
of a molecular “rocking chair”1a or of the temperature induced flipping of the chains in a
[4.4]cyclophane.1c The NMR data obtained for the 1,3ꢁdioxane rings supported the
determination of the stereochemistry of spiranes with sixꢁmembered rings2d,e and of the
atropenantiomers of 2ꢁmethylꢁ2ꢁarylꢁ1,3ꢁdioxane derivatives.2f
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
The preorganization of the substrates with spiroꢁ1,3ꢁdioxanes or with bis(1,3ꢁdioxanꢁ2ꢁ
yl)arenes facilitated the macrocyclization reactions.1 The axialꢁaxial orientation of the
aromatic ring for both 1,3ꢁdioxane units in I ensured the favorable disposition of the
reactive groups and the good yields obtaining of [7.7]cyclophanes II or [4.4]cyclophanes III
(Chart 1).1
Chart 1. [7.7]Cyclophanes (II) and [4.4]cyclophanes (III) with 1,3ꢁdioxane units
2
ACS Paragon Plus Environment

Page 3 of 22
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
Cryptands with C3 symmetry are attractive targets for the building of host molecules, and
such compounds with 1,3,5ꢁtrisubstituted benzene,3 tertiary amines4 or phosphines,5
cyclotribenzylene6 and 1,3,5ꢁtriazine7 units were successfully obtained and investigated.
Some tripodands with 1,3,5ꢁtris(2’ꢁRꢁ1’,3’ꢁdioxanꢁ2’ꢁyl)ꢁbenzene core (IV) were already
reported (Chart 2)8 and the structural investigations revealed a favourable arrangement of
the substrate (the aromatic unit is axial for all 1,3ꢁdioxane rings) for the access to cryptand
like compounds (Chart 2).
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
The target in this work was to synthesize and to investigate series of cryptands exhibiting
1,3ꢁdioxane moieties in the main structural unit (Chart 2, V and VI). The synthetic strategy
was based on etherification, esterification and “click” reactions using as substrates the
already obtained tripodands with 1,3,5ꢁtris(2’ꢁRꢁ1’,3’ꢁdioxanꢁ2’ꢁyl)ꢁbenzene core IV (Chart
2).8
Chart 2. Tripodands with 1,3ꢁdioxane units (IV) and target cryptands (V and VI).
Results and discussions
Cryptands 4 and 5 exhibiting ether groups in the chains we obtained in good yields by
reacting the tripodand 1 (IV, X = OH; Chart 2, Scheme 1) with 1,3,5ꢁ
tris(bromomethyl)benzene
respectively (Scheme 1).
2
and N,N,Nꢁtris(4ꢁbromomethylꢁbenzeneꢁ1ꢁyl)amine 3,
3
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 4 of 22
1
2
3
4
5
6
7
8
Tripodand 6 bearing propargyl groups at the extremities of the pendant arms (IV, X = Oꢁ
CH2ꢁC≡CH; Chart 2, obtained from 1 in reaction with propargyl bromide) was submitted to
a “click” reaction with triazide 7 (obtained from 2 in reaction with NaN3) in order to give
cryptand 8 (Scheme 2).
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Scheme 1
Despite the abundance of macrocycles,9 there are only a reduced number of reports on
the synthesis of macrocyclic compounds by “click” reactions.10 The obtaining of rotaxanes
(the click reaction generates the axle or attaches the stoppers),11 of catenanes (clipping by
click reaction),12 of a rotaxaneꢁcatenane (click obtaining of the axle)13, of knots14 and of a
cryptand7b are the most spectacular encountered examples. The major difficulties in
investigating in solution the cyclophanes and cryptands obtained by "click" reaction were
caused by the poor solubility of these compounds in manifold solvents.
In the case of 8 the 1,3ꢁdioxane units ensured a favourable preorganization of the
substrate for the obtaining of the cryptand and also increased significantly the solubility of
4
ACS Paragon Plus Environment

Page 5 of 22
The Journal of Organic Chemistry
1
2
the final compound (8) in many solvents (e.g. dichloromethane, chloroform, acetone,
3
4
5
ethylacetate).
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Scheme 2
The reaction of 1 with 1,3,5ꢁbenzene tricarboxylic acid trichloride 9, surprisingly, lead to
the obtaining of cryptand 10 which corresponds to the 2+2 reaction (dimer, 38 %, Scheme
3). MS investigations of the crude product revealed the formation of small amounts of the
3+3 cryptand (trimer; could not be isolated), in addition to the main compound (the dimer)
but no formation of monomer (target 1+1 product) was observed.
Scheme 3
In order to investigate the structure and the properties of a more simple [4.4.4]cyclophane
the deprotection of the carbonyl groups in cryptand 4 was carried out (Scheme 4).
Conditions employed for the already reported similar [4.4]cyclophane,1d i.e. the
deprotection with cerium ammonium nitrate (CAN) and HCl, produced mixtures of monoꢁ,
5
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 6 of 22
1
2
3
4
5
6
7
diꢁ and trideprotected products which are difficult to separate, while the deprotection
reaction with trifluoroacetic acid (TFA) gave in good yields (92 %) the completely
deprotected product, the target cryptand 11.
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Scheme 4
Structural investigations in solid state
Suitable crystals for single crystal Xꢁray diffractometry investigations were obtained only
for 4.
The single crystal Xꢁray diffraction on compound 4 reveals that the asymmetric unit, having
a threefold symmetry, consists of a single molecule solvate with chloroform (Figure 1). The
aromatic rings of the cryptand are perfectly parallel [angle between planes defined by the
rings is 0º within standard deviation].
a
b
Figure 1. Views of the asymmetric unit of 4·x CHCl3 solvate (a), and of the cryptand 4
(solvent was removed for clarity) along the a axis (b) with 40% probability ellipsoids).
6
ACS Paragon Plus Environment

Page 7 of 22
The Journal of Organic Chemistry
1
2
3
4
Symmetry equivalent atoms are given by ‘prime’ [ꢁy, xꢁy, z], ‘double prime’ [ ꢁx+y, ꢁx, z], ‘*’
[1ꢁy, 1+xꢁy, z] and ‘**’ [ ꢁx+y, 1ꢁx, z].
5
6
7
8
9
Each cryptand molecule is associated through twelve weak hydrogen bonds with three
other neighboring molecules. The H bonds involve the H(12) atom of the basal aromatic
ring, H(9b) atom of the methylene bridge on one hand, and oxygen O(1) of the 1,3ꢁdioxane
ring and oxygen O(3) atom of the bridge on the other hand [C(9)ꢁH(9b)····O(3) = 2.54 Å,
C(12)ꢁH(12)····O(1)= 2.58 Å, ΣrvdW(H,O) = 2.60 Å 15], leading to a sheet like supramolecular
assembly. The orientation of molecules within these sheets is headꢁtoꢁtail (Figures 2 and
3).
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Figure 2. View along c axis of the supramolecular associations through H····O bonds
between headꢁtoꢁtail arranged molecules of 4. Only hydrogen atoms involved in
interactions are shown. Different colours were used for the representation of the differently
oriented molecules.
7
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 8 of 22
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Figure 3. View along b axis of the supramolecular associations through H····O bonds
between headꢁtoꢁtail arranged molecules of 4. Only hydrogen atoms involved in
interactions are shown. The aromatic parts of the cryptand are shown as blue hexagonal
prisms.
Figure 4. View along b axis showing H····π interactions between solvent CHCl3 molecules
and aromatic rings, leading to the three dimensional structure. Solvent molecules are
displayed with van der Waals radii. The aromatic parts of the cryptand are shown as blue
hexagonal prisms.
Strong Hꢁπ interactions are observed between the basal aromatic ring of each cryptand
and a chloroform molecule [centroid(C6H3)····H(13) = 2.374(1) Å, ΣrvdW(H,C) = 3.00 Å 15].
8
ACS Paragon Plus Environment

Page 9 of 22
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
The chloroform molecule is placed exactly above the centroid of the aromatic ring [the
angle between the C(13)ꢁH(13) bond vector and the normal of the plane is 180º (0°) within
standard deviation]. These values are at the extremity of the range for the reported data
for the highest Hꢁπ interactions involving chloroform and aromatic rings (the already
reported distances and angles are in the domains 2.53 ± 0.17 Å and 169 ± 11°,
respectively)16 and suggest the high strength of the Hꢁπ interactions in our case. Overall,
the contacts between adjacent layers are made by the hydrophobic interactions between
the methyl groups located at position 5 of the 1,3ꢁdioxane rings (Figure 4).
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Structural investigations in solution
All cryptands obtained by 1+1 reactions exhibit simple NMR spectra which suggest not
only the equivalence of the chains, but also their flexible behaviour. For 4, 5 and 8 the 1H
NMR spectra (Figure 5) reveals an AB system for the protons of the 1’,5’ꢁdioxaciclohexane
rings (Table 1) and singlets for the other types of protons [Figure 5, Table 1; excepting the
protons of the triphenylamino unit in 5 which give (formally) doublets (AA'XX' system)].
b
a
d
c
9
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 10 of 22
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
e
Figure 5. 1H NMR spectra (fragments) of compounds 4 (a), 5 (b), 8 (c), 10 (e) and 11 (d)
In the case of the 2+2 reaction product 10 (a cartoon representation is given in Chart 3)
similar building blocks become different due to their belonging to either the formal
macrocycles or to the bridges which connect the macrocyclic units.
D
B
A
A
B
C
D
B
A
+
D
D
C
Chart 3. Cartoon representation of the formal synthesis of 10 revealing the differences
among similar building blocks
Thus, the 1,5ꢁdioxaꢁalkylidene units (formally 1,3ꢁdioxane rings) belonging to the
macrocycles (noted with D) are different of those of the chains (noted with C). Similarly the
10
ACS Paragon Plus Environment

Page 11 of 22
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
CH2 groups are different if they are incorporated in the macrocycles or if they belong to the
chains. The 1H NMR spectrum of 10 (Figure 5e) exhibits two signals (intensities ratio 1 / 2;
“inside” and “outside” macrocycle aromatic protons) for each type of aromatic rings (A and
B). The CH2 groups of the chains, the equatorial and axial methyl groups located at the
positions 3’ of the 1’,5’ꢁdioxaalkylidene groups, as well as the protons located at positions
2’ and 4’ of the 1’,5’ꢁdioxaalkylidene groups (saturated heterocycles) show two sets of
signals, one set belonging to the protons of the macrocycles and the other set is given by
the similar protons of the chains (ratio of signals intensities 2 / 1). The signal belonging to
the CH2 groups of the chains appears as one singlet, while the protons of the CH2 groups
of the macrocycles give an AB system (the protons of the same CH2 group are
diastereotopic).
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Table 1. NMR data (selected) for compounds 4, 5, 8 and 11
Compd
Chains (CH2 groups)
(ppm)
Dioxacyclohexane units
(ppm)
CꢁCH2ꢁO
3.81
ꢁCH2ꢁAr
4.25
NꢁCH2ꢁO 2’a,4’a; 2’e, 4’e 3’ꢁCH3 (e) 3’ꢁCH3 (a)
4
ꢁ
3.20; 3.37
3.44; 3.53
3.39; 3.50
ꢁ
0.50
0.62
0.64
ꢁ
1.24
1.30
1.29
ꢁ
5
3.39
3.82
ꢁ
4.72
ꢁ
8
3.34
5.40
11
4.49
4.72
Similarly, positions 2’ and 4’ of the dioxacyclohexane rings belonging to the bridges (type
C) are equivalent in NMR and give one AB system, while the protons of the similar
positions (2’ and 4’) of the dioxacyclohexane rings of the macrocycles (type D) are
diastereotopic and give different signals in the NMR spectrum (two AB systems, Figure
5e). Hence, a comparison can be made between compound 10 and a [4.4]cyclophane in
11
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 12 of 22
1
2
3
4
5
6
7
8
which the aromatic units were replaced by the “rigid” macrocycles. The NMR differences
between the signals of the chains and of the similar units included in the macrocycles can
be explained by the flexibility of the chains (usual flipping of the chains in
[4.4]cyclophanes)1d,17 and the hindrance of this equilibrium in the macrocycles. The flipping
of the chains render equivalent positions 2’ and 4’ of the 1’,5’ꢁdioxaalkylidene units on one
side and the H atoms of the CH2 groups on the other side.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Conclusions
The good yields synthesis by various procedures (etherification, esterification and “click”)
of several cryptands exhibiting 1,3,5ꢁtris(2’ꢁRꢁ1’,3’ꢁdioxanꢁ2’ꢁyl)ꢁbenzene units was
reported. The reactions led to the target cryptands in etherification and click procedures,
while the macrocyclization based on esterification reactions determined the formation of
the 2+2 reaction product (dimer). The small cryptand 11 obtained by the deprotection of 4
exhibits three reactive carbonyl groups and it is an interesting building block for further
developments. The molecular structure of 4 revealed the formation of a solvate, with
strong CHꢁꢁꢁπ contact between the chloroform and the cryptand.
Experimental part
General experimental data:
1H NMR (300 MHz, 400 MHz) and 13C NMR (75 MHz, 100 MHz) spectra, COSY, HSQC
and HMBC were recorded in CDCl3 at rt on 300 MHz and 600 MHz spectrometers using
the solvent line as reference. Atmospheric pressure chemical ionisation (APCI, positive
ions mode) high–resolution mass spectra were recorded on LTQ ORBITRAP XL
spectrometer using external mass calibration. Melting points were measured with routine
melting point apparatus and are uncorrected. Thin layer chromatography (TLC) was
12
ACS Paragon Plus Environment

Page 13 of 22
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
conducted on silica gel 60 F254 TLC plates, while preparative column chromatography
was performed using 40–63 ꢂm silica gel. Solvents were dried and distilled under argon
using standard procedures. Chemicals of commercial grade were used without further
purification. Xꢁray diffraction data were collected at room temperature on a diffractometer
using graphite monochromated MoꢁKα radiation (λ = 0.71073 Å). For this purpose the
crystal was mounted on a cryoꢁloop with Paraton oil. The structure was solved by direct
methods (SHELXSꢁ97)18 and refined by full matrix leastꢁsquares procedures based on F2
with all measured reflections (SHELXLꢁ97).18 All nonꢁhydrogen atoms were refined
anisotropically. H atoms were introduced in their idealized positions and refined as riding.
Further details on the data collection and refinement methods can be found in Table 1.
The drawings were created with the Diamond program.19
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
These data can be also obtained free of charge from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223ꢁ336ꢁ033; or eꢁmail:
deposit@ccdc.cam.ac.uk). The deposition number is: CCDC ꢁ 904025 (4).
Compound 1 was already reported in a previous work,20 compounds 2,21 322 and 721 were
obtained according with published procedures.
Procedure for the synthesis of 4 and 5: A solution of triol 1 [0.98 mmol (4) / 0.39 mmol (5)]
in THF (10/5 ml) was added to a suspension of NaH (5.88/2.35 mmol) in anhydrous THF
(300/150 ml), under inert atmosphere (Ar). The mixture was refluxed for 1h, followed by
the addition of the tribrominated derivative 2 (0.98 mmol) or 3 (0.39 mmol) in THF (10 ml)
with a pushꢁsyringe for 72 hours. The reaction mixture was refluxed for another 24h,
cooled to room temperature, the solvent was removed in vacuo and the residue dissolved
in CH2Cl2 and washed with water; the organic layer was separated, dried over anhydrous
MgSO4, filtered and purified by flash chromatography [ethylacetate:pentane = 2:3 (4) or
1:4 (5)].
13
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 14 of 22
1
2
3
4
7,7,13,13,22,22-tris(3’,3’-dimethyl-1’,5’-dioxapentane-1’,5’-diyl)-5,15,20-trioxatetracyclo[8.
8.4.13,17.18,12]tetracosa-1,3(24),8(23),9,11,17-hexaene 4.
5
White solid (347 mg, 56%, Rf = 0.54), mp = 279ꢁ280ºC. 1H NMR (300 MHz, CDCl3) δ(ppm)
0.50 (s, 9H, 3’ꢁCH3eq), 1.24 (s, 9H, 3’ꢁCH3ax), 3.20 (d, J = 12 Hz, 6H, 2’ꢁHax, 4’ꢁHax), 3.37
(d, J = 12 Hz, 6H, 2’ꢁHeq, 4’ꢁHeq), 3.81 (s, 6H, 6ꢁH, 14ꢁH, 21ꢁH), 4.25 (s, 6H, 4ꢁH, 16ꢁH, 19ꢁ
H), 6.85 (s, 3H, 2ꢁH, 18ꢁH, 24ꢁH), 7.14 (s, 3H, 9ꢁH, 11ꢁH, 23ꢁH); 13C NMR (75 MHz, CDCl3)
δ(ppm) 22.1 (3’ꢁCH3eq), 22.9 (3’ꢁCH3ax), 30.2 (3’ꢁC), 70.9 (2’ꢁC, 4’ꢁC), 73.0 (6ꢁC, 14ꢁC, 21ꢁ
C), 75.3 (4ꢁC, 16ꢁC, 19ꢁC), 99.5 (7ꢁC, 13ꢁC, 22ꢁC), 128.0 (9ꢁC, 11ꢁC, 23ꢁC), 130.9 (2ꢁC,
18ꢁC, 24ꢁC), 136.4 (8ꢁC, 10ꢁC, 12ꢁC), 137.00 (1ꢁC, 3ꢁC, 17ꢁC); HRMS (APCI+) m/z calcd
for C36H49O9 [M+H]+: 625.3371; found: 625.3370.
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
9,9,15,15,30,30-tris(3’,3’-dimethyl-1’,5’-dioxapentane-1’,5’-diyl)-1-aza-7,17,28-trioxahexa
cyclo[10.10.8.22,5.219,22.224,26.110,14]heptatricosa-2,4,10(31),11,13,19,21,23,25,32,34,36-
dodecaene 5.
1
Light yellow solid (144 mg, 0.18 mmol, 47%, Rf. = 0.47), mp = 63ºC. H NMR (300 MHz,
CDCl3) δ(ppm) 0.62 (s, 9H, 3’ꢁCH3eq), 1.30 (s, 9H, 3’ꢁCH3ax), 3.39 (s, 6H, 8ꢁH, 16ꢁH, 29ꢁH),
3.44 (d, J = 12 Hz, 6H, 2’ꢁHax, 4’ꢁHax), 3.53 (d, J = 12 Hz, 6H, 2’ꢁHeq, 4’ꢁHeq), 3.82 (s, 6H, 6ꢁ
H, 18ꢁH, 27ꢁH), 7.35 (d, 6H, J = 9 Hz, 3ꢁH, 21ꢁH, 24ꢁH, 33ꢁH, 34ꢁH, 37ꢁH), 7.50 (s, 3H, 11ꢁ
H, 13ꢁH, 31ꢁH), 7.79 (d, 6H, J = 9 Hz, 4ꢁH, 20ꢁH, 25ꢁH, 32ꢁH, 35ꢁH, 36ꢁH); 13C NMR (75
MHz, CDCl3) δ(ppm) 13C NMR (75 MHz, CDCl3) δ 21.9 (3’ꢁCH3eq), 22.7 (3’ꢁCH3ax), 30.2 (3’ꢁ
C), 53.4 (8ꢁC, 16ꢁC, 29ꢁC), 66.0 (6ꢁC, 18ꢁC, 27ꢁC), 71.2 (2’ꢁC, 4’ꢁC), 100.8 (9ꢁC, 15ꢁC, 30ꢁ
C), 120.9 (11ꢁC, 13ꢁC, 31ꢁC), 127.3 (3ꢁC, 21ꢁC, 24ꢁC, 33ꢁC, 34ꢁC, 37ꢁC), 129.4 (4ꢁC, 20ꢁ
C, 25ꢁC, 32ꢁC, 35ꢁC, 36ꢁC), 136.9 (5ꢁC, 19ꢁC, 26ꢁC), 137.9 (10ꢁC, 12ꢁC, 14ꢁC), 146.5 (2ꢁ
C, 22ꢁC, 23ꢁC); HRMS (APCI+) m/z calcd for C48H58NO9 [M+H]+: 792.4106; found:
792.4110.
14
ACS Paragon Plus Environment

Page 15 of 22
The Journal of Organic Chemistry
1
2
1,3,5-tris[1’,1’-(3",3"-dimethyl-1",5"-dioxapentan-1",5"-diyl)-3’-oxahexan-5’-yn-1’-yl]ben
3
4
5
zene 6. Procedure: 1,3,5ꢁtris(5,5ꢁdimethylꢁ2ꢁhydroxymethylꢁ1,3ꢁdioxaneꢁ2ꢁyl)ꢁbenzene
1
6
7
8
9
(1.37 mmol, 700 mg, 1 equiv.) was dissolved in dichloromethane (20 ml); a saturated
aqueous solution of NaOH and tertꢁbutyl ammonium bromide (0.25 equiv.) were added
and then stirred together for 30 min at 10oC. After adding propargyl bromide (0.734 ml sol.
80% in toluene, 6.594 mmol, 4.8 equiv.) the reaction mixture was stirred over night at room
temperature. At the end the final solution was diluted with 60 mL of dichloromethane and
the organic layer was washed with water, dried over anhidrous MgSO4, filtered and atfer
the evaporation (in vacuo) of the solvent, the pure compound was obtained by column
chromatography separation (ethylacetate : pentane = 1:4).
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
White solid (444 mg, 0.71 mmol, 52%, Rf. = 0.53), mp = 126ºC. Calculated for C36H48O9:
C, 69.21; H, 7.74. Found: C, 69.39; H, 7.58. 1H NMR (300 MHz, CDCl3) δ ppm: 0.59 (s,
9H, 3’’ꢁCH3eq), 1.28 (s, 9H, 3’’ꢁCH3ax), 2.28 (t, 3H, J = 2.1 Hz, 6’ꢁH), 3.44 (s, 12H, 4’’ꢁH, 6’’ꢁ
H), 3.62 (s, 6H, 2’ꢁH), 4.16 (d, 6H, J = 2.1 Hz, 4’ꢁH), 7.53 (s, 3H, 2ꢁH, 4ꢁH, 6ꢁH). 13C NMR
(75MHz, CDCl3) δ ppm: 21.9 (3’’ꢁCH3eq), 22.9 (3’’ꢁCH3ax), 30.2 (Cꢁ3’’), 58.9 (Cꢁ4’), 71.3 (Cꢁ
4’, Cꢁ6’), 74.3 (11ꢁCꢁ6’), 76.4 (Cꢁ2’), 79.6 (Cꢁ5’), 100.5 (Cꢁ1’), 127.8 (Cꢁ2, Cꢁ4, Cꢁ6), 137.6
(Cꢁ1, Cꢁ3, Cꢁ5). ESI-MS: m/z = 647.3 [M+Na] +, 663.4 [M+K]+
12,12,18,18,37,37-tris(3’,3’-dimethyl-1’,5’-dioxapentane-1’,5’-diyl)-5,6,7,23,24,25,30,31,
32-nonaaza-10,20,35-trioxaheptacyclo[3.3.9.15,8.113,17.122,25.13,27.130,33]dotetraconta-
1,3(40),6,8(41),13(38),14,16,22(39),23,27,31,33(42)-dodecaene 8. Procedure: Compound
6 (250 mg, 0.4 mmol) was dissolved in a 1:1 mixture of H2O:THF (40 ml). After degassing
the reaction mixture, CuSO4*5H2O (200 mg, 0.8 mmol) and sodium ascorbate (31 mg,
0.16 mmol) were added at room temperature, followed by the addition of 1,3,5ꢁ
tris(azidomethyl)benzene 7 (97 mg, 0.4 mmol) and TBTA {Tris[(1ꢁbenzylꢁ1Hꢁ1,2,3ꢁtriazolꢁ
15
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 16 of 22
1
2
3
4
5
6
7
8
4ꢁyl)methyl]amine; 17 mg, 0.033 mmol}. The new mixture was stirred at room temperature
for 3h; then extracted with dichloromethane and washed with brine was followed. The
layers were separated, the organic phase was dried on anhydrous MgSO4, filtered and
evaporated in order to obtain the crude product. Purification was achieved on column
chromatography (CH2Cl2: MeOH = 95:5, Rf = 0.24) to give compound 8 (243 mg, 0.28
mmol, 70%) as a white solid: mp = 175oC.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1H NMR (300 MHz, CDCl3) δ(ppm) 0.64 (s, 9H, 3’ꢁCH3eq), 1.29 (s, 9H, 3’ꢁCH3ax), 3.34 (s,
6H, 11ꢁH, 19ꢁH, 36ꢁH), 3.39 (d, 6H, J = 11 Hz, 2’ꢁHax, 4’ꢁHax), 3.50 (d, 6H, J = 11 Hz, 2’ꢁHeq,
4’ꢁHeq), 4.72 (s, 6H, 9ꢁH, 21ꢁH, 34ꢁH), 5.40 (s, 6H, 4ꢁH, 26ꢁH, 29ꢁH), 6.85 (s, 3H, 39ꢁH, 41ꢁ
H, 42ꢁH), 7.21 (s, 3H, 14ꢁH, 16ꢁH, 38ꢁH), 7.44 (s, 3H, 2ꢁH, 28ꢁH, 40ꢁH); 13C NMR (75 MHz,
CDCl3) δ(ppm) 22.1 (3’ꢁCH3eq), 22.7 (3’ꢁCH3ax), 30.2 (3’ꢁC), 53.4 (4ꢁC, 26ꢁC, 29ꢁC), 66.2 (9ꢁ
C, 21ꢁC, 34ꢁC), 71.3 (2’ꢁC, 4’ꢁC), 77.2 (11ꢁC, 19ꢁC, 36ꢁC), 100.8 (12ꢁC, 18ꢁC, 37ꢁC), 120.9
(39ꢁC, 41ꢁC, 42ꢁC), 127.1 (14ꢁC, 16ꢁC, 38ꢁC), 129.2 (2ꢁC, 28ꢁC, 40ꢁC), 136.9 (13ꢁC, 15ꢁC,
17ꢁC), 137.72 (1ꢁC, 3ꢁC, 27ꢁC), 146.3 (8ꢁC, 22ꢁC, 33ꢁC); HRMS (APCI+) m/z calcd for
C45H58N9O9 [M+H]+: 868.4352; found: 868.4357.
7,7,13,13,25,25,31,31,40,40,47,47-hexakis(3’,3’-dimethyl-1’,5’-dioxapentane-1’,5’-diyl)-5,
15,23,33,48,45-hexaoxaheptacyclo[26.8.4.410,19.13,35.18,12.117,21.126.30]octatetraconta-1,3
(41),8(48),9,11,17
(43),18,20,26(42),27,29,35-dodecaene
10.
Procedure:
1,3,5ꢁ
Benzenetricarbonyl trichloride 9 (1.47 mmol) in anhydrous THF (10 ml) was added via a
pushꢁsyringe over 24 hours, to a solution of compound 1 (0.98 mmol) in a mixture of dry
THF (50 ml), acetonitrile (200 ml) and DMAP (1.96 mmol). The reaction mixture was
stirred over night at room temperature, and then the mixture of solvents was removed in
vacuo, the residue dissolved in diethylether and washed with water. The organic layer was
separated, dried over anhydrous MgSO4, filtered, the solvents were removed in vacuo and
16
ACS Paragon Plus Environment

Page 17 of 22
The Journal of Organic Chemistry
1
2
3
4
the crude product was purified by column chromatography (ethyl acetate: pentane = 1:3;
Rf = 0.50) giving a white solid (496 mg, 0.372 mmol, 38%), mp = 360ºC (dec.).
5
1H NMR (300 MHz, CDCl3) δ(ppm) 0.62 (s, 12 H, 3’ꢁCH3eq”D”), 0.79 (s, 6H, 3’ꢁCH3eq”C”),
1.18 (s, 12H, 3’ꢁCH3ax”D”), 1.27 (s, 6H, 3’ꢁCH3ax”C”), 3.27, 3.37, 3.43, 3.47 [four d (rings D), J
= 12 Hz, 16H, 2’ꢁHax, 4’ꢁHax, 2’ꢁHeq, 4’ꢁHeq], 3.58, 3.65 [two d (rings C), J = 12 Hz, 8H, 2’ꢁ
Hax, 4’ꢁHax, 2’ꢁHeq, 4’ꢁHeq], 3.96, 4.49 [two d, J = 12 Hz, 8H, 14ꢁH, 32ꢁH, 39ꢁH, 46ꢁH), 4.79
(s, 4H, 6ꢁH, 24ꢁH), 7.52 (s, 2H, 18ꢁH, 36ꢁH), 7.58 (s, 2H, 11ꢁH, 29ꢁH), 7.70 (s, 4H, 2ꢁH, 20ꢁ
H, 41ꢁH, 43ꢁH), 8.02 (s, 4H, 9ꢁH, 27ꢁH, 42ꢁH, 48ꢁH); 13C NMR (75 MHz, CDCl3) δ(ppm)
22.3 (3’ꢁCH3eq”D”), 22.5 (3’ꢁCH3eq”C”), 22.8 (3’ꢁCH3ax”C”), 22.9 (3’ꢁCH3ax”D”), 30.2 (3’ꢁC”C”),
30.4 (3’ꢁC”D”), 69.2 (6ꢁC, 24ꢁC), 69.4 (14ꢁC, 32ꢁC, 39ꢁC, 46ꢁC), 71.0, 71.5, 71.9 [(2’ꢁC”C”, 4’ꢁ
C”C”), 2’ꢁC”D”, 4’ꢁC”D”], 99.6 (13ꢁC, 31ꢁC, 40ꢁC, 47ꢁC), 100.6 (7ꢁC, 25ꢁC), 127.5 (2ꢁC, 20ꢁC,
41ꢁC ,43ꢁC), 129.77 (3ꢁC, 21ꢁC), 130.10 (18ꢁC, 36ꢁC), 130.33 (1ꢁC, 17ꢁC, 19ꢁC, 35ꢁC),
132.6 (9ꢁC, 27ꢁC, 42ꢁC, 48ꢁC), 137.3 (8ꢁC, 26ꢁC), 137.7 (11ꢁC, 29ꢁC), 138.7 (10ꢁC, 12ꢁC,
28ꢁC, 30ꢁC), 162.3 (4ꢁC, 16ꢁC, 22ꢁC, 34ꢁC), 163.8 (37ꢁC, 44ꢁC); HRMS (APCI+) m/z calcd
for C72H85O24 [M+H]+: 1333.5425; found:1333.5429.
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
5,15,20-trioxatetracyclo[8.8.4.13,17.18,12]tetracosa-1,3(23),8(24),9,11,17-hexaene-7,13,22-
trione 11. Procedure: Trifluoroacetic acid (TFA, 0.25 mL) and a drop of water were added
to a stirred solution of compound 4 (24 mg, 0.038 mmol) in MeCN (1 mL). The solution
was refluxed for 48 h. After cooling to room temperature, TFA was evaporated in vacuo,
and then water (5mL) was added and the mixture was extracted with dichloromethane,
and washed with saturated NaHCO3 solution (3*10 mL). The organic layers were dried
with MgSO4, filtered, and the solvent was evaporated in vacuo. The crude product was
further purified by washing with pentane, and reꢁcrystallization in diethyl ether giving 11
(13 mg, 0.035 mmol, 92%, Rf = 0.41 (pentane:ethyl acetate=20:1) as a white solid: mp
17
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 18 of 22
1
2
3
4
5
6
7
8
=154ꢁ155˚C; 1H NMR (400 MHz, CDCl3) δ(ppm) 4.50 (s, 6 H, 6 –H, 14 –H, 21ꢁH), 4.72 (s,
6H, 4ꢁH, 16ꢁH, 19ꢁH), 6.81 (s, 3H, 2ꢁH, 18ꢁH, 24ꢁH), 8.11 (s, 3H,9ꢁH, 11ꢁH, 23ꢁH);. 13C
NMR (100 MHz, CDCl3) δ(ppm) 76.3 (4ꢁC, 16ꢁC, 19ꢁC), 79.3 (6ꢁC, 14ꢁC, 21ꢁC), 130.6 (2ꢁ
C, 18ꢁC, 24ꢁC), 135.2 (9ꢁC, 11ꢁC, 23ꢁC), 137.0 (1ꢁC, 3ꢁC, 17ꢁC), 139.0 (8ꢁC, 10ꢁC, 12ꢁC),
201.5 (7ꢁC, 13ꢁC, 22ꢁC); HRMS (APCI+) m/z calcd for C21H19O6 [M+H]+: 367.1176; found:
367.1175.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Acknowledgments
We are grateful to CNCS–UEFISCDI for the financial support of this work, project PNꢁIIꢁIDꢁ
PCCEꢁ2011ꢁ2ꢁ0050
Supporting Information Available: General data regarding the Xꢁray diffractometry
measurement, the table of the parameters for the crystallographic determinations, Cif file
and the copies of 1H and 13C NMR spectra for 4-6, 8, 10 and 11. This material is available
free of charge via the Internet at http://pubs.acs.org.
References
1. (a) Balog, M.; Grosu, I.; Plé, G.; Ramondenc, Y.Condamine, E.; Varga, R. J. Org.
Chem. 2004, 69, 1337ꢁ1345; (b) Bogdan, N; Grosu, I.; Benoît, G. Toupet, L.; Ramondenc,
Y.; Condamine, E.; Silaghi Dumitrescu, I.; Plé, G. Org. Lett. 2006, 8, 2619ꢁ2622; (c)
Bogdan, N.; Condamine, E.; Toupet, L.; Ramondenc, Y.; SilaghiꢁDumitrescu, I.; Grosu I.
Tetrahedron Lett. 2008, 49, 5204ꢁ5207; (d) Bogdan, N. D.; Grosu, I. Curr. Org. Chem.
2008, 13, 502ꢁ531.
2. (a) Eliel, E. L.; Wilen, S. H.; Mander, L. N. Stereochemistry of Organic Compounds,
New York, Wiley; 1994, p. 740–754; (b) Anteunis, M. J. O.; Tavernier, D.; Borremans, F.
18
ACS Paragon Plus Environment

Page 19 of 22
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
Heterocycles 1976, 4, 293ꢁ371; (c) Kleinpeter, E. Adv. Het. Chem. 2004, 86, 41ꢁ127; (d)
Kleinpeter, E. Adv. Het. Chem. 1998, 69, 217ꢁ269; (d) Grosu, I.; Mager, S.; Plé, G.; Horn,
M. J. Chem. Soc. Chem. Commun. 1995, 167ꢁ168; (e) Opris, D.; Grosu, I.; Toupet, L.;
Plé, G.; Terec, A.; Mager, S.; Muntean, L. J. Chem. Soc. Perkin Trans. 1 2001, 2413ꢁ
2420; (f) Grosu, I.; Plé, G.; Mager, S.; Mesaros, E.; Dulau, A.; Gego, C. Tetrahedron 1998,
54, 2905ꢁ2916,
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
3. (a) Seel, C.; Vögtle, F. Angew. Chem. Int. Ed. 1992, 31, 528ꢁ549; (b) Mastalerz, M.
Angew. Chem. Int. Ed. 2010, 49, 5042 – 5053; (c) Sambasivan, S.; Kim, S. G.; Choi, S.
M.; Rhee, Y. M.; Ahn, K. H. Org. Lett. 2010, 12, 4228ꢁ4231; (d) GomezꢁLor, B.; Hennrich,
G.; Alonso, B.; Monge, A.; GutierrezꢁPuebla, E.; Echavarren, A. M. Angew. Chem. Int. Ed.
2006, 45, 4491ꢁ4494; (e) Kumazawa, K.; Yamanoi, Y.; Yoshizawa, M.; Kusukawa, T.;
Fujita, M. Angew. Chem. Int. Ed. 2004, 43, 5936ꢁ5940; (f) Meier, H.; Karpouk, E.
Tetrahedron Lett. 2004, 45, 4477–4480.
4. (a) Ballester, P. Chem. Soc. Rev. 2010, 39, 3810ꢁ3830; (b) Kang, S. O.; Llinares, J. M.;
Day, V. W.; BowmanꢁJames, K. Chem. Soc. Rev. 2010, 39, 3980ꢁ4003.
5. (a) Stollenz, M.; Barbasiewicz, M.; NawaraꢁHultzsch, A. J.; Fiedler, T.; Laddusaw, R. M.;
Bhuvanesh, N.; Gladysz, J. A. Angew. Chem. Int. Ed. 2011, 50, 6647ꢁ6651; (b) Bauer, I.;
Habicher, W. D. Collect. Czech. Chem. Commun. 2004, 69, 1195ꢁ1230
6. (a) Brotin, T.; Dutasta, J.ꢁP. Chem. Rev. 2009, 109, 88–130; (b) Holman, K. T.; Drake,
S. D.; Steed, J. W.; Orr, G. W.; Atwood, J.L. Supramol. Chem. 2010, 22, 870–890; (c) Li,
M. J.; Lai, C. C.; Liu, Y. H.; Peng, S. M.; Chiu, S. H. Chem. Commun. 2009, 5814–5816.
7. (a) Naseer, M. M.; Wang, D. X.; Zhao, L. A.; Huang, Z. T.; Wang, M. X. J. Org. Chem.
2011, 76, 1804ꢁ1813; (b) MoralesꢁSanfrutos, J.; OrtegaꢁMunoz, M.; LopezꢁJaramillo, J.;
HernandezꢁMateo, F.; SantoyoꢁGonzalez, F. J. Org. Chem. 2008, 73, 7772ꢁ7774; (c) Pop,
19
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 20 of 22
1
2
3
4
F.; Socaci, C.; Terec, A.; Condamine, E.; Varga, A. R.; RaŃ, C. I.; Roncali, J.; Grosu, I.
Tetrahedron, 2012, 68, 8581ꢁ8588.
5
6
7
8
9
8. Cîrcu, M.; Paꢀcanu, V.; Soran, A.; Braun, B.; Terec, A.; Socaci, C.; Grosu, I.
CrystEngComm 2012, 14, 632–639.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
9. a) Davis, F.; Higson, S. Macrocycles: Construction, Chemistry and Nanotechnology
Applications 2011, John Wiley & Sons, Ltd, Chichester, UK. ; b) Diederich, F.; Stang, P.
G.; Tykwinski R. R. (eds.) Modern Supramolecular Chemistry-Strategies for Macrocycle
Synthesis 2008, WileyꢁVCH, Weinheim, Germany; c) Parker D. (ed.) Crown
Ethers/Macrocycle Synthesis: A practical Approach 1996, Oxford University Press, Oxford,
UK.
10. (a) Pirali, T.; Tron, G. C.; Zhu, J. P. Org. Lett. 2006, 8, 4145ꢁ4148; (b) Haridas, V.;
Sahu, S.; Venugopalan, P. Tetrahedron 2011, 67, 727ꢁ733; (c) Zhao, Y. J.; Li, Y. L.;
Huang, C. S.; Liu, H. B. A.; Lai, S. W.; Che, C. M.; Zhu, D. B. Org. Biomol. Chem. 2010, 8,
3923ꢁ3927; (d) Bogdan, A. R.; James, K. Chem. Eur. J. 2010, 16, 14506ꢁ14512; (e)
Leyden, R.; Murphy, P. V. Synlett. 2009, 1949–1950; (f) Hou, J.ꢁT.; Zhang, Q.ꢁF.; Xu, B.ꢁ
Y.; Lu, Q.ꢁS.; Liu, Q.; Zhang, J.; Yu, X.ꢁQ. Tetrahedron Lett. 2011, 52, 4927–4930.
11. (a) Hänni, K. D.; Leigh, D. A. Chem. Soc. Rev. 2010, 39, 1240–1251; (b) Crowley, J.
D.; Goldup, S. M.; Lee, A.ꢁL.; Leigh, D. A.; McBurney, R. T. Chem. Soc. Rev. 2009, 38,
1530–1541; (c) Boyle, M. M.; Forgan, R. S.; Friedman, D. C.; Gassensmith, J. J.;
Smaldone, R. A.; Stoddart, J. F.; Sauvage, J.ꢁP. Chem. Commun. 2011, 47, 11870–
11872; (d) Aprahamian, I.; Dichtel, W. R.; Ikeda, T.; Heath, J. R.; Stoddart, J. F. Org. Lett.
2007, 9, 1287ꢁ1290; (e) Lahlali, H.; Jobe, K.; Watkinson, M.; Goldup, S. M. Angew. Chem.
Int. Ed. 2011, 50, 4151ꢁ4155; (f). Braunschweig, A. B.; Dichtel, W. R.; Miljanić, O. Š.;
Olson, M. A.; Spruell, J. M.; Khan, S. I.; Heath, J. R.; Stoddart J. F. Chem. Asian J. 2007,
2, 634ꢁ647; (g) Collin, J. P.; Durola, F.; Frey, J.; Heitz, V.; Reviriego, F.; Sauvage, J.ꢁP.;
20
ACS Paragon Plus Environment

Page 21 of 22
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
Trolez, Y.; Rissanen, K. J. Am. Chem. Soc. 2010, 132, 6840ꢁ6850; (h) Collin, J. P.;
Sauvage, J.ꢁP.; Trolez, Y.; Rissanen, K. New J. Chem. 2009, 33, 2148ꢁ2154; (i)
Gassensmith, J. J.; Barr, L.; Baumes, J. M.; Paek, A.; Nguyen, A.; Smith, B. D. Org. Lett.
2008, 10, 3343ꢁ3346; (j) Aucagne, V.; Berna, J.; Crowley, J. D.; Goldup, S. M.; Hänni, K.
D.; Leigh, D. A.; Lusby, P. J.; Ronaldson, V. E.; Slawin, A. M. Z.; Viterisi, A.; Walker, D. B.
J. Am. Chem. Soc. 2007, 129, 11950ꢁ11963. (k) Blanco, V.; Carlone, A.; Hänni, K. D.;
Leigh, D. A.; Lewandowski B. Angew. Chem. Int. Ed. 2012, 51, 5166 –5169; (l) Durola, F.;
Russo, L.; Sauvage, J.ꢁP.; Rissanen, K.; Wenger, O. S. Chem.–Eur. J. 2007, 13, 8749–
8753; (m) Prikhod’ko, A. I.; Durola, F.; Sauvage, J.ꢁP. J. Am. Chem. Soc. 2008, 130, 448–
449; (n) Prikhod’ko, A. I.; Sauvage, J.ꢁP. J. Am. Chem. Soc., 2009, 131, 6794–6807; (o)
Spruell, J. M.; Dichtel, W. R.; Heath, J. R.; Stoddart J. F. Chem.–Eur. J. 2008, 14, 4168–
4177; (p) Chwalek, M.; Auzély R.; Fort, S. Org. Biomol. Chem. 2009, 7, 1680–1688; (q)
Collin, J.ꢁP.; Durot, S.; Keller, M.; Sauvage, J.ꢁP.; Trolez, Y.; Cetina, M.; Rissanen, K.
Chem. Eur. J. 2011, 17, 947 – 957.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
12. (a) Miljanić, O. Š.; Dichtel, W. R.; Khan, S. I.; Mortezaei, S.; Heath, J. R.; Stoddart, J.
F., J. Am. Chem. Soc., 2007, 129, 8236ꢁ8246; (b) Megiatto Jr, J. D.; Schuster, D. I. J. Am.
Chem. Soc. 2008, 130, 12872ꢁ12873; (c) Megiatto Jr., J. D.; Schuster, D. I. Chem.–Eur. J.,
2009, 15, 5444–5448; (d) Romuald, C.; Coutrot, F. Angew. Chem. Int. Ed. 2012, 51, 2544
– 2545.
13. Barin, G.; Coskun, A.; Friedman, D. C.; Olson, M. A.; Colvin, M. T.; Carmielli, R.; Dey,
S. K.; Bozdemir, O. A.; Wasielewski, M. R.; Stoddart, J. F. Chem. Eur. J. 2011, 17, 213ꢁ
222;
14. Romuald, C.; Coutrot, F. Angew. Chem. Int. Ed. 2012, 51, 2544 – 2545.
15. Emsley, J. Die Elemente, Walter de Gruyter, Berlin, 1994.
21
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 22 of 22
1
2
3
4
16 Nishio, M. Phys. Chem. Chem. Phys. 2011, 13, 13873–13900; Takahashi, O.; Kohno,
Y.; Nishio, M. Chem. Rev. 2010, 110, 6049ꢁ6076.
5
6
7
8
9
17. (a) Asami, M.; Krieger, C.; Staab, H. A. Tetrahedron Lett. 1991, 32, 2117–2120; (b)
Sakakibara, K.; Naka, K.; Yamaguchi, Y.; Asami, M.; Chen, K.ꢁH.; Lii, J.ꢁH.; Allinger, N. L.
J. Phys. Chem. A 2004, 108, 3048–3055.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
18. Sheldrick, G. M. Acta Crystallogr., Sect. A: Found. Crystallogr., 2008, A64, 112–122.
19. Brandenburg, K. DIAMOND, Crystal Impact GbR, Bonn, Germany, 2006.
20. Florian, M. C.; Cîrcu, M. V.; Toupet, L.; Terec, A.; Grosu, I.; Ramondenc, Y.; Dincă, N.;
Plé, G. Cent. Eur. J. Chem., 2006, 4, 808–821.
21. Moses, J. E.; Ritson, D. J.; Zhang, F.; Lombardo, C. M.; Haider, S.; Oldhama, N.;
Neidle, S. Org. Biomol. Chem. 2010, 8, 2926–2930.
22. Mongin, O.; Porrès, L.; Katan, C.; Pons, T.; Mertz J.; BlanchardꢁDesce, M.
Tetrahedron Lett., 2003, 44, 8121ꢁ8125.
22
ACS Paragon Plus Environment