Synthesis and Structure of 1,2-Dimethylene[2.10]metacyclophane and Its Conversion into Chiral [10]Benzenometacyclophanes

Article abstract of DOI:10.1002/ejoc.201601647

Bromination of 5,21-di-tert-butyl-8,24-dimethoxy-1,2-dimethyl[2.10]metacyclophan-1-ene (MCP-1-ene; 1) with benzyltrimethylammonium tribromide exclusively afforded 1,2-bis(bromomethyl)-5,21-di-tert-butyl-8,24-dimethoxy[2.10]MCP-1-ene (2). Debromination of

Full text of DOI:10.1002/ejoc.201601647

A Journal of
Accepted Article
Title: Synthesis and structure of 1,2-dimethylene[2.10]metacyclophane
and its conversion to chiral [10]benzenometacyclophanes
Authors: Thamina Akther, Md. Monarul Islam, Taisuke Matsumoto,
Junji Tanaka, Pierre Thuéry, Carl Redshaw, and Takehiko
Yamato
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201601647
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10.1002/ejoc.201601647
European Journal of Organic Chemistry
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Synthesis and structure of 1,2-dimethylene[2.10] metacyclophane
and its conversion to chiral [10]benzenometacyclophanes
Thamina Akther,[a] Md. Monarul Islam,[a], [b] Taisuke Matsumoto,[c] Junji Tanaka,[c] Pierre Thuéry,[d] Carl
Redshaw,[e] and Takehiko Yamato*[a]
Abstract: Bromination of 5,21-di-tert-butyl-8,24-dimethoxy-1,2-
dimethyl[2.10]metacyclophan-1-ene (MCP-1-ene) with
compounds, but few researchers have investigated the
flexible conformations of the synthesized macrocyclic
compounds and their conversion into rigid structures to
provide as suitable platforms for diverse complexation
experiments.4 Our interest in this field stems from
investigations of cyclic diynes in which two double bonds
were part of the ring system.5
1
benzyltrimethylammonium tribromide exclusively afforded 1,2-
bis(bromomethyl)-5,21-di-tert-butyl-8,24-dimethoxy[2.10]MCP-1-ene
2. Debromination of 2 with Zn and AcOH in CH2Cl2 solution at room
temperature for 24 h produced the identical dimethylene[2.10]MCP 7
in 92% yield, which is a stable solid compound. Subsequently,
compound 7 was reacted with dimethyl acetylenedicarboxylate
(DMAD) to provide 1,2-(3',6'-dihydrobenzo)-5,21-di-tert-butyl-8,24-
dimethoxy[2.10]MCP-4',5'-dimethylcarboxylate 8 in good yield. Diels-
Alder adduct 8 was converted to a novel and inherently chiral areno-
The syntheses of [n]MCP-diynes and conversion of the
propargylic moieties into allenic moieties in the presence of
strong bases was reported by Ramming and Gleiter.6
Kawase and co-workers described the synthetic procedure
for [2.n]MCP-ynes by bromination–dehydrobromination of
the corresponding MCP-enes, which are considerably
strained with bent triple bonds.7 On the other hand, although
the parent [2.2]MCP was first explored as early as in 1899 by
Pellegrin,8 the synthesis of syn-[2.2]MCP was achieved 85
years later. A successful preparative method for syn-
[2.2]MCP has been introduced which uses (arene)
chromium–carbonyl complexation at low temperature.9
Further, Boekelheide10 and Staab11 have succeeded in
synthesizing intra–annularly substituted [2.2]MCP, respec-
tively. For alkene-containing MCPs, the McMurry reaction
holds is a promising one-step pathway, but this reaction route
has a preference for coupling two identical functional groups
to facilitate the synthesis of the direct cyclophanes
precursors.12–16
However, reports on the synthesis of [2.n]MCP-dienes
containing long carbon chain as well as their chirality have
not yet been published. Inherent chirality is a property of
molecules whose lack of symmetry does not originate from a
classic stereogenic element, but is rather the effect of the
presence of curvature within a structure that would be
lacking of symmetry axes in any two-dimensional
representation.17 A large number of inherently racemic chiral
macromolecules have been reported, and some of them
have been resolved into enantiomerically pure form.17
Applications of inherently chiral molecules in molecular
recognition18 and asymmetric catalysis19 have been
reported.
bridged
dimethoxy[2.10]MCP-4',5'-dimethylcarboxylate
with dichlorodicyano-p-benzoquinone
9
by
aromatization
(DDQ),
possessing C1 symmetry. Also a new type of N-phenyl-maleimide
substituted 1,2-(3',6'-dihydrobenzo)-5,21-di-tert-butyl-8,24-dimethoxy
[2.10]MCP-4',5'-N-phenylmaleimide 10 was synthesised from 7 via
treatment with N-phenylmaleimide in toluene at 110°C followed by
aromatization with DDQ. Single crystal X-ray analysis of 9 revealed
the adoption of a syn-isomer.
Introduction
Cyclophanes are a class of compound that has undergone
extensive studies in recent decades.1 Metacyclophanes (=
MCPs) have been known for nearly 45 years,2 with the short
chain (n = 4–6) members having attracted the appreciation
of chemists as exemplary compounds to test the limits of
bending aromatic rings.3 Some of the reports focus on
synthesis and conformational studies of the macrocyclic
[a]
T. Akther, Dr. M. M. Islam, Dr. Prof. T. Yamato
Department of Applied Chemistry, Faculty of Science and
Engineering
Saga University
Honjo-machi 1, Saga 840-8502 Japan
E-mail: yamatot@cc.saga-u.ac.jp
Dr. M. M. Islam
[b]
[c]
Chemical Research Division,
Our group has published a series of papers describing
McMurry coupling reactions of tethered dialdehydes and
ketones, in which the restrain length ranged from 2 to 10 and
every accessible position on the aromatic rings was at some
point substituted.20 In this paper, we describe the first prepa-
ration of inherently chiral areno–bridged [2.10]MCP by using
a bromination reaction and Diels–Alder reactions followed by
aromatization with DDQ.
Bangladesh Council of Scientific and Industrial Research (BCSIR),
Dhanmondi, Dhaka-1205, Bangladesh
Dr. T. Matsumoto, Dr. J. Tanaka
Institute of Materials Chemistry and Engineering,
Kyushu University,
6-1, Kasugakoen, Kasuga 816-8580, Japan
Dr. P. Thuéry
NIMBE, CEA, CNRS, Université Paris-Saclay,
CEA Saclay, 91191 Gif-sur-Yvette, France
Dr. Prof. C. Redshaw
[d]
[e]
School of Mathematics and Physical Sciences
The University of Hull
Cottingham Road, Hull, Yorkshire HU6 7RX, UK
Results and Discussions
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Very recently, we reported a synthesis and conformational
study of [2.n]MCP-1-enes and the reaction with BBr3 to afford
tetrahydrobenzofuranophane.21 We also reported inherent
chirality in the MCP structure.22 As part of our continued interest
in the synthesis of inherently chiral MCPs, we undertook a
systematic investigation of the starting compound 5,21-di-tert-
butyl-8,24-dimethoxy-1,2-dimethyl[2.10]MCP-1-ene 1 containing
both decane and ethylene bridges, which were synthesized from
1,10-bis(5-tert-butyl-2-methoxylphenyl)decane in four steps by
using the tert-butyl group as a positional protective group on the
aromatic ring.23 Formylation of 1,10-bis(5-tert-butyl-2-methoxyl-
phenyl)decane with dichloromethyl methyl ether (Cl2CHOCH3) in
the presence of titanium tetrachloride in CH2Cl2 for 2 h afforded
bis(bromomethyl)-5,21-di-tert-butyl-8,24-dimethoxy[2.10]MCP-1-
ene 2 in 80% yield (Scheme 1). Here we use BTMA-Br3 because
it is easy to handle and a mild brominating reagent allowing us to
control the reaction pathway. No bromination of compound 2 at
the alkene bridge (double bond) was observed. This result is
entirely different from the bromination of the corresponding
[2.10]MCP-1-ene which afforded the cis–addition product (to the
bridging double bond).25 The presumed mechanism involves the
initial formation of the bromonium ion followed by consecutive
deprotonation and HBr elimination to afford diene 2.26,27
1,10-bis(5-tert-butyl-3-formyl-2-methoxyphenyl)decane.
The
bisformylated compound was converted to the bis-alcohol
derivative in 87% yield by reaction with the Grignard reagent
MeMgI in ether and then oxidation with pyridinium chlorochromate
(PCC) to afford the bisacetyl derivative in 71% yield, which was
subjected to reductive coupling by the McMurry reaction following
the improved Grützmacher’s procedure16 to afford the desired
compound 1 in 90% yield.23
None of the corresponding anti-isomer was observed under
the conditions used. The structure of 1 was confirmed by
comparing the melting point and 1H NMR spectroscopic data with
the reported data. Previously we failed to get single crystal of
compound 1, although we tried several times using different
conditions. However, we have now succeeded in growing single
crystals by slow evaporation of a saturated dichloromethane
solution. The conformation was assigned by using both single
crystal X-ray crystallography and 1H NMR (CDCl3, 300 MHz)
spectroscopic analysis. The 1H NMR (CDCl3, 300 MHz) spectrum
of 1 exhibits a single peak at δ 3.65 ppm for the methoxy protons
indicating that the two methoxy groups are outside of the two
benzene rings (syn-conformation) and methoxy protons appear at
the normal position as for anisole. The aromatic protons appear
in the high field region at δ 6.77 & 6.85 ppm due to shielding by
the adjacent ring current; this is a common consequence of face-
to-face benzene rings due to the syn-conformation.24 The crystal
structure was found to belong to the monoclinic crystal system
with space group P 21/n (SI Table S1) and is fully consistent with
the 1H NMR spectroscopic data for compound 1.
Scheme 1. Synthesis of syn-1,2-bis(bromomethyl)-5,21-di-tert-butyl-8,24-
dimethoxy[2.10]MCP 2.
On changing the amount of BTMA-Br3 used in this reaction
there is the possibility of recovering the starting material. For
example, when the compound 1 was treated with 1.2 equiv. of
BTMA-Br3 at room temperature for 24 h, 2 was formed in 30%
yield with 60% recovery of compound 1 (Table 1). When the ratio
was increased to around 2.4 equiv. under the same reaction
conditions, the yield of compound 2 increased to about 65% and
became 80% when employing 4.4 equiv. of BTMA-Br3. Here,
isolated yields are decreased in terms of the purification process.
Table
1.
Bromination
of
5,21-di-tert-butyl-8,24-dimethoxy-1,2-
dimethyl[2.10]MCP-1-ene 1.
The X-ray structure (CCDC no: 908365) of 1 (Figure 1) clearly
demonstrates that 1 exists as the syn-conformer in the solid state
and that the two methoxy groups lie on the correlative side of the
18 membered inner ring, which contains the long bridging C19–
C27 chain pointing toward the outer direction thereby minimizing
steric repulsion with the bridge chain. The selected bond lengths
of C27–C28 and C1–C27 in the decamethylene chains and C3–
C12 and C16–C13 in the ethylenic chains have typical values at
1.53, 1.50, 1.50 and 1.49 Å, respectively. The length of the double
bond in C12–C13 is 1.34 Å, which is similar to that of ethylene.
The bond angles defined by C3–C12–C13 and C12–C13–C16 are
123.6(2)° and 122.7(2)°, reveal that compound 1 displays a non-
distorted conformation. The two benzene rings of 1 slightly deviate
from planarity. The intramolecular distances of C3–C16, C2–C17,
C5–C20, C4–C21, C1–C18, C6–C19 are 2.98, 4.18, 5.07, 3.59,
5.67 and 6.04 Å.
Products yield [%]a
BTMABr3
[equiv.]
Run
1
2
Recovery of 1
1.2
30
65
2
2.4
65
80
30
20
3

a Isolated yields are shown in parentheses.
The structure of product 2 was estimated on the basis of
elemental analyses and spectral data. The mass spectral data for
diene 2 (M+ = 676, 678 and 680) strongly supported a dibominated
1
structure. The H NMR spectrum of 2 disclosed a singlet for the
methoxy protons at δ 3.65 ppm as well as resonances at δ 6.67
and 6.91 ppm (J = 2.4 Hz) for the two protons of the aromatic rings.
Previously reported17b 1,2-bis(bromomethyl)[2.3]MCP-1-ene
exhibited a lower-field shift for the methoxy protons at δ 3.22 ppm
along with δ 6.99 and 7.19 ppm (J = 2.4 Hz) for the two aromatic
Bromination of 1 with 4.4 equiv. of benzyltrimethyl- ammonium
tribromide (BTMA-Br3)25 in dry CH2Cl2 solution at room
temperature for 24
h
afforded the corresponding 1,2-
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10.1002/ejoc.201601647
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protons because of the short carbon chain length. The methylene
protons of the bromomethyl group were observed as a doublet at
δ 4.52 and 4.84 ppm (J = 10.0 Hz). Thus, the introduction of the
bromo group at the methyl group might restrict the rotation
throughout the single bond of C–CH2Br, thereby causing the
methylene protons to be in a diasterotopic environment.
chemical conversion, compound 4 is assigned to the structure,
1,2-bis(acetoxymethyl)-5,21-di-tert-butyl-8,24-
dimethoxy[2.10]MCP-1-ene 4.
Elemental analysis and spectral data were used to evaluate
the structure of compound 5. The structure of compound 5 was
1
confirmed by the H NMR spectrum. The methoxy protons were
detected by a single peak at δ 3.74 ppm, and additional peaks at
δ 6.77 and 6.95 ppm (J = 2.4 Hz) for the two aromatic protons.
The methylene protons of the hydroxyl group were observed as a
doublet at δ 4.50 and 4.80 ppm (J = 12.6 Hz). Using the spectral
data, compound
5 is assigned to the structure syn-1,2-
bis(hydroxymethyl)-5,21-di-tert-butyl-8,24-dimethoxy[2.10]MCP-
1-ene 5.
Scheme 2. Synthetic strategy for debromination of 1,2-bis(bromomethyl)-5,21-
di-tert-butyl-8,24-dimethoxy[2.10]MCP-1-ene 2 via diol 6.
To synthesize the diene body in the dehydration reaction for
the Diels-Alder reaction, the reduction reaction of the double
bonds does not proceed. Interestingly, treatment of 2 with Zn and
dropwise addition of AcOH in dry CH2Cl2 solution at room
temperature for 24 h afforded the identical 1,2-dimethylene[2.10]
MCP 7 in 75% yield (Scheme 3). This type of reaction has been
widely used to eliminate a bromine group to form a double bond.
Figure 1. Single-crystal structure of 1 showing (a) the side view (b) the top view.
Thermal ellipsoids are drawn at the 50% probability level. All hydrogen atoms
are omitted for clarity.
Treatment of 1,2-bis(bromomethyl)-5,21-di-tert-butyl-8,24-
dimethoxy[2.10]MCP-1-ene 2 with silver acetate in acetic acid at
100 °C for 24 h resulted in the analogous acetate compound 4 in
78% yield. Compound 4 was further converted to the 1,2-
bis(hydroxymethyl) derivative 5 in quantitative yield by hydrolysis
with KOH in presence of EtOH for 2 h in 72% yield (Scheme 2).
After that, hydrogenation of compound 5 in presence of 10% Pd
/C for 24 h failed to afford the expected compound 6. Only the
starting compound 5 was recovered. This result might be due to
the cyclophane structure of compound 5. However, the
explanation of the present result is pending definition.
The cyclic dimeric structure was strongly supported by the
mass spectral data for compound 4 (M+ = 634). The 300 MHz 1H
NMR spectrum of 4 in CDCl3 showed a single peak at δ 3.68 ppm
for the methoxy protons together with δ 6.79 and 6.95 ppm (J =
2.4 Hz) for the two aromatic protons. The methylene protons of
the acetate group were observed as a doublet at δ 5.14 and 5.20
ppm (J = 12.6 Hz). On the basis of the spectral data and the
Scheme 3. Synthesis of syn-1,2-dibenzo-5,21-di-tert-butyl-8,24-dimethoxy
[2.10]MCP-4′,5′-dimethylcarboxylate 9.
The structure of the diene obtained in the present work was
determined from the elemental analyses and spectral data. The
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300 MHz 1H NMR spectrum of 7 in CDCl3 exhibited a doublet at δ
6.92 and 7.05 ppm for the two protons of the aromatic rings. The
exo-methylene protons of the ethano-bridge were displayed as
broad singlets at δ 5.53 and 5.69 ppm, and the protons of the
methoxy group were observed at δ 3.64 ppm. The decamethylene
bridge protons gave rise to a abstruse signal pattern as predicted
for a rigid [2.10]MCP. The protons of the benzylic CH2 group were
observed as two multiplets at δ 2.11–2.38 and 2.73–2.90 ppm,
which were additionally split by coupling with the protons of the
central CH2 groups. This central CH2 groups was also observed
as multiplets centered at δ 0.91–1.15 ppm. It was also observed
that these methylene peaks did not merge up to 120 °C in CDBr3.
These findings suggested that the introduction of two double
bonds of the ethano-bridge might inhibit the syn–syn
conformational flipping of 1,2-dimethylene[2.10]MCP 7 above this
temperature which would exchange HA and HB of each CH2 group.
These perceptions suggested that the introduction of two double
bonds of the ethano–bridge might restrict the syn-conformation of
1,2-dimethylene[2.10]MCP 7.
Compound 7 is a stable solid and easy to purify. Compound 7
is conveniently employed in the reaction with dimethyl
acetylenedicarboxylate (DMAD) to provide 8 in good yield. Diels-
Alder adduct 8 was converted to areno–bridged [2.10]MCP 9 by
aromatization with dichlorodicyano-p-benzoquinone (DDQ). The
present Diels–Alder reaction of 7 with DMAD was completed
within 24 h in toluene at reflux. Thus, the Diels–Alder reactivity of
compound 7 exceeds that of 2,3-diphenyl-1,3-butadiene. This
result suggests that the energy of the fixed s-cis conformation in7
in the ground and transition state might lower the Diels–Alder
barriers due to the inflexibility of the MCP ring. The Diels–Alder
reaction of 7 with suitable dienophiles followed by aromatization
can be used to prepare a range of areno–bridged [2.n]MCPs.
Owing to the intrinsic structural features, we envisaged that
MCP 9 would led to inherent chirality macrocycles due to
intramolecular overcrowding like helicenes28 or MCPs.29 The
synthesis and optical resolution of inherently chiral MCPs are
challenging, but because of their potential uses in supramolecular
chemistry, they remain attractive.30 The design and synthesis of
inherently chiral MCPs with novel structures therefore is a topic of
great significance.
The structure of product 9 was determined by spectroscopic
methods (1H NMR and 13C NMR), mass spectrometry and
elemental analyses. The cyclic dimeric structure was confirmed
by the mass spectral data for compound 9 (M+ = 657). The 300
MHz 1H NMR spectrum of 9 in CDCl3 exhibited a single peak at δ
3.68 ppm for the methoxy protons together with δ 6.84 and 7.05
ppm (J = 2.4 Hz) for the two aromatic protons. On the basis of the
spectral data and the chemical conversion, compound 9 is
assigned to the structure, 1,2-dibenzo-5,21-di-tert-butyl-8,24-
dimethoxy[2.10]MCP-4',5'-dimethylcarboxylate (9).
Figure 3. Schematic diagram of M-9 (left side) and P-9 (right side).
In anticipation of future investigations into the ability of MCPs
to be employed as chiral catalysts and ligands, efforts were made
to access the solid-state structures and also the high-resolution
NMR spectral data. Inherent chirality is a particular feature
Figure 2. Single-crystal structure of 9 showing (a) the side view (b) the top view.
Thermal ellipsoids are drawn at the 50% probability level. All hydrogen atoms
are omitted for clarity.
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associated with some MCPs and 9 is predicted to have a plane of
chirality. This is because it has two different types of substituents
and bridged linkages which are fixed in a C1 symmetrical structure
and does not sustain a conformational change at or near ambient
temperature.
Electronic Supplementary Information (ESI) available: Details
of single-crystal X-ray crystallographic data. 1H, 13C NMR and MS
spectra of 1 to 10.
Compound 9 was crystallized by the slow, room temperature
evaporation of a dichloromethane solution, into the space group
P-1. Interestingly, the X-ray analysis disclosed that areno–bridged
9 adopts helical chirality, yet surprisingly, the dihedral angle of the
Acknowledgements
We would like to thank the OTEC at Saga University for financial
support. This work was performed under the Cooperative
Research Program of “Network Joint Research Center for
Materials and Devices (Institute for Materials Chemistry and
Engineering, Kyushu University)”. CR thanks the EPSRC for a
travel award.
arylenes connected by the phenyl unit is 33.98°. As
a
consequence, the compound is chiral and the M– and P– isomers
are packed alternatively in the crystal as depicted schematically
in Figure 3 (CCDC no: 908368).
The removal of the external substituted COOMe group in
compound
9 is more preferable than that of the internal
Keywords: 1,2-Dimethylene[2.10]metacyclophane • Chirality •
Diels–Alder reaction • Conformation studies
substituted OMe group. However, this process required very
high temperatures and also prolonged reaction times. In
order to improve the reaction conditions to more suitable
milder conditions, the reaction pathway was initiated from
[1]
a) Cyclophanes (Eds.: P. M. Keehn and S. M. Rosenfield), Academic
Press: New York, 1983, vol. 1, chapter 6, p. 428; b) F. Vögtle, Cyclophane-
Chemistry, Wiley: Chichester, 1993.
1,2-dimethylene[2.10]MCP 7. Compound 7 was treated with
N-phenylmaleimide with toluene at 110 °C for 24 h to
synthesized compound 10 (53% yield) as illustrated in
Scheme 4.
[2]
a) D. J. Cram, Cyclophanes, Vol. 1.P. M. Keehn and S. N. Rosenfeld,
Eds., Academic Press, New York, 1983, 1–21; b) L. K.Doamekpor, V. K.
Nartey, R. K. Klake, T. Yamato, International Journal of Organic Chemistry
2012, 2, 152–158.
[3]
[4]
V. V. Kane, W. H. de Wolf, F. Bickelhaupt, Tetrahedron 1994, 50, 4575.
L. K. Doamekpor, R. K. Klake1, V. K. Nartey, T. Yamato, O. Gyamfi, D.
Adotey, International Journal of Organic Chemistry 2015, 5, 126–135.
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a) T. Kawase, N. Ueda, H. R. Darabi, M. Oda, Angew. Chem. 1996, 108,
1658; Angew. Chem. Int. Ed. Engl. 1996, 35, 1556; b) T. Kawase, H. R.
Darabi, M. Oda, Angew. Chem. 1996, 108, 2803; Angew. Chem. Int. Ed.
Engl. 1996, 35, 2664; c) T. Kawase, N. Ueda, M. Oda, Tetrahedron Lett.
1997, 38, 6681.
Scheme 4. Synthesis of 1,2-dibenzo-5,21-di-tert-butyl-8,24-dimethoxy[2.10]
MCP-4′,5′-p-dimethylbenzylamine 10.
[8]
[9]
M. Pelligrin, Recl. Trav. Chim. Pays-Bas Belg. 1889, 18, 458.
R. H. Mitchell, T. K. Vinod, G. W. Bushnell, J. Am. Chem. Soc. 1985, 107,
3340.
1
The structure of 10 was characterized by H and 13C NMR,
[10]
a) R. H. Mitchell, V. Boekelheide, J. Am. Chem. Soc. 1974, 96, 1547; b)
Y.-H. Lai, H.-L. Eu, J. Chem. Soc., Perkin Trans. 1 1993, 233.
H. A. Staab, W. R. K. Riebel, C. Krieger, Chem. Ber. 1985, 118, 1230.
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1978, 43, 3255; b) J. E. McMurry, Acc. Chem. Res. 1983, 16, 405; c) J. E.
McMurry, G. J. Haley, J. R. Matz, J. C. Clardy, G. V. Duyne, J. Am. Chem.
Soc. 1984, 106, 5018; d) J. E. McMurry, Chem. Rev. 1989, 89, 1513; e)
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mass spectra and elemental analysis. The cyclic dimeric structure
was strongly supported by the mass spectral data for compound
[11]
[12]
1
10 (M+ = 689). The H NMR spectrum of 10 (300 MHz, CDCl3)
exhibits a single peak at δ 3.64 ppm for the methoxy protons
together with six aromatic protons appeared as doublets at δ 6.69,
6.89 and a singlet at δ 7.33 ppm, respectively, which are
associated with the unsymmetrical structure of 10.
[13]
[14]
[15]
[16]
[17]
Conclusions
H. -F. Grützmacher, E. Neumann, Chem. Ber. 1993, 126, 1495.
a) V. Böhmer, D. Kraft, M. Tabatabai, J. Incl. Phenom. Mol. Recog. Chem.
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Chem. 2011, 71, 35–56; c) S.-Y. Li, Y.-W.Xu, J.-M. Liu, C.-Y. Su, Int. J. Mol.
Sci. 2011, 12, 429–455; d) M. J. Mclldowie, M. Mocerino, M. I. Ogden,
Supramol. Chem. 2010, 22, 13–39.
We have described a simple and effective method for the
synthesis of areno-bridged [2.10]MCP 9 by successive Diels-
Alder reaction from 1,2-dimethylene[2.10]MCP 7, and also its
chiral conformation. To explore the rates of conformational
behaviour of the described [2.10]MCPs, a series of electrophilic
substitution reactions such as bromination, acylation and
hydroxylation reactions of [2.10]MCPs were studied. Further
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[b]
A simple and effective method for the
synthesis of areno-bridged
[2.10]MCPs by successive Diels-Alder
reaction starting from 1,2-
T. Akther,[a] M. Islam,[a],
T.
Matsumoto,[c] J. Tanaka,[c] P. Thuéry,[d] C.
Redshaw[e] and T. Yamato*[a]
Page No. – Page No.
dimethylene[2.10]MCP, together with
their chiral structures are discussed.
Synthesis and structure of 1,2-
dimethylene[2.10]metacyclophane
and
its
conversion
to
chiral
[10]benzenometacyclophanes
Keywords:
1,2-
Dimethylene[2.10]metacyclophane/
Conformation studies/ Diels-Alder
reaction/ Chirality
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Author(s), Corresponding Author(s)*
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Title
Text for Table of Contents
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