One-pot synthesis of cyclophane-type macrocycles using manganese(iii)- mediated oxidative radical cyclization

Article abstract of DOI:10.1039/c0ob00683a

Cyclophane-type macrocyclic compounds from 21 to 56 members having two fused dihydrofuran rings were synthesized by the manganese(iii)-mediated oxidation of terminal dienes with bis(3-oxobutanoate)s containing aromatics. The reaction detail, characterization and reaction pathways are described. The Royal Society of Chemistry 2011.

Full text of DOI:10.1039/c0ob00683a

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PAPER
One-pot synthesis of cyclophane-type macrocycles using
manganese(III)-mediated oxidative radical cyclization†
Yosuke Ito, Yuichi Tomiyasu, Takahiro Kawanabe, Keisuke Uemura, Yuu Ushimizu and Hiroshi Nishino*
Received 7th September 2010, Accepted 9th November 2010
DOI: 10.1039/c0ob00683a
Cyclophane-type macrocyclic compounds from 21 to 56 members having two fused dihydrofuran rings
were synthesized by the manganese(III)-mediated oxidation of terminal dienes with
bis(3-oxobutanoate)s containing aromatics. The reaction detail, characterization and reaction pathways
are described.
went the manganese(III)-oxidation to afford the corresponding
Introduction
cyclophane-type macrocyclic compound. In this paper, we report
The synthesis of cyclophanes remains an attractive area for investi-
the convenient synthesis and structure determination of the
gation from the standpoint of their constitutive and physicochem-
cyclophane-type macrodiolides.
ical properties.1,2 In particular, macrocyclic compounds reveal
supramolecular behaviors such as molecular recognition,3 anion
binding,4 metal ion transport,5 enzymatic catalysis,6 chemical
switching,7 etc. Therefore, many chemists have been interested
in the synthesis and the properties of macrocyclic compounds
for more than five decades.8 In recent years, we have developed
various manganese(III)-based oxidative cyclization reactions.9 In
connection with our study, we found the straightforward access to
the functionalized large ring compounds which were obtained by
the oxidation of oligomethylene di(3-oxobutanoate)s10 or N,N¢-
oligomethylenebis(3-oxobutanamide)s11 with manganese(III) ac-
etate in the presence of terminal alkadienes. The reaction gave
macrodiolides or macrocyclic diamides containing 11 to 62
members in good yields.10,11 We also found the intramolecular
macrocyclization of 2-propenoxyoligomethylene 3-oxobutanoates
and N-(w-alkenyl)-3-oxobutanamides, giving the corresponding
macrolides and macrocyclic amides from 8 to 26 members
in good yields.12 These reactions prompted us to investigate
the synthesis of cyclophane-type macromolecules using ter-
minal dienes and bis(3-oxobutanoate)s containing aromatics,
since some naturally occurring macrocyclic compounds are also
known13 and the manganese(III)-enolate complex prepared in situ
must undergo a specific reaction during the macrocyclization.10a
In fact, a mixture of 1,1,10,10-tetraphenyl-1,9-octadiene and
p-phenylenebis(oxapropyl) bis(3-oxobutanoate) initially under-
Results and Discussion
Reaction of alkadienes 1 with bis(3-oxobutanoate)s 2 containing
aromatics in the presence of manganese(III) acetate
1,9-Octadiene 1(6) was prepared by the Grignard reaction
of diethyl octanedioate with phenylmagnesium bromide fol-
lowed by dehydration. Bis(3-oxobutanoate) containing aromatics,
2(1)-para, was synthesized by the reaction of hydroquinone with
bromoacetate under basic conditions, followed by reduction
with lithium aluminium hydride14 and then esterification with a
diketene.13
With the diene 1(6) and the bis(3-oxobutanoate) 2(1)-para in
hand, we examined the reaction of 1(6) with 2(1)-para in the
presence of manganese(III) acetate. Since it was recognized that the
dissolved molecular oxygen influenced the manganese(III)-based
oxidation,10b the mixture was degassed under reduced pressure
using an ultrasonicator, followed by displacement with argon
before carrying out the reaction. The reaction was carried out
using a stoichiometric amount of the oxidant under high dilution
conditions to give the cyclic compound 3(6)(1)-para together with
the unchanged 1(6) (Scheme 1 and Table 1, Entry 1). Since the
diene 1(6) was recovered, an excess amount of the oxidant and
Department of Chemistry, Graduate School of Science and Technol-
ogy, Kumamoto University, Kurokami 2-39-1, Kumamoto, 860-8555,
Japan. E-mail: nishino@sci.kumamoto-u.ac.jp; Fax: (+81)-96-342-3374;
Tel: (+81)-96-342-3374
† Electronic supplementary information (ESI) available: The synthetic
procedures and spectroscopic data of the substrates 1(m), 1(O), 2(n)-arom,
2(CH )y-arom, 4(m), 6, and 8 with references; the X-ray data collection and
2
processing parameters of [22]paracyclophane 3(8)(1)-para. CCDC reference
number CCDC 769197. For ESI and crystallographic data in CIF or other
electronic format see DOI: 10.1039/c0ob00683a
Scheme 1 Reaction of diene 1(6) with bis(3-oxobutanoate) 2(1)-para in the
presence of manganese(III) acetate.
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Table 1 Reaction of octadiene 1(6) with bis(3-oxobutanoate) 2(1)-para in
Entries 1–14). Although the tendency might be assigned to the
symmetric and/or steric problem of 3(m)(n)-meta, we do not have
any explanations at this moment. The use of 4-oxaheptadiene
1(O) also afforded 3(O)(n)-arom in low yields (Table 2, Entries 15–
20). Because the oxamethylene chain of 1(O) would be much
shorter than that of the reactant bis(3-oxobutanoate)s 2(n)-arom,
the intramolecular cyclization would probably be suppressed. The
biphenyl-inserted bis(3-oxobutanoate)s 2(n)-biphen also gave the
corresponding cyclophanes 3(m)(n)-biphen containing between 28
and 50 members in low yields (Table 2, Entries 21–29). It seemed
that the 2(n)-arom containing the biphenyl chain might be more
rigid than that including the phenylene chain. The oxamethylene
tethered 2(n)-arom would undergo an over-oxidation with man-
ganese(III) acetate since the 2(n)-arom, having the successive ether
chain, might be much more sensitive to the metal oxidant than
the presence of manganese(III) acetatea
1
(6)/2(1)-para/
Entry Mn(III)b
AcOH/ mL Time/ min 3(6)(1)-para %c Rec. 1(6)
%
1
2
3
4
5
1 : 1.3 : 4
1 : 1.3 : 4
1 : 1.3 : 7
1 : 1.3 : 7
1 : 1.3 : 10
200
100
100
50
150
15
30
90
150
30
51
54
46
43
14
18
—
5
100
—
a The reaction with 1(6) (0.2 mmol) was carried out in glacial acetic acid at
100 ◦C under an argon atmosphere. b Molar ratio. c Isolated yield based
on the amount of 1(6) used.
the slightly concentrated conditions were adopted and the desired
cyclic compound 3(6)(1)-para was obtained with a 54% yield (Entry
3). A greater excess of the oxidant and concentrated conditions
led to a decrease in the yield of 3(6)(1)-para (Entries 4 and 5).
In order to examine other combinations of the terminal alka-
dienes and bis(3-oxobutanoate)s containing aromatics, alkadienes
1(m) (m = 8,16) were prepared by a manner similar to that of the
octadiene 1(6), and 4-oxaheptadiene 1(O) was synthesized by the
Reformatsky reaction of benzophenone with ethyl bromoacetate,
followed by its reduction and then condensation. Other bis(3-
oxobutanoate)s containing aromatics 2(n)-arom (n = 1,2,3) were
also prepared by the Williamson ether synthesis of the corre-
sponding phenolic diols with (chloroethoxy)ethanols followed by
esterification with a diketene.14 When the reaction of the dienes
1(m) and 1(O) with bis(3-oxobutanoate)s 2(n)-arom was carried out
under the optimized reaction conditions (Scheme 2), the desired
cyclic compounds, 3(m)(n)-arom and 3(O)(n)-arom, were produced in
the yields shown in Table 2.
the inactive methylene tethered 2(CH )y-arom, and therefore, the use
2
of the methylene tethered 2(CH )y-arom instead of the oxamethylene
2
tethered 2(n)-arom led to the good yield of the cyclophanes 3(m)(CH
arom (Table 3).
-
)y
2
Characterization of 3(6)(1)-para
The structure of 3(6)(1)-para was characterized by a spectroscopic
method. All the peaks of the 1H NMR and the 13C NMR spectrum
were correlated by the HMQC spectrum. The 1H NMR spectrum
showed the existence of two dihydrofurans and a hydroquinone
part at d 3.67 (2H, t, J = 5.4 Hz), 2.29 (6H, s), and 6.74
(4H, s) ppm, assigned to a methine and a methyl proton of
the dihydrofuran and aromatic protons of the hydroquinone,
respectively. The 13C NMR spectrum also revealed two sp2 carbons
at d 165.5 and 107.7, a methine carbon at d 48.9 and a quaternary
carbon at d 95.3 ppm due to the dihydrofuran. These peaks,
as well as an ester carbonyl carbon at 167.0 ppm, appeared
as two slightly different peaks, due to the diastereomixture of
the cyclic compound that contained two asymmetric carbons.10a
Interestingly, eight protons of the methylene chain were extremely
shifted upfield at d 0.58–0.31 (4H, m) and 0.08–-0.23 (4H, m)
ppm because of the strong ring current effect just below the
hydroquinone group. These data supported the fact that the ter-
minal diene 1(6) must undergo oxidative macrocyclization with the
We also applied the reaction to methylene-tethered bis(3-
oxobutanoate)s 2(CH )y-arom (y = 6,8) which were prepared in a
2
manner similar to that of the 2(n)-arom (Scheme 3). As a result, the
corresponding cyclic compounds 3(m)(CH )y-arom were obtained in
2
the yields shown in Table 3.
Both reactions gave cyclophane-type macrocyclic compounds
containing between 21 and 50 members, having two-fused di-
hydrofurans in moderate yields. The yield of 3(m)(n)-meta was
slightly lower than those of 3(m)(n)-ortho and 3(m)(n)-para (Table 2,
Scheme 2 Reaction of dienes 1(m) and 1(O) with bis(3-oxobutanoate)s 2(n)-arom in the presence of manganese(III) acetate.
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Table 2 Reaction of terminal dienes 1(m) and 1(O) with bis(3-oxobutanoate)s 2(n)-arom in the presence of manganese(III) acetatea
Entry
Diene
Butanoate
1/2/Mn(III)b
Time/ min
Cyclophane (%)c
Ring size
1
2
3
4
5
6
7
8
1(6)
1(6)
1(6)
1(6)
1(6)
1(6)
1(8)
1(8)
1(8)
1(8)
1(8)
1(16)
1(16)
1(16)
1(O)
1(O)
1(O)
1(O)
1(O)
1(O)
1(6)
1(6)
1(6)
1(8)
1(8)
1(8)
1(16)
1(16)
1(16)
2(1)-para
1 : 1.3 : 7
1 : 1.3 : 7
1 : 1.3 : 7
1 : 1.3 : 7
1 : 1.3 : 7
1 : 1.3 : 7
1 : 1.3 : 8
1 : 1.3 : 7
1 : 1.3 : 7
1 : 1.3 : 8
1 : 1.3 : 7
1 : 1.3 : 8
1 : 1.3 : 8
1 : 1.3 : 7
1 : 1.3 : 7
1 : 1.3 : 7
1 : 1.3 : 7
1 : 1.3 : 7
1 : 1.3 : 7
1 : 1.3 : 7
1 : 1.3 : 7
1 : 1.3 : 7
1 : 1.3 : 7
1 : 1.3 : 7
1 : 1.3 : 7
1 : 1.3 : 7
1 : 1.3 : 7
1 : 1.3 : 7
1 : 1.3 : 7
30
60
80
60
70
70
45
60
60
20
60
40
60
60
20
80
90
80
80
80
75
35
30
90
30
40
30
30
30
3(6)(1)-para (54)
3(6)(2)-ortho (58)
3(6)(2)-meta (33)
3(6)(2)-para (64)
3(6)(3)-ortho (42)
3(6)(3)-para (46)
3(8)(1)-para (62)
3(8)(2)-ortho (60)
3(8)(2)-meta (33)
3(8)(2)-para (52)
3(8)(3)-para (42)
3(16)(1)-para (44)
3(16)(2)-para (38)
3(16)(3)-para (43)
3(O)(1)-para (23)
3(O)(2)-ortho (30)
3(O)(2)-meta (22)
3(O)(2)-para (29)
3(O)(3)-ortho (19)
3(O)(3)-para (20)
3(6)(1)-biphen (28)
3(6)(2)-biphen (41)
3(6)(3)-biphen (33)
3(8)(1)-biphen (35)
3(8)(2)-biphen (43)
3(8)(3)-biphen (22)
3(16)(1)-biphen (43)
3(16)(2)-biphen (23)
3(16)(3)-biphen (30)d
24
28
29
30
34
36
26
30
31
32
38
34
40
46
21
25
26
27
31
33
28
34
40
30
36
42
38
44
50
2(2)-ortho
2(2)-meta
2(2)-para
2(3)-ortho
2(3)-para
2(1)-para
2(2)-ortho
2(2)-meta
2(2)-para
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
2(3)-para
2(1)-para
2(2)-para
2(3)-para
2(1)-para
2(2)-ortho
2(2)-meta
2(2)-para
2(3)-ortho
2(3)-para
2(1)-biphen
2(2)-biphen
2(3)-biphen
2(1)-biphen
2(2)-biphen
2(3)-biphen
2(1)-biphen
2(2)-biphen
2(3)-biphen
a The reaction with the terminal diene 1 (0.2 mmol) was carried out in glacial acetic acid (100 mL) at 100 ◦C under an argon atmosphere. b Molar ratio of
the terminal diene 1(m), 1(O) : bis(3-oxobutanoate)s 2(n)arom : manganese(III) acetate. c Isolated yield based on the amount of the terminal diene 1(m) and 1(O)
used. d The corresponding diploid was isolated in 17% yield.
Scheme 3 Reaction of dienes 1(m) with bis(3-oxobutanoate)s 2(CH )y-arom in the presence of manganese(III) acetate.
2
bis(3-oxobutanoate) 2(1)-para during the double dihydrofurana-
tion. In addition, the exact molecular ion peak appeared at
m/z 804.3673 (calculated for C52H52O8: 804.3662) in the high-
resolution FAB mass spectrum. Therefore, the product 3(6)(1)-para
was determined to be a [20]paracyclophane. Fortunately, the
product 3(8)(1)-para was crystallized from chloroform–hexane to
provide a single crystal, which was measured by X-ray diffraction.
As a result, it was confirmed that the product 3(8)(1)-para was a
[22]paracyclophane, having two fused dihydrofuran rings (Fig. 1).
Although the strong ring current effect of the hydroquinone group
upfield shift of the methylene protons was particularly remarkable
in the 3(6)(1)-biphen containing the biphenol part, appearing at d
0.29 (2H), 0.12 (2H), and -0.20 (4H) ppm, respectively.
The reaction of icosadiene 1(16) with bis(3-oxobutanoate) 2(3)-
biphen containing the biphenyl moiety deserves comments. The
other cyclic product, which was very similar to the NMR spectrum
of 3(16)(3)-biphen, was isolated (Table 2, Entry 29). The cyclic
product was determined to be the diploid (Fig. 2) since the
high-resolution FAB mass spectrum showed a molecular ion
peak at m/z 2393.3213 (calculated for C152H184O24: 2393.3178)
was observed in most of the cyclophane-type compounds 3(m)(n)
-
(see Experimental section). Another diploid of 3(6)(CH )6-para was
2
arom and 3(m)(CH )y-arom except for 3(O)(n)-arom and the macrocyclic
compounds produced by the reaction using icosadiene 1(16), the
also isolated from the reaction of octadiene 1(6) with bis(3-
oxobutanoate) 2(CH2)6-para (Table 3, Entry 2).
2
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Table 3 Reaction of terminal dienes 1(m) with bis(3-oxobutanoate)s 2(CH )y-arom in the presence of manganese(III) acetatea
2
Entry
Diene
Butanoate
1/2/Mn(III)b
Time/ min
Cyclophane (%)c
Ring size
1
2
3
4
5
6
7
8
9
1(6)
1(6)
1(6)
1(8)
1(8)
1(8)
1(16)
1(16)
1(16)
2(CH2)6-ortho
2(CH2)6-para
2(CH2)8-para
2(CH2)6-ortho
2(CH2)6-para
2(CH2)8-para
2(CH2)6-ortho
2(CH2)6-para
2(CH2)8-para
1 : 1.5 : 7
1 : 1.5 : 7
1 : 1.5 : 7
1 : 1.5 : 7
1 : 1.5 : 7
1 : 1.5 : 7
1 : 1.5 : 7
1 : 1.5 : 7
1 : 1.5 : 7
35
25
25
40
25
25
30
30
25
3(6)(CH2)6-ortho (57)
3(6)(CH2)6-para (58)d
3(6)(CH2)8-para (55)
3(8)(CH2)6-ortho (50)
3(8)(CH2)6-para (57)
3(8)(CH2)8-para (50)
3(16)(CH2)6-ortho (50)
3(16)(CH2)6-para (60)
3(16)(CH2)8-para (50)
30
32
36
32
34
38
40
42
46
a The reaction with the terminal diene 1 (0.2 mmol) was carried out in glacial acetic acid (100 mL) at 100 ◦C under an argon atmosphere. b Molar ratio
of the terminal diene 1(m) : bis(3-oxobutanoate)s 2(CH2)y-arom : manganese(III) acetate. c Isolated yield based on the amount of the terminal diene 1(m) used.
d The corresponding diploid was isolated in 20% yield.
which underwent a Grignard reaction followed by dehydration
of the reduction product and subsequent esterification with a
diketene.
The reaction of p-phenylenebis(1,4-oxa-7,7-diphenylhept-6-
ene) (4(1)) with p-phenylene-1-oxaethyl bis(3-oxobutanoate) (2(1)-
para) was carried out under the same reaction conditions as
above to afford the corresponding [12.12]paracyclophane-type
macrocyclic compound 5(1)(1)-para with 36% yield (Scheme 4 and
Table 4, Entry 1). The existence of two sets of dihydrofuran
and hydroquinone parts was confirmed in the NMR spectrum
of 5(1)(1)-para, and in addition, the molecular ion peak of 5(1)(1)
-
para was identified at m/z 944.3765 (calculated for C58H56O12
944.3772) in the high-resolution FAB mass spectrum. The re-
action of other terminal dienes with bis(3-oxobutanoate)s also
gave the corresponding [x.x]paracyclophane-type macrodiolides
containing between 32 and 56 members in the same yields as
above (Table 4, Entries 2–13), along with some dipliods as a by-
product in some cases (Entries 7,8,10–13). Using the tetrakis(4-
chlorophenyl)-substituted terminal diene 4(1)-Cl instead of the
tetraphenyl-substituted 4(1) in the reaction with 2(1)-para also af-
forded the corresponding [12.12]paracyclophane-type macrocyclic
compound 5(1)(1)-Cl,para in 31% yield.
Fig. 1 X-ray crystal structure of [22]paracyclophane 3(8)(1)-para.
Mechanism for the formation of cyclophane-type macrodiolides
The manganese(III)-mediated macrocyclization was explained
by a two-step mechanism. The formation of the dihydro-
furans using manganese(III) acetate was first investigated by
Heiba and Dessau,16 and after that, many chemists developed
the reaction further.17,18 Manganese(III)-enolate complexes are
formed reversibly by the reaction of manganese(III) acetate
with 1,3-dicarbonyl compounds, such as 2,4-pentandione and
3-oxobutanoates, and undergo addition to electron-rich 1,1-
disubstituted alkenes via a one-electron transfer oxidation to
give tertiary radicals followed by oxidative cyclization, producing
dihydrofurans.19,20 In the macrocyclization, the terminal bis(3-
oxobutanoate)s 2-arom would react with manganese(III) acetate
to give the corresponding manganese(III)-enolate complexes A
(Scheme 5) which attack the terminal dienes 1 to produce the
monodihydrofuran during the first stage. The intramolecular
dihydrofuranation must then occur between the other pair of
enolates and the terminal double bond at the second stage via
the electron donor–acceptor-like interaction such as B,10a,21 and
Fig. 2 Diploid of 3(16)(3)-biphen.
Reaction of alkadienes 4(m) and 6 with di(3-oxobutanoate)s 2(n)-para
and 8 in the presence of manganese(III) acetate
Since we were delighted to obtain the desired cyclophane-
type macrodiolides, we explored the reaction of the termi-
nal alkadienes containing aromatics 4(m) and 6 with bis(3-
oxobutanoate)s 2(n)-para and 8 in order to synthesize the
[x.x]cyclophanes (Scheme 4). The terminal alkadienes contain-
ing aromatics 4(m) were prepared by the reaction of hydro-
quinone with (chloroethoxy)ethanols followed by the reaction
with 3-bromo-1,1-diphenylpropene. p-phenylenebis(7,7-diphenyl-
6-heptene) 6 and p-phenylenebis(heptyl) bis(3-oxobutanoate) 8
were synthesized by the reaction of terephthaloyl dichloride with
1-morpholino-1-cyclohexene followed by decomposition with
sodium hydroxide in ethanol, the Wolff–Kishner reduction,15
and then esterification to give diethyl p-phenylenebis(heptanoate),
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Table 4 Reaction of terminal dienes 4(m) and 6 with bis(3-oxobutanoate)s 2(n)-para and 8 in the presence of manganese(III) acetatea
Entry
Diene
Butanoate
Diene/butanaoate/Mn(III)b
Time/ min
Cyclophane(%)c
Diploid (%)c
Ring size monomer
d
1
2
3
4
5
6
7
8
4(1)
4(1)
4(1)
4(2)
4(2)
4(2)
4(3)
4(3)
4(3)
6
2(1)-para
2(2)-para
2(3)-para
2(1)-para
2(2)-para
2(3)-para
2(1)-para
2(2)-para
2(3)-para
2(1)-para
2(2)-para
2(3)-para
8
1 : 1.5 : 8
1 : 1.5 : 9
1 : 1.5 : 9
1 : 1.5 : 9
1 : 1.5 : 7
1 : 1.5 : 7
1 : 1.5 : 7
1 : 1.5 : 9
1 : 1.5 : 7
1 : 1.5 : 7
1 : 1.5 : 7
1 : 1.5 : 9
1 : 1.5 : 7
40
30
30
40
20
20
30
30
40
30
20
50
20
5(1)(1)-para (36)
5(1)(2)-para (46)
5(1)(3)-para (37)
5(2)(1)-para (33)
5(2)(2)-para (35)
5(2)(3)-para (21)
5(3)(1)-para (38)
5(3)(2)-para (41)
5(3)(3)-para (38)
7(1)-para (62)
7(2)-para (61)
7(3)-para (57)
9 (49)
—
—
—
—
—
—
9
8
—
9
7
4
18
32
38
44
38
44
50
44
50
56
32
38
44
40
d
d
d
d
d
d
9
10
11
12
13
6
6
6
a The reaction with the terminal diene (0.2 mmol) was carried out in glacial acetic acid (100 mL) at 100 ◦C under an argon atmosphere. b Molar ratio of
the terminal diene, bis(3-oxobutanoate), and manganese(III) acetate. c Isolated yield based on the amount of the terminal diene used. d The corresponding
diploid was not isolated.
Scheme 4 Reaction of dienes 4(m) and 6 with bis(3-oxobutanoate)s 2(n)-para and 8 in the presence of manganese(III) acetate.
finally, the cyclophane-type macrodiolides 3-arom were obtained.
The reaction pathway is outlined in Scheme 5. The intramolecular
Conclusions
We have developed the synthesis of cyclophane-type macrodi-
olides 3, 5, 7, and 9 using the manganese(III)-mediated oxidative
radical cyclization of the terminal dienes 1, 4, and 6 with bis(3-
oxobutanoate)s containing aromatics 2 and 8. The cyclophanes
were obtained as a 1 : 1 diastereomixture because they contain
cyclization during the second stage must be specific in the
manganese(III) acetate oxidation because of producing a huge
ring such as 56 members. The production of other cyclophane-
type macrodiolides 5(m)(n)-para, 7(n)-para, and 9 would be realized
by the same reaction pathway.
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Scheme 5 Reaction pathway for the reaction of dienes 1 with bis(3-oxobutanoate)s 2-arom in the presence of manganese(III) acetate.
two asymmetric carbons and the stereoselectivity of the macro-
cyclization was not observed under the conditions. However, the
produced macrocycles were quite stable in air. Although many
ionic macrocyclizations promoted by metal cations are known,8,22
the oxidative radical macrocyclization should be characteristic
for the manganese(III)-based oxidation chemistry. Efforts are
currently underway in our laboratory to investigate the function
of the cyclophane-type macrodiolides.
bis(allyoxy)ethyl ethers 4(m) (m = 1,2,3) were prepared by the
Williamson ether synthesis of the corresponding aromatic diols
with (chloroethoxy)ethanols, followed by esterification with the
diketene or the reaction of 3-bromo-1,1-diphenylpropene under
basic conditions.10a,14 p-phenylenebis(7,7-diphenyl-6-heptene) (6)
and p-phenylenebis(heptyl) bis(3-oxobutanoate) (8) were synthe-
sized by the modified method described in literature.15 That is,
terephthaloyl dichloride was allowed to react with 1-morpholino-
1-cyclohexene followed by the Wolff–Kishner reduction and
esterification, giving diethyl p-phenylenebis(heptanoate), which
underwent same reactions as mentioned above.
Experimental section
Measurements
The melting points are uncorrected. The IR spectra were measured
neat or in CHCl3 solution and expressed in cm-1. The NMR spectra
General procedure for the manganese(III)-based oxidation of
terminal dienes with bis(3-oxobutanoate)s containing aromatics
1
were measured at 300 MHz for H and at 75 Hz for 13C with
To a solution of the terminal diene 1(m), 1(O), 4(m), or 6 (0.2 mmol)
tetramethylsilane as the internal standard. The chemical shifts
are reported in d values (ppm) and the coupling constants in
Hertz. The EIMS spectra were recorded at the ionizing voltage
of 70 eV. The high-resolution mass spectra were measured at the
Institute for Materials Chemistry and Engineering, Kyushu Uni-
versity, Fukuoka, Japan, and the Analytical Center of Kumamoto
University, Kumamoto, Japan.
and bis(3-oxobutanoate) 2(n)-arom, 2(CH )y-arom, or 8 (0.26 mmol)
2
in glacial acetic acid (100 mL), manganese(III) acetate dehydrate
(1.4 mmol) was added and the mixture was sufficiently degassed
under reduced pressure for 30 min using an ultrasonicator for
exchange with an argon atmosphere. The mixture was then heated
at 100 ◦C under an argon atmosphere for the period described in
the tables until the brown color of manganese(III) disappeared.
The color typically turned a transparent yellow. The solvent
was evaporated and the residue was treated with 2 M HCl
(20 mL), which was extracted with CHCl3 (20 mL ¥ 3). The
combined extracts were washed with a saturated aqueous solution
of NaHCO3 (30 mL) and water, and then concentrated to dryness.
The crude products were separated by silica gel TLC (Wakogel
B-10) while eluting with CHCl3, CHCl3–MeOH, or Et2O–hexane.
The molar ratio and product yields are summarized in Tables 1, 2,
3, and 4. The specific details are given below. The data were shown
as a diastereomixture except for 3(O)(1)-para.
Preparation of terminal alkadienes and bis(3-oxobutanoate)s
a,a,w,w-tetraphenyl-a,(w-1)-alkadienes 1(m) (m = 6,8,16) were
prepared by the Grignard reaction of the corresponding alka-
nedioates with phenylmagnesium bromide followed by dehy-
dration. 4-oxa-1,6-heptadiene 1(O) was prepared by the Refor-
matsky reaction of benzophenone with ethyl a-bromoacetate
followed by reduction with lithium aluminium hydride and
then dehydration.14,23 Oxamethylene bis(3-oxobutanoate)s con-
taining aromatics 2(n)-arom (n
= 1,2,3) and p-phenylene
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[20]Paracyclophane 3(6)(1)-para. Diastereomer ratio, 49 : 51. Rf
0.64 (CHCl3–MeOH = 98 : 2 v/v). Colorless microcrystals (from
CHCl3–hexane), m.p. 219 C. IR (CHCl3): n 1693 (C O), 1647
CO-), 153.2, 153.1 (2C, arom. CO-), 145.4 (2C, arom. C),
140.8 (2C, arom. C), 129.9, 128.0, 127.63, 127.61, 127.2, 127.0,
126.7, 126.2 (20C, arom. CH), 116.0 (4C, arom. CH), 107.9 (2C,
C<), 95.1 (2C, >C<), 69.5, 68.6, 68.5 (6C, -CH2O-), 62.5 (2C,
-CO2CH2-), 49.0, 48.9 (2C, >CH-), 31.4, 29.5, 29.4, 26.1, 26.0 (6C,
-CH2-), 14.6 (2C, -CH3) ppm. FAB HRMS (acetone/NBA): calcd
for C56H60O10 892.4186 (M+); found 892.4187.
◦
(C C) cm-1. 1H NMR (300 MHz, CDCl3): d 7.51–7.48 (4H,
m, arom. H), 7.31–7.17 (16H, m, arom. H), 6.74 (4H, s, arom.
H), 4.90–4.86 (2H, m, -CH2O-), 4.07–4.02 (6H, m, -CH2O-),
3.67 (2H, t, J = 5.4 Hz, >CH-), 2.29 (6H, s, -CH3), 1.15–0.92
(4H, m, -CH2-), 0.58–0.31 (4H, m, -CH2-), 0.08–-0.23 (4H, m,
-CH2) ppm. 13C NMR (75 MHz, CDCl3): d 167.0 (2C, -CO2-),
165.5 (2C, CO-), 153.0 (2C, arom. CO-), 145.3 (2C, arom. C),
140.7 (2C, arom. C), 128.0, 127.7, 127.5, 127.0, 126.7, 126.2 (20C,
arom. CH), 115.0 (4C, arom. CH), 107.7 (2C, C<), 95.3 (2C,
>C<), 67.2 (2C, -CH2O-), 61.4 (2C, -CO2CH2-), 48.9 (2C, >CH-),
31.7, 31.6, 29.7(2C), 26.8, 26.7 (6C, -CH2-), 14.4 (2C, -CH3) ppm.
FAB HRMS (acetone/NBA): calcd for C52H52O8 804.3662 (M+);
found 804.3673.
[32]Orthocyclophane 3(6)(3)-ortho. Colorless amorphous. IR
(CHCl3): n 1691 (C O), 1646 (C C) cm-1. 1H NMR (300 MHz,
CDCl3): d 7.51–7.47 (4H, m, arom. H), 7.33–7.14 (16H, m, arom.
H), 6.90 (4H, s, arom. H), 4.35–4.27 (2H, m, -CO2CH2-), 4.19–
4.13 (2H, m, -CO2CH2-, 4H, t, J = 4.5 Hz, -CH2OArOCH2-),
3.85 (4H, t, J = 4.5 Hz, -CH2O-), 3.82–3.68 (10H, m, -CH2O-),
3.67–3.62 (4H, m, -CH2O-, >CH-), 2.26 (6H, s, -CH3), 1.30–1.12
(6H, m, -CH2-), 0.87–0.71 (3H, m, -CH2-), 0.71–0.56 (3H, m,
-CH2-) ppm. 13C NMR (75 MHz, CDCl3): d 166.6 (2C, -CO2-),
[26]Orthocyclophane 3(6)(2)-ortho. Colorless amorphous. IR
(CHCl3): n 1691 (C O), 1646 (C C) cm-1. 1H NMR (300 MHz,
CDCl3): d 7.50–7.48 (4H, m, arom. H), 7.31–7.11 (16H, m, arom.
H), 6.91 (4H, s, arom. H), 4.37–4.30 (2H, m, -CO2CH2-), 4.22–
4.18 (2H, m, -CO2CH2-), 4.17–4.11 (4H, m, -CH2OArOCH2-),
3.84–3.72 (10H, m, -CH2O-, >CH-), 2.26 (6H, s, -CH3), 1.26–
1.18 (4H, m, -CH2-), 0.86–0.73 (4H, m, -CH2-), 0.73–0.64 (4H, m,
-CH2-) ppm. 13C NMR (75 MHz, CDCl3): d 166.5 (2C, -CO2-),
165.5 (2C, CO-), 148.9 (2C, arom. CO-), 145.1 (2C, arom. C),
140.7 (2C, arom. C), 128.5, 128.2, 127.9, 127.4, 127.0, 126.8,
126.5, 126.0 (20C, arom. CH), 121.6, 114.8 (4C, arom. CH),
107.9 (2C, C<), 95.0 (2C, >C<), 69.4 (4C), 68.9 (6C, -CH2O-),
62.4 (2C, -CO2CH2-), 48.4, 48.3 (2C, >CH-), 31.6, 29.2, 25.8 (6C,
-CH2-), 14.4 (2C, -CH3) ppm. FAB HRMS (acetone/NBA): calcd
for C56H61O10 893.4265 (M+H); found 893.4326.
165.7 (2C,
CO-), 149.0 (2C, arom. CO-), 145.2 (2C,
arom. C), 140.8 (2C, arom. C), 128.0, 127.64, 127.61,
127.1, 127.0, 126.7, 126.2 (20C, arom. CH), 121.6, 114.6
(4C, arom. CH), 108.0 (2C,
70.9, 70.6, 69.8, 69.4, 69.0 (10C, -CH2O-), 62.5 (2C,
-CO2CH2-), 48.7 (2C, >CH-), 31.7, 29.5, 26.21, 26.15 (6C,
-CH2-), 14.6 (2C, -CH3) ppm. FAB HRMS (acetone/NBA): calcd
for C60H69O12 981.4789 (M+H); found 981.4816.
C<), 95.2 (2C, >C<),
[32]Paracyclophane
3(6)(3)-para. Colorless amorphous. IR
(CHCl3): n 1689 (C O), 1646 (C C) cm-1. 1H NMR (300 MHz,
CDCl3): d 7.51–7.48 (4H, m, arom. H), 7.36–7.12 (16H, m, arom.
H), 6.85 (4H, s, arom. H), 4.21–4.18 (4H, m, -CO2CH2-), 4.09 (4H,
t, J = 4.5 Hz, -CH2OArOCH2-), 3.80 (4H, t, J = 4.5 Hz, -CH2O-),
3.71–3.56 (14H, m, -CH2O-, >CH-), 2.27 (6H, s, -CH3), 1.32–
1.16 (6H, m, -CH2-), 0.96–0.88 (1H, m, -CH2-), 0.75–0.69 (2H, m,
-CH2-), 0.69–0.50 (3H, m, -CH2-) ppm. 13C NMR (75 MHz,
CDCl3): d 166.2 (2C, -CO2-), 165.6 (2C, CO-), 153.1(2C, arom.
CO-), 145.3 (2C, arom. C), 140.8 (2C, arom. C), 129.9, 128.0,
127.6, 127.2, 127.0, 126.7, 126.2 (20C, arom. CH), 115.9 (4C, arom.
CH), 108.1 (2C, C<), 95.0 (2C, >C<), 70.9, 70.6, 69.8, 69.3,
68.4 (10C, -CH2O-), 62.6 (2C, -CO2CH2-), 48.9 (2C, >CH-), 31.5,
29.6, 29.5, 26.23, 26.16 (6C, -CH2-), 14.8 (2C, -CH3) ppm. FAB
HRMS (acetone/NBA): calcd for C60H69O12 981.4789 (M+H);
found 981.4780.
[26]Metacyclophane 3(6)(2)-meta. Diastereomer ratio, 49 : 51.
Colorless amorphous. IR (CHCl3):
n 1691 (C O), 1646
(C C) cm-1. 1H NMR (300 MHz, CDCl3): d 7.48–7.46 (4H,
m, arom. H), 7.16–7.12 (17H, m, arom. H), 6.54–6.46 (3H,
m, arom. H), 4.31–4.26 (2H, m, -CO2CH2-), 4.22-4.17 (2H, m,
-CO2CH2-), 4.04 (4H, t, J = 4.2 Hz, -CH2OArOCH2-), 3.84-3.68
(10H, m, -CH2O-, >CH-), 2.29 (6H, s, -CH3), 1.26–1.03 (4H, m,
-CH2-), 1.03–0.80 (2H, m, -CH2-), 0.80–0.60 (3H, m, -CH2-), 0.60–
0.42 (3H, m, -CH2-) ppm. 13C NMR (75 MHz, CDCl3): d 166.7
(2C, -CO2-), 165.7 (2C, CO-), 159.9 (2C, arom. CO-), 145.3
(2C, arom. C), 140.8 (2C, arom. C), 129.9 (arom. CH), 128.0,
127.6, 127.1, 126.9, 126.7, 126.7, 126.1 (20C, arom. CH), 107.9,
107.8 (2C, C<), 107.2 (arom. CH), 101.1 (arom. CH), 95.1 (2C,
>C<), 69.5, 69.3, 67.5, 67.3 (6C, -CH2O-), 62.6 (2C, -CO2CH2-),
48.8, 48.7 (2C, >CH-), 31.4, 29.6, 29.5, 26.0, 26.9 (6C, -CH2-),
14.5 (2C, -CH3) ppm. FAB HRMS (acetone/NBA): calcd for
C56H61O10 893.4265 (M+H); found 893.4262.
[22]Paracyclophane 3(8)(1)-para. Diastereomer ratio, 50 : 50.
Rf 0.67 (CHCl3–MeOH = 98 : 2 v/v). Colorless microcrystals
(CHCl3–hexane); m.p. 120 ◦C. IR (CHCl3): n 1693 (C O), 1647
(C C) cm-1. 1H NMR (300 MHz, CDCl3): d 7.53–7.51 (4H,
m, arom. H), 7.35–7.15 (16H, m, arom. H), 6.77 (4H, s, arom.
H), 4.89–4.85 (2H, m, -CO2CH2-), 4.11–3.99 (6H, m, -CO2CH2-,
-CH2OArOCH2-), 3.80–3.70 (2H, m, >CH-), 2.30 (6H, s, -CH3),
1.63 (1H, m, -CH2-), 1.37–1.14 (4H, m, -CH2-), 0.82–0.62 (4H,
m, -CH2-), 0.62–0.38 (7H, m, -CH2-) ppm. 13C NMR (75 MHz,
CDCl3): d 167.2 (2C, -CO2-), 165.7 (2C, CO-), 152.9 (2C, arom.
CO-), 145.3 (2C, arom. C), 140.8 (2C, arom. C), 128.1, 127.7,
127.6, 127.0, 126.7, 126.2 (20C, arom. CH), 115.1 (4C, arom. CH),
107.9 (2C, C<), 95.3 (2C, >C<), 66.9, (2C, -CH2O-), 61.5 (2C,
-CO2CH2-), 49.14, 49.08 (2C, >CH-), 31.9, 30.1, 29.9, 26.9 (8C,
-CH2-), 14.4 (2C, -CH3) ppm. FAB HRMS (acetone/NBA): calcd
for C54H56O8 832.3975 (M+); found 832.3975.
[26]Paracyclophane 3(6)(2)-para. Diastereomer ratio, 50 : 50.
Colorless amorphous. IR (CHCl3):
n 1690 (C O), 1646
(C C) cm-1. 1H NMR (300 MHz, CDCl3): d 7.50–7.47 (4H,
m, arom. H), 7.33–7.13 (16H, m, arom. H), 6.83 (4H, s,
arom. H), 4.27–4.21 (4H, m, -CO2CH2-), 4.06 (4H, t, J = 4.8,
-CH2OArOCH2-), 3.80–3.69 (10H, m, -CH2O-, >CH-), 2.26
(6H, s, -CH3), 1.30–1.08 (4H, m, -CH2-), 1.08–0.80 (2H, m,
-CH2-), 0.80–0.49 (4H, m, -CH2-), 0.49–0.30 (2H, m, -CH2-) ppm.
13C NMR (75 MHz, CDCl3): d 166.5 (2C, C O), 165.7 (2C,
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[28]Orthocyclophane 3(8)(2)-ortho. Colorless amorphous. IR
(CHCl3): n 1691 (C O), 1646 (C C) cm-1. 1H NMR (300 MHz,
CDCl3): d 7.52–7.50 (4H, m, arom. H), 7.34–7.17 (16H, m, arom.
H), 6.92 (4H, s, arom. H), 4.39–4.31 (2H, m, -CO2CH2-), 4.27–4.18
(2H, m, -CO2CH2-) 4.20 (4H, t, J = 5.1 Hz, -CH2OArOCH2-),
3.83 (4H, t, J = 5.1 Hz, -CH2O-), 3.79–3.78 (6H, m, -CH2-,
>CH-), 2.27 (6H, s, -CH3), 1.55–1.05 (6H, m, -CH2-), 1.05–0.70
(10H, m, -CH2-) ppm. 13C NMR (75 MHz, CDCl3): d 166.6 (2C,
-CO2-), 165.7 (2C, CO-), 149.0 (2C, arom. CO-), 145.3 (2C,
arom. C), 140.9 (2C, arom. C), 128.6, 128.2, 128.0, 127.6, 127.1,
127.0, 126.6, 126.2, 125.7, 125.5, (20C, arom. CH), 121.8, 121.6,
115.1 (4C, arom. CH), 108.2, 108.1 (2C, C<), 95.2 (2C, >C<),
69.61, 69.58, 69.0, 68.8 (6C, -CH2O-), 62.5 (2C, -CO2CH2-), 48.7
(2C, >CH-), 31.81, 31.77, 29.5, 28.92, 28.88, 26.02, 25.99 (8C,
-CH2-), 14.6 (2C, -CH3) ppm. FAB HRMS (acetone/NBA): calcd
for C58H65O10 921.4578 (M+H); Found 921.4574.
CDCl3): d 166.4 (2C, -CO2-), 165.7 (2C, CO-), 153.1 (2C, arom.
CO-), 145.4 (2C, arom. C), 140.9 (2C, arom. C), 128.1, 127.7,
127.0, 126.8, 126.2 (20C, arom. CH), 115.8 (4C, arom. CH),
108.1 (2C, C<), 95.1 (2C, >C<), 71.0, 70.7, 69.9, 69.4, 68.4
(10C, -CH2O-), 62.7 (2C, -CO2CH2-), 49.1 (2C, >CH-), 31.6,
29.8, 29.2, 26.1 (8C, -CH2-), 14.7 (2C, -CH3) ppm. FAB HRMS
(acetone/NBA): calcd for C62H73O12 1009.5102 (M+H); found
1009.5050.
[30]Paracyclophane 3(16)(1)-para. Rf 0.76 (CHCl3). Colorless
amorphous. IR (CHCl3): n 1693 (C O), 1645 (C C) cm-1.
1H NMR (300 MHz, CDCl3): d 7.54–7.47 (4H, m, arom. H),
7.34–7.19 (16H, m, arom. H), 6.83 (4H, s, arom. H), 4.53–4.46
(2H, m, -CO2CH2-), 4.40–4.33 (2H, m, -CO2CH2-), 4.12 (4H, t,
J = 4.8 Hz, -CH2OArOCH2-), 3.81 (2H, t, J = 5.1 Hz, >CH-),
2.29 (6H, s, -CH3), 1.47–1.24 (4H, m, -CH2-), 1.24–1.04 (16H, m,
-CH2-), 0.93 (12H, m, -CH2-) ppm. 13C NMR (75 MHz,
[28]Metacyclophane 3(8)(2)-meta. Colorless amorphous. IR
(CHCl3): n 1691 (C O) cm-1. 1H NMR (300 MHz, CDCl3):
d 7.52–7.49 (4H, m, arom. H), 7.32–7.11 (17H, m, arom.
H), 6.52 (2H, m, arom. H), 6.46 (1H, t, J = 2.1 Hz, arom.
H), 4.38 (2H, dt, J = 12.3, 4.5 Hz, -CO2CH2-), 4.16 (2H,
dt, J = 12.3, 4.5 Hz, -CO2CH2-), 4.04 (4H, t, J = 4.8 Hz,
-CH2OArOCH2-), 3.85–3.70 (10H, m, -CH2O-, >CH-), 2.25
(6H, s, -CH3), 1.46–1.10 (4H, m, -CH2-), 1.04–0.77 (6H, m,
-CH2-), 0.77–0.59 (6H, m, -CH2-) ppm. 13C NMR (75 MHz,
CDCl3): d 166.8 (2C, -CO2-), 165.8 (2C, CO-), 159.9 (2C, arom.
CO-), 145.3 (2C, arom. C), 140.8 (2C, arom. C), 129.8 (arom.
CH), 128.0, 127.6, 127.0, 126.7, 126.6, 126.2 (20C, arom. CH),
107.99, 107.97 (2C, arom. CH), 107.3 (2C, C<), 101.0 (arom.
CH), 95.2 (2C, >C<), 69.6, 69.4, 67.4 (6C, -CH2O-), 62.6 (2C,
-CO2CH2-), 48.9 (2C, >CH-), 31.7, 29.8, 29.2, 26.2, 26.1 (8C, -
CH2-), 14.5 (2C, -CH3) ppm. FAB HRMS (acetone/NBA): calcd
for C58H65O10 921.4578 (M+H); found 921.4579.
CDCl3):
d
167.1 (2C, -CO2-), 165.8 (2C,
CO-),
153.1 (2C, arom. CO-), 145.3 (2C, arom. C), 140.9 (2C,
arom. C), 128.1, 127.7, 127.0, 126.7, 126.2 (20C, arom. CH),
115.5 (4C, arom. CH), 108.1 (2C, C<), 95.4 (2C, >C<), 66.7
(2C, -CH2O-), 61.9 (2C, -CO2CH2-), 48.7 (2C, >CH-), 31.7, 29.4,
29.3, 29.1, 28.9, 25.9 (16C, -CH2-), 14.6 (2C, -CH3) ppm. FAB
HRMS (acetone/NBA): calcd for C62H72O8 944.5227 (M+); found
944.5227.
[36]Paracyclophane 3(16)(2)-para. Rf 0.52 (CHCl3–MeOH =
98 : 2 v/v). Colorless amorphous. IR (CHCl3): n 1692 (C O),
1647 (C C) cm-1. 1H NMR (300 MHz, CDCl3): d 7.54–7.51 (4H,
m, arom. H), 7.34–7.18 (16H, m, arom. H), 6.81 (4H, s, arom.
H), 4.40–4.35 (2H, m, -CO2CH2-), 4.23–4.16 (2H, m, -CO2CH2-),
4.04 (4H, t, J = 4.8 Hz, -CH2OArOCH2-), 3.83–3.77 (10H, t, J =
4.8 Hz, -CH2O-, m, >CH-), 2.27 (6H, s, -CH3), 1.40–1.27 (4H,
m, -CH2-), 1.27–1.00 (18H, m, -CH2-), 1.00–0.85 (10H, m, -CH2-)
ppm. 13C NMR (75 MHz, CDCl3): d 166.8 (2C, -CO2-), 165.8 (2C,
CO-), 153.1 (2C, arom. CO-), 145.3 (2C, arom. C), 140.9 (2C,
arom. C), 128.1, 127.7, 127.0, 126.8, 126.2 (20C, arom. CH), 115.4
(4C, arom. CH), 108.1 (2C, C<), 95.2 (2C, >C<), 69.7 (2C),
67.9 (6C, -CH2O-), 62.5 (2C, -CO2CH2-), 48.9 (2C, >CH-), 31.7,
29.8, 29.7, 29.63, 29.58, 29.50, 29.3, 26.2 (16C, -CH2-), 14.6 (2C,
-CH3) ppm. FAB HRMS (acetone/NBA): calcd for C66H80O10
1032.5751 (M+); found 1032.5754.
[28]Paracyclophane 3(8)(2)-para. Rf 0.60 (CHCl3–MeOH =
98 : 2 v/v). Colorless amorphous. IR (CHCl3): n 1692 (C O),
1647 (C C) cm-1. 1H NMR (300 MHz, CDCl3): d 7.53–7.50 (4H,
m, arom. H), 7.34–7.17 (16H, m, arom. H), 6.80 (4H, s, arom.
H), 4.36–4.31 (2H, m, -CO2CH2-), 4.24–4.18 (2H, m, -CO2CH2-),
4.03 (4H, t, J = 4.5 Hz, -CH2OArOCH2-), 3.84–3.75 (10H, m,
-CH2O-, >CH-), 2.28 (6H, s, -CH3), 1.68 (1H, m, -CH2-), 1.41–
1.12 (4H, m, -CH2-), 0.95–0.68 (4H, m, -CH2-), 0.68–0.58 (3H, m,
-CH2-), 0.58–0.41 (4H, m, -CH2-) ppm. 13C NMR (75 MHz,
CDCl3): d 166.7 (2C, -CO2-), 165.8 (2C, CO-), 153.1 (2C, arom.
CO-), 145.4 (2C, arom. C), 140.8 (2C, arom. C), 128.1, 127.6,
127.0, 126.8, 126.2 (20C, arom. CH), 115.6 (4C, arom. CH), 107.9
(2C, C<), 95.1 (2C, >C<), 69.5, 69.4, 68.3 (6C, -CH2O-), 62.5
(2C, -COOCH2-), 49.1 (2C, >CH-), 31.5, 29.9, 29.3, 26.1 (8C, -
CH2-), 14.5 (2C, -CH3) ppm. FAB HRMS (acetone/NBA): calcd
for C58H64O10 920.4499 (M+); found 920.4498.
[42]Paracyclophane
3(16)(3)-para. Colorless amorphous, IR
(neat) n 1690 (C O), 1646 (C C) cm-1. H NMR (300 MHz,
CDCl3): d 7.54–7.51 (4H, m, arom. H), 7.51–7.19 (16H, m, arom.
H), 6.83 (4H, s, arom. H), 4.34–4.28 (2H, m, -CO2CH2-), 4.24-4.20
(2H, m, -CO2CH2-), 4.05 (4H, t, J = 4.5 Hz, -CH2OArOCH2-),
3.82 (4H, t, J = 4.5 Hz, -CH2O-), 3.79–3.65 (14H, m, -CH2O-,
>CH-), 2.28 (6H, s, -CH3), 1.40–1.26 (4H, m, -CH2-), 1.26–1.20
(2H, m, -CH2-), 1.20–1.00 (16H, m, -CH2-), 1.00–0.81 (10H, m,
-CH2-) ppm. 13C NMR (75 MHz, CDCl3): d 166.6 (2C, -CO2-),
165.7 (2C, CO-), 153.0 (2C, arom. CO-), 145.3 (2C, arom. C),
140.8 (2C, arom. C), 128.1, 127.6, 127.0, 126.7, 126.2 (20C, arom.
CH), 115.5 (4C, arom. CH), 108.1 (2C, C<), 95.1 (2C, >C<),
70.8, 70.6, 69.9, 69.5, 68.0 (10C, -CH2O-), 62.5 (2C, -CO2CH2-),
49.0 (2C, >CH-), 31.7, 29.8, 29.74, 29.70, 29.64, 29.57, 29.3, 26.1
(16C, -CH2-), 14.6 (2C, -CH3) ppm. FAB HRMS (acetone/NBA):
calcd for C70H89O12 1121.6354 (M+H); found 1121.6361.
1
[34]Paracyclophane 3(8)(3)-para. Rf 0.35 (CHCl3–MeOH =
98 : 2 v/v). Colorless amorphous. IR (neat) n 1686 (C O), 1647
1
(C C) cm-1. H NMR (300 MHz, CDCl3): d 7.52–7.50 (4H, m,
arom. H), 7.33–7.18 (16H, m, arom. H), 6.83 (4H, s, arom. H),
4.22 (4H, t, J = 4.5 Hz, -CO2CH2-) 4.07 (4H, t, J = 4.5 Hz,
-CH2OArOCH2-), 3.80 (4H, t, J = 4.5 Hz, -CH2O-), 3.76–3.62
(14H, m, -CH2O-, >CH-), 2.27 (6H, s, -CH3), 1.38–1.18 (4H, m,
-CH2-), 0.96–0.63 (12H, m, -CH2-) ppm. 13C NMR (75 MHz,
1498 | Org. Biomol. Chem., 2011, 9, 1491–1507
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[17]Paracyclophane 3(O)(1)-para. Diastereomer ratio, 49 : 51. Rf
0.38 (CHCl3). Colorless amorphous. IR (CHCl3): n 1694 (C O),
3.81–3.65 (8H, m, -CH2O-), 3.64–3.59 (2H, m, >CH-), 2.96 (1H,
dd, J = 9.2, 2.4 Hz, >CHCH2O-), 2.74 (2H, d, J = 4.5 Hz,
>CHCH2O-), 2.67 (1H, dd, J = 9.2, 6.6 Hz, >CHCH2O-), 2.32,
2.29 (6H, s, -CH3) ppm. 13C NMR (75 MHz, CDCl3): d 168.7,
168.3 (2C, -CO2-), 165.3, 165.2 (2C, CO-), 160.1, 159.9 (2C,
arom. CO-), 145.8, 145.2 (2C, arom. C), 140.8, 140.4 (2C, arom.
C), 130.1, 129.8 (1C, arom. CH), 128.0, 127.6, 127.42, 127.37,
126.8, 126.5, 126.4, 126.3 (20C, arom. CH), 107.0, 106.9 (1C, arom.
CH), 103.0, 102.7 (2C, C<), 101.4, 100.9 (2C, arom. CH), 94.61,
94.58 (2C, >C<), 69.5, 69.4, 69.1, 69.0, 68.6, 68.3, 68.0, 67.7 (8C,
-CH2O-), 62.42, 62.36 (2C, -CO2CH2-), 51.4, 50.9 (2C, >CH-),
14.7, 14.6 (2C, -CH3) ppm. FAB HRMS (acetone/NBA): calcd
for C52H53O11 853.3588 (M+H); found 853.3585.
1
1641 (C C) cm-1. H NMR (300 MHz, CDCl3): d 7.38–7.06
(20H, m, arom. H), 6.82, 6.79 (4H, s, arom. H), 4.54–4.48 (2H,
dt, J = 10.8, 2.7 Hz, -CO2CH2-), 4.31 (4H, t, J = 2.7 Hz, -
CH2OArOCH2-), 4.27–4.23 (2H, m, -CO2CH2-), 3.54 (2H, br. d,
J = 10.2 Hz, >CH-), 2.76 (2H, dd, J = 10.2, 2.1 Hz, >CHCH2O-),
2.33 (6H, s, -CH3), 2.27 (2H, m, >CHCH2O-) ppm. 13C NMR
(75 MHz, CDCl3): d 169.1 (2C, -CO2-), 165.3 (2C, CO-), 154.0
(2C, arom. CO-), 144.8 (2C, arom. C), 140.7 (2C, arom. C),
128.1, 128.0, 127.8, 127.7, 127.2, 127.1, 127.0, 126.6, 126.4 (20C,
arom. CH), 116.8, 116.7 (4C, arom. CH), 102.5 (2C, C<), 95.0
(2C, >C<), 68.5 (2C, >CHCH2O-), 68.1 (2C, -CH2OAr-), 64.1
(2C, -COOCH2-), 50.2 (2C, >CH-), 14.7 (2C, -CH3) ppm. FAB
HRMS (acetone/NBA): calcd for C48H44O9 764.2985 (M+); found
764.2957.
[23]Paracyclophane 3(O)(2)-para. Diastereomer ratio, 49 : 51.
Colorless amorphous. IR (CHCl3):
n 1693 (C O), 1645
1
(C C) cm-1. H NMR (300 MHz, CDCl3): d 7.56–7.52 (4H, m,
arom. H), 7.41–7.14 (16H, m, arom. H), 6.81, 6.73 (4H, s, arom.
H), 4.31–4.16 (4H, m, -CO2CH2-), 4.00 (4H, q, J = 4.8 Hz, -
CH2OArOCH2-), 3.76–3.57 (10H, m, -CH2O-, >CH-), 2.78 (1H,
dd, J = 9.2, 2.5 Hz, >CHCH2O-), 2.64 (1H, d, J = 9.2 Hz,
>CHCH2O-), 2.53–2.43 (2H, m, >CHCH2O-), 2.31, 2.27 (6H, s,
-CH3) ppm. 13C NMR (75 MHz, CDCl3): d 168.6, 168.2 (2C,
-CO2-), 165.2, 165.1 (2C, CO-), 153.2 (2C, arom. CO-), 145.7,
145.1 (2C, arom. C), 140.7, 140.5 (2C, arom. C), 128.1, 128.0,
127.7, 127.5, 127.4, 127.3, 126.8, 126.6, 126.5 (20C, arom. CH),
116.0, 115.9 (4C, arom. CH), 102.8 (2C, C<), 94.7 (2C, >C<),
69.6, 69.5 (2C), 69.4, 69.3, 68.7, 68.6, 68.0 (8C, -CH2O-), 62.4 (2C,
-CO2CH2-), 51.2, 50.8 (2C, >CH-), 14.8 (2C, -CH3) ppm. FAB
HRMS (acetone/NBA): calcd for C52H53O11 853.3588 (M+H);
found 853.3644.
Diastereoisomer of 3(O)(1)-para. Rf 0.30 (CHCl3). Colorless
1
amorphous. IR (CHCl3): n 1694 (C O), 1641 (C C) cm-1. H
NMR (300 MHz, CDCl3): d 7.47–7.10 (20H, m, arom. H), 6.82,
6.79 (4H, s, arom. H), 4.46–4.40 (2H, m, -CO2CH2-), 4.32–4.30
(2H, m, -CO2CH2-), 4.25–4.24 (4H, m, -CH2OArOCH2-), 3.53
(2H, br. d, J = 10.2 Hz, >CH-), 2.44 (2H, m, >CHCH2O-),
2.27 (6H, s, -CH3), 2.18 (2H, dd, J = 10.2, 2.0 Hz, >CHCH2O-)
ppm. 13C NMR (75 MHz, CDCl3): d 168.8 (2C, -CO2-), 165.0
(2C, CO-), 154.0 (2C, arom. CO-), 145.0 (2C, arom. C), 140.5
(2C, arom. C), 128.1, 127.8, 127.3, 127.1, 127.0, 126.6, 126.4
(20C, arom. CH), 116.7 (4C, arom. CH), 102.5 (2C, C<), 94.7
(2C, >C<), 68.7 (2C, >CHCH2O-), 67.8 (2C, -CH2OAr-), 63.6
(2C, -CO2CH2-), 50.0 (2C, >CH-), 14.5 (2C, -CH3) ppm. FAB
HRMS (acetone/NBA): calcd for C48H44O9 764.2985 (M+); found
764.2977.
[29]Orthocyclophane 3(O)(3)-ortho. Diastereomer ratio, 50 : 50.
[23]Orthocyclophane 3(O)(2)-ortho. Diastereomer ratio, 49 : 51.
Colorless amorphous. IR (CHCl3): n 1693 (C O), 1646
1
Colorless amorphous. IR (CHCl3):
n
1694 (C O), 1645
(C C) cm-1. H NMR (300 MHz, CDCl3): d 7.57–7.49 (4H, m,
arom. H), 7.37–7.12 (16H, m, arom. H), 6.88 (4H, s, arom. H),
4.36–4.29 (2H, m, >CHCH2O-), 4.22–4.10 (6H, m, >CHCH2O-,
-CH2OArOCH2-), 3.88–3.57 (18H, m, -CH2O-, >CH-), 3.14 (1H,
dd, J = 9.5, 2.4 Hz, >CHCH2O-), 2.89 (2H, d, J = 5.1 Hz,
>CHCH2O-), 2.74 (1H, dd, J = 9.5, 7.8 Hz, >CHCH2O-), 2.32
(6H, s, -CH3 ¥ 2) ppm. 13C NMR (75 MHz, CDCl3): d 168.1, 167.9
(2C, -CO2-), 165.2 (2C, CO-), 148.9 (2C, arom. CO-), 145.3,
145.1 (2C, arom. C), 140.5, 140.4 (2C, arom. C), 128.1, 127.7,
127.3, 126.92, 126.86, 126.41, 126.35 (20C, arom. CH), 121.5,
114.5 (4C, arom. CH), 103.2, 103.0 (2C, C<), 94.7, 94.6 (2C,
>C<), 70.9, 70.5, 69.8, 69.3, 69.0 (12C, -CH2O-), 62.6, 62.5 (2C,
-CO2CH2-), 51.2 (2C, >CH-), 14.7, 14.6 (2C, -CH3) ppm. FAB
HRMS (acetone/NBA): calcd for C56H61O13 941.4112 (M+H);
found 941.4114.
(C C) cm-1. 1H NMR (300 MHz, CDCl3): d 7.53–7.47 (4H,
m, arom. H), 7.36–7.08 (16H, m, arom. H), 6.90 (2H), 6.89,
6.86 (4H, s, arom. H), 4.44–4.36 (2H, m, -CO2CH2-), 4.23–
4.14 (2H, m, -CO2CH2-), 4.10–4.03 (4H, m, -CH2OArOCH2-
), 3.83–3.69 (10H, m, -CH2O-, >CH-), 3.02 (1H, dd, J =
10.2, 2.9 Hz, >CHCH2O-), 2.92 (1H, dd, J = 10.0, 2.9 Hz,
>CHCH2O-), 2.83 (1H, dd, J = 10.2, 6.9 Hz, >CHCH2O-), 2.76
(1H, dd, J = 10.0, 6.9 Hz, >CHCH2O-), 2.28 (6H, s, -CH3) ppm.
13C NMR (75 MHz, CDCl3): d 168.1, 167.8 (2C, -CO2-), 165.3
(2C, CO-), 149.03, 148.96 (2C, arom. CO-), 145.5, 145.2 (2C,
arom. C), 140.6, 140.4 (2C, arom. C), 128.3, 128.1, 127.64, 127.57,
127.3, 127.0, 126.8, 126.7, 126.4, 126.3 (20C, arom. CH), 121.6
(2C), 114.7, 114.4 (4C, arom. CH), 103.3, 103.1 (2C, C<), 94.6,
94.5 (2C, >C<), 69.8, 69.7, 69.5, 69.2, 69.0 (8C, -CH2O-), 62.6
(2C, -CO2CH2-), 51.33, 51.27 (2C, >CH-), 14.7, 14.5 (2C, -CH3)
ppm. FAB HRMS (acetone/NBA): calcd for C52H53O11 853.3588
(M+H); found 853.3585.
[29]Paracyclophane 3(O)(3)-para. Colorless amorphous. IR
(CHCl3): n 1692 (C O), 1645 (C C) cm-1. 1H NMR (300 MHz,
CDCl3): d 7.56–7.50 (4H, m, arom. H), 7.38–7.13 (16H, m,
arom. H), 6.82, 6.81 (4H, s, arom. H), 4.21–4.17 (4H, m,
>CHCH2O-), 4.05 (4H, dd, J = 5.3, 3.9 Hz, -CH2OArOCH2-),
3.79–3.75 (4H, m, -CH2O-), 3.68–3.58 (14H, m, -CH2O-, >CH-),
2.96 (1H, dd, J = 9.6, 2.7 Hz, >CHCH2O-), 2.78 (1H, dd, J = 9.6,
2.7 Hz, >CHCH2O-),.2.69 (1H, dd, J = 14.4, 7.2 Hz, >CHCH2O-
), 2.66 (1H, dd, J = 14.4, 7.2 Hz, >CHCH2O-), 2.30, 2.29 (6H, s,
-CH3) ppm. 13C NMR (75 MHz, CDCl3): d 167.9, 167.8 (2C,
[23]Metacyclophane 3(O)(2)-meta. Diastereomer ratio, 50 : 50.
Colorless amorphous. IR (CHCl3):
n 1693 (C O), 1646
(C C) cm-1. H NMR (300 MHz, CDCl3): d 7.50–7.48 (4H, m,
arom. H), 7.39–7.09 (17H, m, arom. H, arom. H), 6.58 (1H, dd, J =
8.2, 2.4 Hz, arom. H), 6.49 (1H, dd, J = 8.2, 2.4 Hz, arom. H) 6.39
(1H, t, J = 2.4 Hz, arom. H), 4.42–4.29 (2H, m, -CO2CH2-), 4.14–
4.05 (2H, m, -CO2CH2-), 4.00 (4H, J = 4.5 Hz, -CH2OArOCH2-),
1
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-CO2-), 165.1 (2C, CO-), 153.1 (2C, arom. CO-), 145.4, 145.1
(2C, arom. C), 140.6, 140.4 (2C, arom. C), 128.1, 128.0, 127.65,
127.38, 126.9, 126.8, 126.7, 126.4 (20C, arom. CH), 116.04, 115.99
(4C, arom. CH), 103.14, 102.99 (2C, C<), 94.6 (2C, >C<),
70.9, 70.7, 69.9, 69.3, 68.7, 68.6, 68.5 (12C, -CH2O-), 62.4 (2C,
-CO2CH2-), 51.2, 50.9 (2C, >CH-), 14.9 (2C, -CH3) ppm. FAB
HRMS (acetone/NBA): calcd for C56H61O13 941.4112 (M+H);
found 941.4117.
67.9 (10C, -CH2O-), 62.7, 62.5 (2C, -CO2CH2-), 49.1, 49.0 (2C,
>CH-), 42.7, 31.6, 31.4, 29.5, 26.2 (6C, -CH2-), 14.8 (2C, -CH3)
ppm. FAB HRMS (acetone/NBA/NaI): calcd for C66H72O12Na
1079.4921 (M+ +Na); found 1079.5010.
[22]Biphenylcyclophane 3(8)(1)-biphen. Diastereomer ratio,
49 : 51. Rf 0.63 (CHCl3–MeOH = 98 : 2 v/v). Colorless amorphous.
IR (CHCl3): n 1693 (C O), 1645 (C C) cm-1. 1H NMR
(300 MHz, CDCl3): d 7.52–7.49 (4H, m, arom. H), 7.38–7.37
(4H, m, arom. H), 7.38–7.12 (16H, m, arom. H), 6.94–6.90 (4H,
m, arom. H), 4.69–4.64 (2H, m, -CO2CH2-), 4.36–4.22 (6H, m,
-CO2CH2-, -CH2OArOCH2-), 3.70–3.60 (2H, m, >CH-), 2.28
(6H, s, -CH3), 1.11–1.04 (4H, m, -CH2-), 0.50–0.38 (2H, m,
-CH2-), 0.19–0.01 (10H, m, -CH2-) ppm. 13C NMR (75 MHz,
CDCl3): d 167.1, 167.0 (2C, -CO2-), 165.6 (2C, CO-), 158.0
(2C, arom. CO-), 145.4 (2C, arom. C), 140.7 (2C, arom. C),
133.5 (2C, arom. -C–C-), 128.1, 127.7, 127.5, 127.4, 127.0, 126.9,
126.8, 126.24, 126.20, (20C, arom. CH), 115.3 (8C, arom. CH),
107.8, 107.7 (2C, C<), 95.2 (2C, >C<), 66.9 (2C, -CH2O-),
62.3 (2C, -CO2CH2-), 49.2, 49.1 (2C, >CH-), 31.3, 31.2, 30.1
(2C), 29.8, 29.7, 26.3, 26.2 (8C, -CH2-), 14.5 (2C, -CH3) ppm.
FAB HRMS (acetone/NBA): calcd for C60H60O8 908.4288 (M+);
found 908.4299.
[20]Biphenylcyclophane 3(6)(1)-biphen. Diastereomer ratio,
49 : 51. Rf 0.53 (CHCl3–MeOH
= 98 : 2 v/v). Colorless
amorphous. IR (CHCl3): n 1695 (C O) 1643 (C C) cm-1.
1H NMR (300 MHz, CDCl3): d 7.48–7.42 (4H, m, arom. H),
7.38–7.34 (4H, m, arom. H), 7.33–7.08 (16H, m, arom. H),
6.98–6.91 (4H, m, arom. H), 4.45–4.34 (8H, m, -CO2CH2-,
-CH2OArOCH2-), 3.55-3.49 (2H, m, >CH-), 2.25, 2.24 (6H, s,
-CH3), 0.98–0.73 (4H, m, -CH2-), 0.44-0.22 (2H, m, -CH2-),
0.22–0.03 (2H, m, -CH2-), minus 0.06-minus 0.36 (4H, m, -CH2-)
ppm. 13C NMR (75 MHz, CDCl3): d 166.6, 166.5 (2C, -CO2-),
165.4 (2C, CO-), 158.1, 158.0 (2C, arom. CO-), 145.4, 145.3
(2C, arom. C), 140.7 (2C, arom. C), 133.9 (2C, arom. -C–C-),
128.1, 127.7, 127.60, 127.55, 127.0, 126.9, 126.8, 126.2, 126.1,
126.1 (20C, arom. CH), 116.2 (8C, arom. CH), 107.9, 107.7 (2C,
C<), 95.12, 95.06 (2C, >C<), 67.3 (2C, -CH2O-), 63.1 (2C,
-CO2CH2-), 49.1, 48.9 (2C, >CH-), 30.9, 30.7, 29.2 (2C), 26.0, 25.6
(6C, -CH2-), 14.7 (2C, -CH3) ppm. FAB HRMS (acetone/NBA):
calcd for C58H56O8 880.3975 (M+); found 880.3974.
[28]Biphenylcyclophane
3(8)(2)-biphen. Diastereomer ratio,
50 : 50. Rf 0.33 (CHCl3–MeOH = 98 : 2 v/v). Colorless amorphous.
IR (CHCl3): n 1690 (C O), 1647 (C C) cm-1. 1H NMR
(300 MHz, CDCl3): d 7.50–7.47 (4H, m, arom. H), 7.43–7.38
(4H, m, arom. H), 7.33–7.12 (16H, m, arom. H), 7.00–6.93
(4H, m, arom. H) 4.36–4.31 (2H, m, -CO2CH2-), 4.22–4.15 (6H,
m, -CO2CH2-, -CH2OArOCH2-), 3.85–3.82 (4H, m, -CH2O-),
3.80–3.75 (4H, m, -CH2O-), 3.75–3.68 (2H, m, >CH-), 2.27,
2.23 (6H, s, -CH3), 1.25–1.20 (6H, m, -CH2-), 1.50–0.78 (2H,
m, -CH2-), 0.63–0.43 (8H, m, -CH2-) ppm. 13C NMR (75 MHz,
CDCl3): d 166.44, 166.40 (2C, -CO2-), 165.7 (2C, CO-), 158.0
(2C, arom. CO-), 145.4 (2C, arom. C), 140.8 (2C, arom. C),
133.63, 133.59 (2C, arom. -C–C-), 128.0, 127.6, 127.6, 127.0,
126.8, 126.2 (20C, arom. CH), 115.5, 114.8 (8C, arom. CH),
[26]Biphenylcyclophane 3(6)(2)-biphen. Diastereomer ratio,
49 : 51. Rf 0.30 (CHCl3–MeOH = 98 : 2 v/v). Colorless amorphous.
IR (CHCl3): n 1690 (C O), 1647 (C C) cm-1. 1H NMR
(300 MHz, CDCl3): d 7.55–7.35 (8H, m, arom. H), 7.35–7.21
(6H, m, arom. H), 7.20–7.11 (10H, m, arom. H), 7.03–7.00 (4H,
m, arom. H), 4.36–4.31 (2H, m, -CO2CH2-), 4.23–4.20 (4H,
m, -CH2OArOCH2-), 4.11–4.06 (2H, m, -CO2CH2-), 3.83–3.80
(4H, m, -CH2O-), 3.79–3.71 (4H, m, -CH2O-), 3.65–3.57 (2H,
m, >CH-), 2.18, 2.17 (6H, s, -CH3), 1.21–0.98 (4H, m, -CH2-),
0.70–0.53 (2H, m, -CH2-), 0.52–0.36 (2H, m, -CH2-), 0.36–0.11
(4H, m, -CH2-) ppm. 13C NMR (75 MHz, CDCl3) d 166.2 (2C,
-CO2-), 165.6 (2C, CO-), 158.0 (2C, arom. CO-), 145.3 (2C,
arom. C), 140.7 (2C, arom. C), 133.7 (2C, arom. -C–C-), 128.0,
127.6, 127.0, 126.8, 126.2 (20C, arom. CH), 115.8 (8C, arom. CH),
108.0 (2C, C<), 95.0 (2C, >C<), 70.0, 69.5, 68.3 (6C, -CH2O-),
62.6 (2C, -CO2CH2-), 49.2, 49.1 (2C, >CH-), 31.2, 29.4, 26.2
(6C, -CH2-), 14.7 (2C, -CH3) ppm. FAB HRMS (acetone/NBA):
calcd for C62H64O10 968.4499 (M+); found 968.4480.
108.0 (2C,
C<), 95.05, 95.03 (2C, >C<), 69.7, 69.6, 68.2
(6C, -CH2O-), 62.6 (2C, -CO2CH2-), 49.2, 49.1 (2C, >CH-),
31.3, 29.8, 29.2, 26.1 (8C, -CH2-), 14.6 (2C, -CH3) ppm. FAB
HRMS (acetone/NBA): calcd for C64H68O10 996.4812 (M+);
found 996.4874.
[34]Biphenylcyclophane 3(8)(3)-biphen. Rf 0.26 (CHCl3–MeOH =
98 : 2 v/v). Colorless amorphous. IR (CHCl3): n 1690 (C O),
1647 (C C) cm-1. 1H NMR (300 MHz, CDCl3): d 7.53–7.42 (8H,
m, bip-arom. H), 7.27–7.15 (16H, m, arom. H), 6.98–6.95 (4H, m,
arom. H), 4.21–4.17 (8H, m, -CO2CH2-, -CH2OArOCH2-), 3.85
(4H, t, J = 3.3 Hz, -CH2O-), 3.70–3.63 (14H, m, -CH2O-, >CH-
), 2.28, 2.24 (6H, s, -CH3), 1.41–1.22 (4H, m, -CH2-), 1.01–0.82
(3H, m, -CH2-), 0.82–0.77 (2H, m, -CH2-), 0.76–0.69 (3H, m,
-CH2-), 0.68–0.58 (4H, m, -CH2-) ppm. 13C NMR (75 MHz,
[32]Biphenylcyclophane 3(6)(3)-biphen. Rf 0.21 (CHCl3–MeOH =
98 : 2 v/v). Colorless amorphous. IR (CHCl3): n 1690 (C O),
1647 (C C) cm-1. 1H NMR (300 MHz, CDCl3): d 7.52–7.43 (8H,
m, arom. H), 7.43–7.12 (16H, m, arom. H), 7.00–6.97 (4H, m,
arom. H), 4.22–4.14 (8H, m, -CO2CH2-, -CH2OArOCH2-), 3.84–
3.83 (4H, m, -CH2O-), 3.72–3.49 (14H, m, -CH2O-, >CH-), 2.27,
2.22 (6H, s, -CH3), 1.40–1.06 (4H, m, -CH2-), 0.83–0.66 (3H, m,
-CH2-) 0.66–0.54 (3H, m, -CH2-), 0.54–0.39 (2H, m, -CH2-) ppm.
13C NMR (75 MHz, CDCl3): d 166.2, 166.0 (2C, -CO2-), 165.6
(2C, CO-), 158.0 (2C, arom. CO-), 145.4 (2C, arom. C), 140.8
(2C, arom. C), 133.7 (2C, arom. -C–C-), 128.0, 127.7, 127.6, 127.0,
126.8, 126.2 (20C, arom. CH), 115.4 (8C, arom. CH), 108.1 (2C,
C<), 95.1, 95.0 (2C, >C<), 71.4, 71.1, 70.7, 70.5, 69.9, 69.4,
CDCl3): d 166.1 (2C, -CO2-), 165.6 (2C,
CO-), 157.9 (2C,
arom. CO-), 145.4 (2C, arom. C), 140.8 (2C, arom. C), 133.7 (2C,
arom. -C–C-), 128.0, 127.7, 127.6, 127.0, 126.8, 126.2 (20C, arom.
CH), 115.3 (8C, arom. CH), 108.2 (2C, C<), 95.0 (2C, >C<),
71.1, 70.7, 69.9, 69.4, 67.9 (10C, -CH2O-), 62.7 (2C, -CO2CH2-),
49.2 (2C, >CH-), 31.5, 29.8, 29.2, 26.1 (8C, -CH2-), 14.8 (2C,
1500 | Org. Biomol. Chem., 2011, 9, 1491–1507
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-CH3) ppm. FAB HRMS (acetone/NBA/NaI): calcd for
Diploid of 3(16)(3)-biphen. Rf 0.27 (CHCl3–MeOH = 98 : 2 v/v).
C68H76O12 1084.5337 (M+ +Na); found 1084.5272.
Colorless amorphous. IR (CHCl3): n 1688 (C O), 1647
1
(C C) cm-1. H NMR (300 MHz, CDCl3): d 7.54–7.52 (8H, m,
arom. H), 7.47–7.44 (8H, m, arom. H), 7.42–7.19 (32H, m, arom.
H), 6.98–6.94 (8H, m, arom. H), 4.30–4.24 (8H, m, -CO2CH2-),
4.18 (8H, m, -CH2OArOCH2-), 3.90–3.79 (8H, m, -CH2O-), 3.79–
3.59 (28H, m, -CH2O-, >CH-), 2.28 (12H, s, -CH3), 1.53–1.29
(8H, m, -CH2-), 1.29–1.00 (40H, m, -CH2-), 1.00–0.78 (16H, m,
-CH2-) ppm. 13C NMR (75 MHz, CDCl3): d 166.3 (4C, -CO2-
), 165.7 (4C, CO-), 157.9, 157.8 (4C, arom. CO-), 145.4 (4C,
arom. C), 140.9 (4C, arom. C), 133.7, 133.6 (4C, arom -C–C-),
128.3, 128.2, 128.1, 127.7, 127.1, 126.8, 126.3, 125.7, 125.6 (40C,
arom. CH), 114.9 (16C, arom CH), 108.2 (4C, C<), 95.1 (4C,
>C<), 72.5, 71.4, 70.9, 70.7, 70.6, 70.4, 69.8, 69.4, 67.5 (20C,
-CH2O-), 62.6, 61.8 (4C, -CO2CH2-), 49.1 (4C, >CH-), 31.6, 29.7,
29.6, 29.5, 29.2, 26.2, 26.0 (32C, -CH2-), 14.8 (4C, -CH3) ppm. FAB
HRMS (acetone/NBA): calcd for C152H184O24 2393.3178 (M+);
found 2393.3213.
[30]Biphenylcyclophane 3(16)(1)-biphen. Rf 0.16 (CHCl3). Color-
less amorphous. IR (CHCl3): n 1695 (C O), 1647 (C C) cm-1.
1H NMR (300 MHz, CDCl3): d 7.54–7.52 (4H, m, arom. H), 7.46–
7.43 (4H, m, arom. H), 7.35–7.17 (16H, m, arom. H), 6.95–6.92
(4H, m, arom. H), 4.66 (2H, dt, J = 12.0, 4.8 Hz, -CO2CH2-), 4.30
(2H, dt, J = 12.0, 4.8 Hz, -CO2CH2-), 4.20 (4H, t, J = 4.8 Hz,
-CH2OArOCH2-), 3.80 (2H, t, J = 5.4 Hz, >CH-), 2.31 (6H, s,
-CH3), 1.38–1.23 (4H, m, -CH2-), 1.16–0.99 (16H, m, -CH2-),
0.98–0.77 (12H, m, -CH2-) ppm. 13C NMR (75 MHz, CDCl3):
d 167.3 (2C, -CO2-), 165.8 (2C, CO-), 157.8 (2C, arom. CO-),
145.3 (2C, arom. C), 140.8 (2C, arom. C), 133.7 (2C, arom. -
C–C-), 128.1, 127.7, 127.0, 126.7, 126.2 (20C, arom. CH), 114.7
(8C, arom. CH), 108.1 (2C, C<), 95.5 (2C, >C<), 66.2 (2C,
-CH2O-), 61.7 (2C, -CO2CH2-), 48.8 (2C, >CH-), 32.0, 29.85,
29.80, 29.7, 29.6, 29.4, 26.4 (16C, -CH2-), 14.5 (2C, -CH3) ppm.
FAB HRMS (acetone/NBA): calcd for C68H76O8 1020.5540 (M+);
found 1020.5518.
[28]Orthocyclophane
3(6)(CH2)6-ortho. Diastereomer
ratio,
49 : 51. Rf 0.22 (CHCl3). Colorless amorphous. IR (CHCl3): n
1684 (C O), 1647 (C C) cm-1. 1H NMR (300 MHz, CDCl3): d
7.51–7.48 (4H, m, arom. H), 7.32–7.13 (16H, m, arom. H), 6.79
(4H, s, arom. H), 4.17–4.11 (2H, m, -CO2CH2-), 4.07–3.96 (6H,
m, -CH2OArOCH2-, -CO2CH2-), 3.70 (2H, t, J = 5.4 Hz, >CH-),
2.26 (6H, s, -CH3), 1.81 (4H, quin, J = 6.6 Hz, -CH2-), 1.66 (4H,
quin, J = 6.9 Hz, -CH2-), 1.59–1.52 (4H, m, -CH2-), 1.49–1.44
(4H, m, -CH2-), 1.26–1.16 (4H, m, -CH2-), 0.80–0.68 (8H, m,
-CH2-) ppm. 13C NMR (75 MHz, CDCl3): d 166.23, 166.18 (2C,
-CO2-), 166.0, 165.9 (2C, CO-), 149.2 (2C, arom. CO-), 145.3
(2C, arom. C), 140.9 (2C, arom. C) 128.0, 127.61, 126.98, 126.74,
126.71, 126.2 (20C, arom. CH), 121.2, 114.1 (4C, arom. CH),
108.33, 108.30 (2C, C<), 95.13, 95.11 (2C, >C<), 69.0 (2C,
-CH2O-), 63.4 (2C, -CO2CH2-), 49.8, 48.7 (2C, >CH-), 31.8, 29.4,
29.3, 28.7, 26.3, 26.2, 25.9, 25.8 (14C, -CH2-), 14.5 (2C, -CH3)
ppm. FAB HRMS (acetone/NBA): calcd for C60H68O8 916.4914
(M+); found 916.4900.
[36]Biphenylcyclophane
3(16)(2)-biphen. Rf 0.29 (CHCl3–
MeOH = 98 : 2 v/v). Colorless amorphous. IR (CHCl3): n 1692
(C O), 1645 (C C) cm-1. 1H NMR (300 MHz, CDCl3): d
7.54–7.51 (4H, m, arom. H), 7.44–7.41 (4H, m, arom. H),
7.35–7.18 (16H, m, arom. H), 6.94–6.92 (4H, m, arom. H), 4.40
(2H, dt, J = 12.3, 4.2 Hz, -CO2CH2-), 4.19 (2H, dt, J = 12.3,
4.2 Hz, -CO2CH2-), 4.12 (4H, t, J = 5.1 Hz, -CH2OArOCH2-),
3.86 (4H, t, J = 5.1, 1.8 Hz, -CH2-), 3.82–3.77 (6H, m, -CH2O-,
>CH-), 2.29, 2.23 (6H, s, -CH3), 1.43–1.28 (4H, m, -CH2-),
1.27–1.12 (4H, m, -CH2-), 1.11–0.98 (10H, m, -CH2-), 0.98–0.76
(14H, m, -CH2-) ppm. 13C NMR (75 MHz, CDCl3): d 166.8
(2C, -CO2-), 165.8 (2C, CO-), 157.8 (2C, arom. CO-), 145.3
(2C, arom. C), 140.7 (2C, arom. C), 133.4 (2C, arom. -C–C-),
128.0, 127.6, 127.5, 127.0, 126.7, 126.1 (20C, arom. CH), 114.6
(8C, arom. CH), 107.9 (2C, C<), 95.1 (2C, >C<), 69.6, 69.4,
67.4 (6C, -CH2O-), 62.5 (2C, -CO2CH2-), 49.0 (2C, >CH-), 31.6,
29.9, 29.8, 29.4, 26.2 (16C, -CH2-), 14.5 (2C, -CH3) ppm. FAB
HRMS (acetone/NBA): calcd for C72H84O10 1108.6064 (M+);
found 1108.6064.
[28]Paracyclophane 3(6)(CH2)6-para. Diastereomer ratio, 49 : 51.
Rf 0.35 (CHCl3). Colorless amorphous. IR (CHCl3): n 1697
(C O), 1653 (C C) cm-1. 1H NMR (300 MHz, CDCl3): d 7.50–
7.48 (4H, m, arom. H), 7.33–7.17 (16H, m, arom. H), 6.80–6.70
(4H, m, arom. H), 4.11–4.00 (4H, m, -CO2CH2-), 3.95 (4H, t,
J = 6.0 Hz, -CH2OArOCH2-), 3.67 (2H, t, J = 5.1 Hz, >CH-
), 2.31 (6H, s, -CH3), 1.73 (4H, quin, J = 6.3 Hz, -CH2-), 1.62
(4H, quin, J = 6.6 Hz, -CH2-), 1.53–1.37 (8H, m, -CH2-), 1.20–
1.31 (4H, m, -CH2-), 0.80–0.55 (4H, m, -CH2-), 0.55–0.42 (4H, m,
-CH2-) ppm. 13C NMR (75 MHz, CDCl3): d 165.9, 165.83 (2C,
-CO2-), 165.79 (2C, CO-), 152.9 (2C, arom. CO-), 145.4 (2C,
arom. C), 140.8 (2C, arom. C) 128.0, 127.63, 127.59, 127.0, 126.8,
126.2 (20C, arom. CH), 115.81, 115.80 (4C, arom. CH), 108.3,
108.2 (2C, C<), 95.0 (2C, >C<), 68.2, 68.1 (2C, -CH2O-), 63.3
(2C, -CO2CH2-), 49.1 (2C, >CH-), 31.5, 29.5, 28.6, 28.5, 26.32,
26.28, 25.5, 25.4, 25.3 (14C, -CH2-), 14.7 (2C, -CH3) ppm. FAB
HRMS (acetone/NBA): calcd for C60H68O8 916.4914 (M+); found
916.4890.
[42]Biphenylcyclophane
3(16)(3)-biphen. Rf 0.37 (CHCl3–
MeOH = 98 : 2 v/v). Colorless amorphous. IR (CHCl3): n 1695
(C O), 1647 (C C) cm-1. 1H NMR (300 MHz, CDCl3): d 7.53–
7.51 (4H, m, arom. H), 7.45–7.42 (4H, m, arom. H), 7.42–7.16
(16H, m, arom. H), 6.95–6.93 (4H, m, arom. H), 4.32–4.20 (4H,
m, -CO2CH2-), 4.15 (4H, t, J = 5.1 Hz, -CH2OArOCH2-), 3.87
(4H, t, J = 5.1 Hz, -CH2O-), 3.80–3.64 (14H, m, -CH2O-, >CH-),
2.28 (6H, s, -CH3), 1.46–1.28 (4H, m, -CH2-), 1.28–1.16 (4H, m,
-CH2-), 1.16–1.01 (10H, m, -CH2-), 0.98–0.82 (14H, m, -CH2-)
ppm. 13C NMR (75 MHz, CDCl3): d 166.4 (2C, -CO2-), 165.6
(2C, CO-), 157.8 (2C, arom. CO-), 145.3 (2C, arom. C), 140.8
(2C, arom. C), 133.5 (2C, arom. -C–C-), 128.0, 127.6, 127.5,
126.9, 126.7, 126.1 (20C, arom. CH), 114.8 (8C, arom. CH), 108.0
(2C, C<), 95.0 (2C, >C<), 70.9, 70.6, 69.7, 69.4, 67.5 (10C,
-CH2O-), 62.6 (2C, -CO2CH2-), 49.0 (2C, >CH-), 31.5, 29.8, 29.8,
29.7, 29.6, 29.2, 26.0 (16C, -CH2-), 14.6 (2C, -CH3) ppm. FAB
HRMS (acetone/NBA): calcd for C76H92O12 1196.6589 (M+);
found 1196.6580.
Diploid of 3(6)(CH2)6-para. Rf 0.12 (CHCl3). Colorless amor-
phous. IR (CHCl3): n 1684 (C O), 1651 (C C) cm-1. 1H NMR
(300 MHz, CDCl3): d 7.60–7.49 (8H, m, arom. H), 7.49–7.05
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(32H, m, arom. H), 6.81 (8H, s, arom. H), 4.16–4.00 (8H, m,
-CO2CH2-), 4.00–3.80 (8H, m, -CH2OArOCH2-), 3.80–3.70 (4H,
m >CH-), 2.32 (12H, s, -CH3), 1.90–1.70 (8H, m, -CH2-), 1.70–
1.66 (8H, m, -CH2-), 1.59–1.35 (18H, m, -CH2-), 1.26–1.04 (8H,
m, -CH2-), 1.04–0.62 (8H, m, -CH2-), 0.62–0.39 (6H, m, -CH2-)
ppm. 13C NMR (75 MHz, CDCl3): d 165.92 (4C, -CO2-), 165.90
(4C, CO-), 153.1 (4C, arom. CO-), 145.3 (4C, arom. C), 140.9
(4C, arom. C) 128.1, 127.6, 127.0, 126.8, 126.2 (40C, arom. CH),
115.4 (8C, arom CH), 108.4 (4C, C<), 95.0 (4C, >C<), 68.4
(4C, -CH2O-), 63.5 (4C, -CO2CH2-), 49.0 (4C, >CH-), 31.6, 29.5,
29.3, 28.7, 25.9, 25.8 (28C, -CH2-), 14.7 (4C, -CH3) ppm. FAB
HRMS (acetone/NBA): calcd for C120H136O16 1832.9828 (M+);
found 1832.9825.
140.9 (2C, arom. C) 128.0, 127.6, 127.0, 126.8, 126.2 (20C, arom.
CH), 115.7 (4C, arom. CH), 108.3 (2C, C<), 95.0 (2C, >C<),
68.2 (2C, -CH2O-), 63.3 (2C, -CO2CH2-), 49.1 (2C, >CH-), 31.7,
29.8, 29.2, 28.7, 28.6, 26.3, 25.6, 25.4 (16C, -CH2-), 14.5 (2C, -CH3)
ppm. FAB HRMS (acetone/NBA): calcd for C62H72O8 944.5227
(M+); found 944.5226.
[34]Paracyclophane 3(8)(CH2)8-para. Rf 0.36 (CHCl3). Colorless
1
amorphous. IR (CHCl3): n 1683 (C O), 1647 (C C) cm-1. H
NMR (300 MHz, CDCl3): d 7.53–7.51 (4H, m, arom. H), 7.29–
7.13 (16H, m, arom. H), 6.79 (4H, s, arom. H), 4.10–4.05 (4H,
m, -CO2CH2-), 3.92 (4H, t, J = 6.3 Hz, -CH2OArOCH2-), 3.75
(2H, t, J = 4.8 Hz, >CH-), 2.26 (6H, s, -CH3), 1.74–1.67 (4H,
quin, J = 6.6 Hz, -CH2-), 1.66–1.54 (4H, m, -CH2-), 1.53–1.23
(22H, m, -CH2-), 1.00–0.70 (10H, m, -CH2-) ppm. 13C NMR
(75 MHz, CDCl3): d 165.78 (2C, -CO2-), 165.71 (2C, CO-),
152.9 (2C, arom. CO-), 145.3 (2C, arom. C), 140.8 (2C, arom. C)
127.9, 127.5, 126.9, 126.7, 126.1 (20C, arom. CH), 115.6, 115.2
(4C, arom. CH), 108.3 (2C, C<), 94.9 (2C, >C<), 68.2 (2C,
-CH2O-), 63.4 (2C, -CO2CH2-), 49.0 (2C, >CH-), 31.6, 29.6, 28.9,
28.7, 28.6, 28.5, 26.1, 25.7, 25.4 (20C, -CH2-), 14.5 (2C, -CH3)
ppm. FAB HRMS (acetone/NBA): calcd for C66H80O8 1000.5853
(M+); found 1000.5860.
[32]Paracyclophane 3(6)(CH2)8-para. Rf 0.37 (CHCl3). Colorless
1
amorphous. IR (CHCl3): n 1688 (C O), 1647 (C C) cm-1. H
NMR (300 MHz, CDCl3): d 7.51–7.49 (4H, m, arom. H), 7.39–
7.15 (16H, m, arom. H), 6.81 (4H, s, arom. H), 4.05 (4H, t, J =
6.6 Hz, -CO2CH2-), 3.96 (4H, t, J = 6.6 Hz, -CH2OArOCH2-),
3.70–3.62 (2H, m, >CH-), 2.26 (6H, s, -CH3), 1.73 (4H, quin,
J = 6.6 Hz, -CH2-), 1.65–1.53 (4H, m, -CH2-), 1.44–1.42 (4H, m,
-CH2-), 1.32 (12H, m, -CH2-), 1.25–1.15 (4H, m, -CH2-), 0.81–
0.60 (4H, m, -CH2-), 0.60–0.50 (4H, m, -CH2-) ppm. 13C NMR
(75 MHz, CDCl3): d 165.9 (2C, -CO2-), 165.7 (2C, CO-), 153.0
(2C, arom. CO-), 145.4 (2C, arom. C), 140.9 (2C, arom. C) 128.0,
127.6, 127.0, 126.8, 126.2 (20C, arom. CH), 115.7 (4C, arom. CH),
108.4 (2C, C<), 95.0 (2C, >C<), 68.3 (2C, -CH2O-), 63.6 (2C,
-CO2CH2-), 49.0 (2C, >CH-), 31.6, 29.5, 28.8, 28.6, 28.53, 28.47,
26.3, 26.2, 25.7, 25.4 (16C, -CH2-), 14.7 (2C, -CH3) ppm. FAB
HRMS (acetone/NBA): calcd for C64H76O8 972.5540 (M+); found
972.5577.
[38]Orthocyclophane 3(16)(CH2)6-ortho. Rf 0.50 (CHCl3). color-
less amorphous. IR (CHCl3): n 1686 (C O), 1647 (C C) cm-1.
1H NMR (300 MHz, CDCl3): d 7.45–7.42 (4H, m, arom. H), 7.22–
7.06 (16H, m, arom. H), 6.77 (4H, s, arom. H), 4.05–3.95 (4H, m,
-CO2CH2-), 3.89 (4H, t, J = 6.6 Hz, -CH2OArOCH2-), 3.71 (2H,
t, J = 5.1 Hz, >CH-), 2.18 (6H, s, -CH3), 1.73 (4H, t, J = 6.6 Hz,
-CH2-), 1.60 (4H, t, J = 6.6 Hz, -CH2-), 1.61–1.39 (8H, m, -CH2-),
1.31–1.24 (4H, m, -CH2-), 1.18–1.01 (18H, m, -CH2-), 1.01–0.82
(10H, m, -CH2-) ppm. 13C NMR (75 MHz, CDCl3): d 166.0 (2C,
-CO2-), 165.8 (2C, CO-), 149.0 (2C, arom. CO-), 145.3 (2C,
arom. C), 140.8 (2C, arom. C) 127.9, 127.5, 126.9, 126.6, 126.1
(20C, arom. CH), 114.1 (4C, arom. CH), 108.3 (2C, C<), 95.0
(2C, >C<), 68.9 (2C, -CH2O-), 63.3 (2C, -CO2CH2-), 48.8 (2C,
>CH-), 31.7, 29.5, 29.2, 29.1, 29.0, 28.7, 26.1, 25.8, 25.6 (24C,
-CH2-), 14.4 (2C, -CH3) ppm. FAB HRMS (acetone/NBA): calcd
for C70H89O8 1057.6557 (M+1); found 1057.6477.
[30]Orthocyclophane 3(8)(CH2)6-ortho. Rf 0.37 (CHCl3). Color-
less amorphous. IR (CHCl3): n 1686 (C O), 1647 (C C) cm-1.
1H NMR (300 MHz, CDCl3): d 7.56–7.50 (4H, m, arom. H), 7.32–
7.14 (16H, m, arom. H), 6.88 (4H, s, arom. H), 4.21–4.13 (2H,
m, -CO2CH2-), 4.07–3.95 (6H, m, -CO2CH2-, -CH2OArOCH2-),
3.74 (2H, t, J = 5.4 Hz, >CH-), 2.32 (6H, s, -CH3), 1.81 (4H,
quin, J = 6.3 Hz, -CH2-), 1.67 (4H, quin, J = 6.6 Hz, -CH2-
), 1.60–1.38 (8H, m, -CH2-), 1.37–1.20 (3H, m, -CH2-), 1.17–
1.15 (1H, m, -CH2-), 1.00–0.75 (12H, m, -CH2-) ppm. 13C NMR
(75 MHz, CDCl3): d 166.3 (2C, -CO2-), 166.0 (2C, CO-), 149.2
(2C, arom. CO-), 145.3 (2C, arom. C), 140.9 (2C, arom. C) 128.2,
128.0, 127.6, 127.0, 126.7, 126.2, 121.1 (20C, arom. CH), 114.1
(4C, arom. CH), 108.4 (2C, C<), 95.1 (2C, >C<), 69.0 (2C,
-CH2O-), 63.4 (2C, -CO2CH2-), 48.9 (2C, >CH-), 31.8, 29.6, 29.2,
28.9, 28.7, 26.2, 26.0, 25.7 (16C, -CH2-), 14.5 (2C, -CH3) ppm.
FAB HRMS (acetone/NBA): calcd for C62H72O8 944.5227 (M+);
found 944.5233.
[38]Paracyclophane 3(16)(CH2)6-para. Rf 0.32 (CHCl3). Colorless
1
amorphous. IR (CHCl3): n 1685 (C O), 1647 (C C) cm-1. H
NMR (300 MHz, CDCl3): d 7.54–7.51 (4H, m, arom. H), 7.35–
7.20 (16H, m, arom. H), 6.78 (4H, s, arom. H), 4.22 (2H, dt,
J = 10.8, 6.0 Hz, -CO2CH2-), 4.01 (2H, dt, J = 10.8, 6.0 Hz,
-CO2CH2-),3.87 (4H, t, J = 6.6 Hz, -CH2OArOCH2-), 3.76 (2H,
t, J = 5.1 Hz, >CH-), 2.28 (6H, s, -CH3), 1.86–1.70 (4H, t, J =
6.6 Hz, -CH2-), 1.70–1.58 (4H, t, J = 6.6 Hz, -CH2-), 1.58–1.39
(8H, m, -CH2-), 1.58–1.24 (6H, m, -CH2-), 1.24–1.03 (16H, m,
-CH2-), 1.02–0.74 (10H, m, -CH2-) ppm. 13C NMR (75 MHz,
CDCl3): d 166.3 (2C, -CO2-), 165.9 (2C, CO-), 153.0 (2C, arom.
CO-), 145.2 (2C, arom. C), 140.8 (2C, arom. C) 128.1, 128.0,
127.5, 126.9, 126.7, 126.1 (20C, arom. CH), 115.1 (4C, arom. CH),
108.2 (2C, C<), 95.0 (2C, >C<), 68.2 (2C, -CH2O-), 63.2 (2C,
-CO2CH2-), 48.9 (2C, >CH-), 31.9, 29.9, 29.82, 29.79, 29.73, 29.66,
29.4, 29.2, 28.7, 26.4, 26.0, 25.7 (24C, -CH2-), 14.5 (2C, -CH3) ppm.
FAB HRMS (acetone/NBA): calcd for C70H88O8 1056.6479 (M+);
found 1056.6432.
[30]Paracyclophane 3(8)(CH2)6-para. Rf 0.45 (CHCl3). Colorless
1
amorphous. IR (CHCl3): n 1686 (C O), 1647 (C C) cm-1. H
NMR (300 MHz, CDCl3): d 7.52–7.50 (4H, m, arom. H), 7.30–
7.16 (16H, m, arom. H), 6.78 (4H, s, arom. H), 4.20–4.05 (4H, m,
-CO2CH2-), 3.92 (4H, t, J = 6.3 Hz, -CH2OArOCH2-), 3.75–3.70
(2H, m, >CH-), 2.26 (6H, s, -CH3), 1.74 (4H, quin, J = 6.3 Hz,
-CH2-), 1.65 (4H, quin, J = 6.3 Hz, -CH2-), 1.57–1.36 (10H, m,
-CH2-), 1.36–1.20 (4H, m, -CH2-), 1.00–0.68 (10H, m, -CH2-)
ppm. 13C NMR (75 MHz, CDCl3): d 166.00, 165.97 (2C, -CO2-),
165.90 (2C, CO-), 153.0 (2C, arom. CO-), 145.4 (2C, arom. C),
1502 | Org. Biomol. Chem., 2011, 9, 1491–1507
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[42]Paracyclophane 3(16)(CH2)8-para. Rf 0.43 (CHCl3). Col-
m, arom. H), 4.37–4.31 (2H, m, -CO2CH2-), 4.22–4.15 (2H, m, -
CO2CH2-), 4.10 (2H, d, J = 8.1 Hz, >CH-), 3.99 (4H, t, J = 4.6 Hz,
-CH2O-), 3.79 (4H, t, J = 4.6 Hz, -CH2O-), 3.73–3.60 (18H, m, -
CH2O-), 3.28–3.21 (2H, m, -CH2O-), 3.14 (2H, t, J = 9.0 Hz,
-CH2O-), 2.97–2.90 (2H, m, -CH2O-), 2.34 (6H, s, CH3) ppm.13C
NMR (75 MHz, CDCl3): d 168.5 (2C, C O), 165.4 (2C, CO-),
152.98, 152.94 (4C, arom. C), 144.9 (2C, arom. C), 140.4 (2C,
arom. C), 128.1, 127.7, 127.6, 127.3, 127.2, 127.1, 126.5 (20C,
arom. CH), 115.5, 115.3 (8C, arom. CH), 102.8 (2C, >C ), 94.8
(2C, >C<), 70.8, 70.7, 69.8, 69.6, 69.4, 68.8, 68.0, 67.5 (16C, -
CH2O-), 62.9 (2C, -CO2CH2-), 51.5 (2C, >CH-), 14.6 (2C, -CH3)
ppm. FAB HRMS (acetone/NBA): calcd for C66H72O16 1120.4820
(M+); found 1120.4744.
orless amorphous. IR (CHCl3):
n
1683 (C O), 1647
(C C) cm-1. 1H NMR (300 MHz, CDCl3): d 7.54–7.51
(4H, m, arom. H), 7.33–7.16 (16H, m, arom. H), 6.77
(4H, s, arom. H), 4.18 (2H, dt,
J
= 10.8, 6.3 Hz,
-CO2CH2-), 4.02 (2H, dt, J = 10.8, 6.3 Hz, -CO2CH2-), 3.87
(4H, t, J = 6.6 Hz, -CH2OArOCH2-), 3.76 (2H, t, J = 5.1 Hz,
>CH-), 2.28 (6H, s, -CH3), 1.73 (4H, quin, J = 6.6 Hz, -CH2-),
1.64 (4H, quin, J = 6.3 Hz, -CH2-), 1.55–1.40 (8H, m, -CH2-),
1.40–1.26 (16H, m, -CH2-), 1.23–1.05 (12H, m, -CH2-) 1.00–0.70
(12H, m, -CH2-) ppm. 13C NMR (75 MHz, CDCl3): d 166.2 (2C,
-CO2-), 166.0 (2C, CO-), 153.1 (2C, arom. CO-), 145.4 (2C,
arom. C), 140.9 (2C, arom. C) 128.0, 127.6, 127.0, 126.8, 126.2
(20C, arom. CH), 115.4 (4C, arom. CH), 108.3 (2C, C<), 95.1
(2C, >C<), 68.5 (2C, -CH2O-), 63.4 (2C, -CO2CH2-), 49.1 (2C,
>CH-), 31.8, 29.91, 28.87, 29.79, 29.7, 29.4, 29.24, 29.19, 29.17,
28.8, 26.9, 26.4, 26.1, 25.9 (28C, -CH2-), 14.5 (2C, -CH3) ppm.
FAB HRMS (acetone/NBA): calcd for C74H96O8 1112.7105 (M+);
found 1112.7113.
[15.15]Paracyclophane 5(2)(1)-para. Rf 0.09 (CHCl3). Colorless
1
amorphous. IR (CHCl3): n 1693 (C O), 1645 (C C) cm-1. H
NMR (300 MHz, CDCl3): d 7.59–7.57 (4H, m, arom. H), 7.36–
7.19 (16H, m, arom. H), 6.81–6.67 (8H, m, arom. H), 4.44–4.29
(4H, m, -CO2CH2-), 4.09–4.02 (6H, m, -CH2O-, >CH-), 3.97 (4H,
t, J = 4.5 Hz, -CH2O-), 3.68 (4H, J = 4.5 Hz, -CH2O-), 3.52
(2H, dd, J = 9.0, 3.0, >CHCH2-), 3.40–3.30 (4H, m, -CH2O-),
3.17 (2H, t, J = 9.0 Hz, >CHCH2-) 2.99–2.92 (2H, m, -CH2O-
), 2.91–2.84 (2H, m, -CH2O-), 2.31 (6H, s, CH3) ppm.13C NMR
(75 MHz, CDCl3): d 168.2 (2C, C O), 165.3 (2C, CO-), 153.1,
153.0 (4C, arom. C), 144.9 (2C, arom. C), 140.5 (2C, arom. C),
128.1, 127.8, 127.3, 127.13, 127.06, 126.5 (20C, arom. CH), 115.7,
115.6 (8C, arom. CH), 103.3 (2C, >C ), 94.7 (2C, >C<), 70.5,
70.0, 69.7, 69.5 (8C, -CH2O-), 68.2, 66.6 (4C, -CH2OArOCH2-
), 62.0 (2C, -CO2CH2-), 51.1 (2C, >CH-), 14.7 (2C, -CH3) ppm.
FAB HRMS (acetone/NBA): calcd for C62H64O14 1032.4296 (M+);
found 1032.4297.
[12.12]Paracyclophane 5(1)(1)-para. Rf 0.18 (CHCl3). Color-
less microcrystals (from CHCl3–hexane), m.p. 208–209 ◦C. IR
(CHCl3): n 1697 (C O), 1645 (C C) cm-1. 1H NMR (300 MHz,
CDCl3): d 7.59–7.57 (4H, m, arom. H), 7.37–7.18 (16H, m, arom.
H), 6.70–6.60 (8H, m, arom. H), 4.52–4.45 (2H, m, -CO2CH2-),
4.30–4.23 (2H, m, -CO2CH2-), 4.12–4.05 (2H, m, >CH-), 4.01
(4H, t, J = 3.9 Hz, -CH2OArOCH2-), 3.73 (4H, t, J = 4.8 Hz,
-OCH2-), 3.59 (2H, dt, J = 9.0, 2.2 Hz, -OCH2-), 3.18 (2H, ddd,
J = 10.3, 7.7, 2.2 Hz, -OCH2-), 3.03–2.90 (4H, m, -OCH2-), 2.33
(6H, m, CH3) ppm.13C NMR (75 MHz, CDCl3): d 168.7 (2C,
C
O), 165.4 (2C, CO-), 153.0, 152.9 (4C, arom. C), 144.8
(2C, arom. C), 140.4 (2C, arom. C), 128.1, 127.8, 127.3, 127.1,
126.4 (20C, arom. CH), 115.7, 115.5 (8C, arom. CH), 103.1 (2C,
>C ), 94.8 (2C, >C<), 69.8, 68.9, 67.8, 66.5 (8C, -CH2O-), 62.0
(2C, -CO2CH2-), 51.1 (2C, >CH-), 14.5 (2C, -CH3) ppm. FAB
HRMS (acetone/NBA): calcd for C58H56O12 944.3772 (M+); found
944.3765.
[18.18]Paracyclophane 5(2)(2)-para. Rf 0.08 (CHCl3). Colorless
1
amorphous. IR (CHCl3): n 1693 (C O), 1645 (C C) cm-1. H
NMR (300 MHz, CDCl3): d 7.61–7.58 (4H, m, arom. H), 7.36–
7.19 (16H, m, arom. H), 6.83–6.74 (8H, m, arom. H), 4.38–4.31
(2H, m, -CO2CH2-), 4.22–4.16 (2H, m, -CO2CH2-), 4.15–4.05 (2H,
m, >CH-), 3.96 (8H, t, J = 4.7 Hz, -CH2OArOCH2-), 3.79–3.65
(12H, m, -CH2O-), 3.56 (2H, dd, J = 9.5, 2.2 Hz, >CHCH2-),
3.36–3.34 (4H, m, -CH2O-), 3.12 (2H, t, J = 9.5 Hz, >CHCH2-),
3.07–3.00 (2H, m, 3.56 -CH2O-), 2.83–2.78 (2H, m, 3.56 -CH2O-),
2.33 (6H, s, CH3) ppm.13C NMR (75 MHz, CDCl3): d 168.3 (2C,
[15.15]Paracyclophane 5(1)(2)-para. Rf 0.38 (CHCl3–MeOH =
98 : 2 v/v). Colorless amorphous. IR (CHCl3): n 1695 (C O),
1645 (C C) cm-1. 1H NMR (300 MHz, CDCl3): d 7.61–7.59 (4H,
m, arom. H), 7.36–7.17 (16H, m, arom. H), 6.89–6.67 (8H, m,
arom. H), 4.39 (2H, dt, J = 12.3, 4.2 Hz, -CO2CH2-), 4.18 (2H, dt,
J = 12.3, 4.3 Hz, -CO2CH2-), 4.10 (2H, d, J = 7.2 Hz, >CH-), 3.91
(4H, t, J = 4.5 Hz, -OCH2-), 3.79–3.77 (8H, m, -CH2O-), 3.65–
3.62 (6H, m, -CH2O-), 3.16 (2H, dd, J = 7.2, 2.4 Hz, >CHCH2-),
3.14 (2H, t, J = 4.5 Hz, >CHCH2-), 2.95–2.90 (2H, m, -CH2O-),
2.32 (6H, s, -CH3) ppm.13C NMR (75 MHz, CDCl3): d 168.7 (2C,
C
O), 165.4 (2C, CO-), 153.0 (4C, arom. C), 144.9 (2C, arom.
C), 140.5 (2C, arom. C), 128.1, 127.7, 127.2, 126.5 (20C, arom.
CH), 115.4 (8C, arom. CH), 103.1 (2C, >C ), 94.8 (2C, >C<),
70.5, 70.0, 69.7, 69.5 (12C, -CH2O-), 68.0 (4C, -CH2OArOCH2-
), 62.8 (2C, -CO2CH2-), 51.3 (2C, >CH-), 14.6 (2C, -CH3) ppm.
FAB HRMS (acetone/NBA): calcd for C66H72O16 1120.4820 (M+);
found 1120.4827.
C
O), 165.4 (2C, CO-), 153.0, 152.9 (4C, arom. C), 144.9 (2C,
arom. C), 140.4 (2C, arom. C), 128.1, 127.7, 127.3, 127.2, 127.1,
126.5 (20C, arom. CH), 115.39, 115.36 (8C, arom. CH), 102.9 (2C,
>C ), 94.9 (2C, >C<), 69.8, 69.7, 69.5, 68.9, 67.9, 67.5 (12C, -
CH2O-), 62.9 (2C, -CO2CH2-), 51.4 (2C, >CH-), 14.5 (2C, -CH3)
ppm. FAB HRMS (acetone/NBA): calcd for C62H64O14 1032.4296
(M+); found 1032.4261.
[21.21]Paracyclophane 5(2)(3)-para. Rf 0.38 (CHCl3–MeOH =
98 : 2 v/v). Colorless amorphous. IR (CHCl3): n 1693 (C O) cm-1.
1H NMR (300 MHz, CDCl3): d 7.62–7.59 (4H, m, arom. H), 7.36–
7.18 (16H, m, arom. H), 6.84–6.77 (8H, m, arom. H), 4.34–4.28
(2H, m, -CO2CH2-), 4.22–4.17 (2H, m, -CO2CH2-), 4.08 (2H, dd,
J = 6.9 Hz, >CH-), 3.98 (8H, dd, J = 9.0, 4.2 Hz, -CH2OArOCH2-
), 3.79–3.76 (4H, m, -CH2O-), 3.69–3.66 (16H, m, -CH2O-), 3.59
(2H, dd, J = 9.5, 2.2 Hz, >CHCH2-), 3.37–3.34 (4H, m, -CH2O-
), 3.12–3.06 (4H, m, -CH2O-), 2.78–2.74 (2H, m, -CH2O-), 2.33
(6H, s, CH3) ppm.13C NMR (75 MHz, CDCl3): d 168.3 (2C,
[18.18]Paracyclophane 5(1)(3)-para. Rf 0.29 (CHCl3–MeOH =
98 : 2 v/v). Colorless amorphous. IR (CHCl3): n 1693 (C O),
1
1645 (C C) cm-1. H NMR (300 MHz, CDCl3): d 7.63–7.60
(4H, m, arom. H), 7.35–7.18 (16H, m, arom. H), 6.72–6.68 (8H,
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C
O), 165.4 (2C, CO-), 153.0 (4C, arom. C), 144.9 (2C, arom.
-CH2O-, -CH2OArOCH2-), 62.7 (2C, -CO2CH2-), 51.4 (2C, >CH-
), 14.6 (2C, -CH3) ppm. FAB HRMS (acetone/NBA): calcd for
C70H80O18 1208.5345 (M+); found 1208.5341.
C), 140.5 (2C, arom. C), 128.1, 127.7, 127.2, 127.1, 126.5 (20C,
arom. CH), 115.5 (8C, arom. CH), 103.0 (2C, >C ), 94.8 (2C,
>C<), 70.8, 70.6, 70.4, 69.8, 69.7, 69.5, 69.3 (16C, -CH2O-), 67.9
(4C, -CH2OAr), 62.7 (2C, -CO2CH2-), 51.4 (2C, >CH-), 14.6 (2C,
-CH3) ppm. FAB HRMS (acetone/NBA): calcd for C70H80O18
1208.5345 (M+); found 1208.5286.
Diploid of 5(3)(2)-para. Rf 0.30 (CHCl3–MeOH = 95 : 5 v/v).
Colorless amorphous. IR (CHCl3):
n 1695 (C O), 1647
1
(C C) cm-1. H NMR (300 MHz, CDCl3): d 7.62–7.59 (8H, m,
arom. H), 7.53–7.15 (32H, m, arom. H), 6.85–6.76 (16H, m, arom.
H) 4.34–4.28 (4H, m, -CO2CH2-), 4.26–4.18 (4H, m, -CO2CH2-
), 4.10–3.95 (20H, m, >CH-, -CH2OArOCH2-), 3.85–3.71 (24H,
m, -CH2O-), 3.69–3.61 (12H, m, -CH2O-), 3.61–3.55 (8H, m, -
CH2O-), 3.30 (8H, t, J = 4.8 Hz, -CH2O-), 3.10–3.01 (8H, m,
-CH2O-), 2.77–2.70 (4H, m, -CH2O-), 2.34 (3H, s, CH3), 2.32
(6H, s, CH3)-2.27 (3H, s, CH3) ppm.13C NMR (75 MHz, CDCl3):
d 165.3 (4C, C O), 165.3 (4C, CO-), 153.0 (8C, arom. C), 145.0
(4C, arom. C), 140.5 (4C, arom. C), 128.1, 127.7, 127.2, 127.2,
126.7, 125.6 (40C, arom. CH), 115.5 (16C, arom. CH), 103.0 (4C,
>C =), 94.8 (4C, >C<), 70.8, 70.6, 70.5, 70.2, 69.8, 69.4, 69.0, 68.0
(40C, -CH2O-), 62.6 (4C, -CO2CH2-), 51.3 (4C, >CH-), 14.7 (4C,
-CH3) ppm. FAB HRMS (acetone/NBA): calcd for C140H160O36
2417.0689 (M+); found 2417.0669.
[18.18]Paracyclophane 5(3)(1)-para. Rf 0.22 (CHCl3–MeOH =
98 : 2 v/v). Colorless amorphous. IR (CHCl3): n 1695 (C O)
1647 (C C) cm-1. H NMR (300 MHz, CDCl3): d 7.60–7.53
1
(4H, m, arom. H), 7.36–7.21 (16H, m, arom. H), 6.84–6.78 (8H,
m, arom. H), 4.46–4.40 (2H, m, -CO2CH2-), 4.35–4.28 (2H, m,
-CO2CH2-), 4.12–4.03 (10H, m, >CH-, -CH2O-), 3.78 (4H, t, J =
4.6 Hz, -CH2O-), 3.67–3.63 (4H, m, -CH2O-), 3.60–3.47 (6H, m,
-CH2O-, >CHCH2-), 3.31–3.29 (4H, m, -CH2O-), 3.10 (2H, t,
J = 9.0 Hz, >CHCH2-), 3.00–2.94 (2H, m, -CH2O-), 2.82–2.75
(2H, m, -CH2O-), 2.31, (6H, s, CH3) ppm.13C NMR (75 MHz,
CDCl3): d 168.2 (2C, C O), 165.2 (2C, CO-), 153.1, 153.0
(4C, arom. C), 144.9 (2C, arom. C), 140.5 (2C, arom. C), 128.52,
128.47, 128.1, 127.7, 127.2, 127.15, 127.05, 126.5 (20C, arom. CH),
115.6, 115.5 (8C, arom. CH), 103.1 (2C, >C ), 94.8 (2C, >C<),
70.8, 70.6, 70.3, 69.9, 69.7, 69.4, 68.13, 67.99, 66.6 (16C, -CH2O-
), 61.9 (2C, -CO2CH2-), 51.3 (2C, >CH-), 14.7 (2C, -CH3) ppm.
FAB HRMS (acetone/NBA): calcd for C66H72O16 1120.4820 (M+);
found 1120.4813.
[24.24]Paracyclophane 5(3)(3)-para. Rf 0.42 (CHCl3–MeOH =
96 : 4 v/v). Colorless amorphous. IR (CHCl3): n 1692 (C O),
1
1645 (C C) cm-1. H NMR (300 MHz, CDCl3): d 7.62–7.59
(4H, m, arom. H), 7.37–7.18 (16H, m, arom. H), 6.83–6.79 (8H,
m, arom. H), 4.32–4.27 (2H, m, -CO2CH2-), 4.21–4.18 (2H, m,
-CO2CH2-), 4.08–4.02 (10H, m, >CH-, -CH2OArOCH2-), 3.89–
3.76 (8H, m, -CH2O-), 3.76–3.61 (18H, m, -CH2O-), 3.61–3.51
(4H, m, -CH2O-), 3.30–3.29 (4H, m, -CH2O-), 3.06 (4H, t, J =
8.1 Hz, -CH2O-), 2.76–2.73 (2H, m, -CH2O-), 2.32 (6H, s, CH3)
ppm.13C NMR (75 MHz, CDCl3): d 168.2 (2C, C O), 165.4 (2C,
CO-), 153.0 (4C, arom. C), 145.0 (2C, arom. C), 140.5 (2C, arom.
C), 128.1, 127.7, 127.25, 127.2, 127.1, 126.5 (20C, arom. CH),
115.5 (8C, arom. CH), 103.0 (2C, >C =), 94.8 (2C, >C<), 70.8,
70.6, 70.2, 69.8, 69.4, 69.3 (20C, -CH2O-), 68.0 (4C, -CH2OAr),
62.7 (2C, -CO2CH2-), 51.4 (2C, >CH-), 14.7 (2C, -CH3) ppm.
FAB HRMS (acetone/NBA): calcd for C74H88O20 1296.5869 (M+);
found 1296.5846.
Diploid of 5(3)(1)-para. Rf 0.15 (CHCl3–MeOH = 98 : 2 v/v).
Colorless amorphous. IR (CHCl3):
n 1697 (C O) 1647
(C C) cm-1. 1H NMR (300 MHz, CDCl3): d 7.60–7.57 (8H,
m, arom. H), 7.35–7.16 (32H, m, arom. H), 6.85–6.78 (16H,
m, arom. H), 4.51–4.40 (4H, m, -CO2CH2-), 4.40-4.30 (4H, m,
-CO2CH2-), 4.24–3.96 (24H, m, >CH-, -CH2O-), 3.86–3.76 (8H,
m, -CH2O-), 3.70–3.60 (8H, m, -CH2O-), 3.60–3.53 (8H, m, -
CH2O-, >CHCH2-), 3.37–3.17 (8H, m, -CH2O-), 3.17–2.88 (8H,
m, -CH2O-), 2.80–2.65 (4H, m, -CH2O-), 2.25 (12H, s, CH3)
ppm.13C NMR (75 MHz, CDCl3): d 168.3 (4C, C O), 165.3 (4C,
CO-), 153.0 (8C, arom. C), 144.9 (4C, arom. C), 140.5 (4C, arom.
C), 128.9, 128.3, 128.1, 127.7, 127.3, 127.2, 126.6, 125.6 (40C,
arom. CH), 115.6, 115.5 (16C, arom. CH), 102.9 (4C, >C ), 94.9
(4C, >C<), 70.8, 70.6, 70.5, 70.2, 69.8, 69.4, 68.0, 66.7, 66.4, 63.7
(32C, -CH2O-), 62.0, 61.5 (4C, -CO2CH2-), 51.4, 49.9 (4C, >CH-
), 14.8 (4C, -CH3) ppm. FAB HRMS (acetone/NBA): calcd for
C132H144O32 2240.9641 (M+); found 2240.9675.
[12.12]Paracyclophane 7(1)-para. Rf 0.49 (CHCl3). Colorless
amorphous. IR (CHCl3): n 1693 (C O), 1643 (C C) cm-1.
1H NMR (300 MHz, CDCl3): d 7.53–7.50 (4H, m, arom. H),
7.34–7.21 (16H, m, arom. H), 6.94–6.80 (4H, m, arom. H), 6.66–
6.60 (4H, m, arom. H), 4.54–4.48 (2H, m, -CO2CH2-), 4.33–4.27
(2H, m, -CO2CH2-), 4.07 (4H, t, J = 5.0 Hz, -CH2OArOCH2-
), 3.79–3.76 (2H, m, >CH-), 2.40–2.37 (4H, m, -CH2Ar-), 2.32
(6H, s, CH3), 1.33–1.27 (9H, m, -CH2-), 0.98–0.96 (7H, m, -CH2-
) ppm.13C NMR (75 MHz, CDCl3): d 167.2 (2C, C O), 165.8
(2C, CO-), 152.8 (2C, arom. C), 145.2 (2C, arom. C), 140.8 (2C,
arom. C), 139.7 (2C, arom. C), 128.1, 127.7, 127.0, 126.6, 126.1
(20C, arom. CH), 115.3 (8C, arom. CH), 108.0 (2C, >C =), 95.4
(2C, >C<), 66.5 (2C, -CH2OAr), 61.8 (2C, -CO2CH2-), 48.6 (2C,
>CH-), 35.1, 31.7, 30.8, 29.0, 25.9 (10C, -CH2-), 14.6 (2C, -CH3)
ppm. FAB HRMS (acetone/NBA): calcd for C62H64O8 936.4601
(M+); found 936.4615.
[21.21]Paracyclophane 5(3)(2)-para. Rf 0.44 (CHCl3–MeOH =
95 : 5 v/v). Colorless amorphous. IR (CHCl3): n 1693 (C O),
1645 (C C) cm-1. 1H NMR (300 MHz, CDCl3): d 7.61–7.58 (4H,
m, arom. H), 7.36–7.18 (16H, m, arom. H), 6.82–6.78 (8H, m,
arom. H), 4.32 (2H, dt, J = 12.0, 4.8 Hz, -CO2CH2-), 4.21 (2H,
dt, J = 12.0, 4.8 Hz, -CO2CH2-), 4.07 (2H, d, J = 7.2 Hz, >CH-),
4.01 (8H, t, J = 3.3 Hz, t, J = 3.3 Hz, -CH2OArOCH2-), 3.80–3.72
(12H, m, -CH2O-), 3.65 (4H, t, J = 4.2 Hz, -CH2O-), 3.61–3.55
(6H, m, -CH2O-), 3.30 (4H, t, J = 4.8 Hz, -CH2O-), 3.10–2.99
(4H, m, -CH2O-), 2.80–2.75 (2H, m, -CH2O-), 2.34 (6H, s, CH3)
ppm.13C NMR (75 MHz, CDCl3): d 168.2 (2C, C O), 165.4 (2C,
CO-), 153.0 (4C, arom. C), 144.9 (2C, arom. C), 140.5 (2C,
arom. C), 128.1, 127.7, 127.2, 127.18, 127.06, 126.5 (20C, arom.
CH), 115.54, 115.47 (8C, arom. CH), 103.0 (2C, >C =), 94.8 (2C,
>C<), 70.8, 70.6, 70.3, 69.9, 69.8, 69.7, 69.4, 68.04, 67.99 (20C,
Diploid of 7(1)-para. Rf 0.24 (CHCl3). Colorless amorphous. IR
(CHCl3): n 1690 (C O), 1645 (C C) cm-1. 1H NMR (300 MHz,
CDCl3): d 7.53–7.51 (8H, m, arom. H), 7.32–7.10 (32H, m, arom.
H), 6.98–6.49 (16H, m, arom. H), 4.55–4.31 (8H, m, -CO2CH2-),
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4.16–4.00 (8H, m, -CH2OArOCH2-), 3.80–3.701 (4H, m, >CH-),
2.38–2.20 (20H, m, -CH2Ar-, CH3), 1.33–1.27 (18H, m, -CH2-),
0.98–0.96 (14H, m, -CH2-) ppm.13C NMR (75 MHz, CDCl3): d
167.2 (4C, C O), 165.8 (4C, CO-), 152.8 (4C, arom. C), 145.2
(4C, arom. C), 140.8 (4C, arom. C), 139.7 (4C, arom. C), 128.1,
127.7, 127.1, 126.6, 126.2 (40C, arom. CH), 115.5, 115.3 (16C,
arom. CH), 108.0 (4C, >C =), 95.4 (4C, >C<), 66.7, 66.4 (4C,
-CH2OAr), 62.5, 61.8 (4C, -CO2CH2-), 48.6 (4C, >CH-), 35.1,
31.7, 31.0, 29.0, 25.9 (20C, -CH2-), 14.6 (4C, -CH3) ppm. FAB
HRMS (acetone/NBA): calcd for C124H128O16 1873.9236 (M+);
found 1872.9220.
-CO2CH2-), 48.9 (2C, >CH-), 35.2, 31.5, 31.0, 29.5, 25.9 (10C,
-CH2-), 14.7 (2C, -CH3) ppm. FAB HRMS (acetone/NBA): calcd
for C70H80O12 1112.5650 (M+); found 1112.5647.
Diploid of 7(3)-para. Rf 0.39 (CHCl3–MeOH = 97 : 3 v/v). Col-
orless amorphous. IR (CHCl3): n 1686 (C O), 1647 (C C) cm-1.
1H NMR (300 MHz, CDCl3): d 7.53–7.51 (8H, m, arom. H), 7.34–
7.15 (32H, m, arom. H), 7.00–6.77 (16H, m, arom. H), 4.31–4.19
(8H, m, -CO2CH2-), 4.02 (8H, t, J = 4.9 Hz, -CH2OArOCH2-),
3.79 (8H, t, J = 4.8 Hz, -CH2O-), 3.79 (4H, m, >CH-), 3.73–3.60
(24H, m, -CH2O-), 2.36–2.16 (8H, m, -CH2ArCH2-), 2.25 (12H, s,
-CH3), 1.33–1.26 (18H, m, -CH2-), 1.10–0.90 (14H, m, -CH2-)
ppm.13C NMR (75 MHz, CDCl3): d 166.6 (4C, C O), 165.7 (4C,
CO-), 153.0 (4C, arom. C), 145.3 (4C, arom. C), 140.8 (4C,
arom. C), 139.8 (4C, arom. C), 128.1, 127.7, 127.1, 126.7, 126.2
(40C, arom. CH), 115.6, 115.5 (16C, arom. CH), 108.0 (4C, >C =),
95.1 (4C, >C<), 70.9, 70.6, 69.8, 69.5, 68.1 (20C, -CH2O-), 62.6
(4C, -CO2CH2-), 48.9 (4C, >CH-), 35.2, 31.6, 31.0, 29.5, 25.9 (20C,
-CH2-), 14.8, 14.7 (4C, -CH3) ppm. FAB HRMS (acetone/NBA):
calcd for C140H160O24 2226.1334 (M+); found 2225.1331.
[15.15]Paracyclophane 7(2)-para. Rf 0.57 (CHCl3). Colorless
1
amorphous. IR (CHCl3): n 1689 (C O), 1645 (C C) cm-1. H
NMR (300 MHz, CDCl3): d 7.53–7.50 (4H, m, arom. H), 7.33–
7.18 (16H, m, arom. H), 6.90–6.85 (4H, m, arom. H), 6.75–6.73
(4H, m, arom. H), 4.42–4.35 (2H, m, -CO2CH2-), 4.20–4.15 (2H,
m, -CO2CH2-), 3.96 (4H, t, J = 4.8 Hz, -CH2OArOCH2-), 3.81–
3.73 (10H, m, >CH-, -CH2O-), 2.31–2.26 (10H, m, -CH2ArCH2-
, CH3), 1.40–1.20 (8H, m, -CH2-), 1.00–0.90 (8H, m, -CH2-)
ppm.13C NMR (75 MHz, CDCl3): d 166.9 (2C, C O), 165.8 (2C,
CO-), 153.0 (2C, hyd-arom. C), 145.3 (2C, hyd-arom. C), 140.8
(2C, arom. C), 139.7 (2C, arom. C), 128.1, 128.0, 127.7, 127.0,
126.7, 126.1 (20C, arom. CH), 115.4 (8C, arom. CH), 108.0 (2C,
>C ), 95.2 (2C, >C<), 69.7, 69.6, 67.9 (6C, -CH2O-), 62.5 (2C,
-CO2CH2-), 48.8 (2C, >CH-), 35.2, 31.6, 31.0, 29.5, 25.9 (10C,
-CH2-), 14.6 (2C, -CH3) ppm. FAB HRMS (acetone/NBA): calcd
for C66H72O10 1024.5125 (M+); found 1024.5048.
[16.16]Paracyclophane 9. Rf 0.81 (CHCl3). Colorless amor-
phous. IR (CHCl3): n 1686 (C O), 1647 (C C) cm-1. 1H NMR
(300 MHz, CDCl3): d 7.53–7.51 (4H, m, arom. H), 7.31–7.19
(16H, m, arom. H), 7.01–6.92 (8H, m, arom. H), 4.16–4.04 (4H,
m, -CO2CH2-), 3.80–3.70 (2H, m, >CH-), 2.54–2.50 (4H, m, -
CH2ArCH2-), 2.32 (6H, s, -CH3), 2.40–2.25 (4H, m, -CH2ArCH2-
), 1.75–1.50 (8H, m, -CH2-), 1.50–1.10 (20H, m, -CH2-), 1.10–0.80
(8H, m, -CH2-) ppm. 13C NMR (75 MHz, CDCl3): d 166.2 (2C,
C
O), 166.0 (2C, CO-), 145.3 (4C, arom. C), 140.9 (2C, arom.
Diploid of 7(2)-para. Rf 0.28 (CHCl3–MeOH = 98 : 2 v/v). Col-
orless amorphous. IR (CHCl3): n 1690 (C O), 1647 (C C) cm-1.
1H NMR (300 MHz, CDCl3): d 7.53–7.50 (8H, m, arom. H), 7.46–
7.03 (32H, m, arom. H), 7.00–6.79 (16H, m, arom. H), 4.41–4.14
(8H, m, -CO2CH2-), 4.09–3.90 (8H, m, -CH2OArOCH2-), 3.90–
3.66 (20H, m, >CH-, -CH2O-), 2.35–2.24 (20H, m, -CH2ArCH2-
, CH3), 1.40–1.20 (16H, m, -CH2-), 1.00–0.90 (16H, m, -CH2-)
ppm.13C NMR (75 MHz, CDCl3): d 166.4 (4C, C O), 165.7
(4C, CO-), 153.0 (4C, arom. C), 145.3 (4C, arom. C), 140.8
(4C, arom. C), 140.0, 139.8 (4C, arom. C), 128.7, 128.1, 127.7,
127.2, 127.1, 126.8, 126.2, 125.7, 125.5 (40C, arom. CH), 115.5,
115.4 (16C, arom. CH), 108.1 (4C, >C =), 95.1 (4C, >C<), 69.8,
69.7, 69.5, 67.9 (12C, -CH2O-), 62.5 (4C, -CO2CH2-), 49.0 (4C,
>CH-), 35.2, 31.5, 31.0, 29.4, 28.9, 25.9 (20C, -CH2-), 14.8 (4C,
-CH3) ppm. FAB HRMS (acetone/NBA): calcd for C132H144O20
2050.0285 (M+); found 2049.0256.
C), 139.8 (2C, arom. C), 128.2, 128.0, 127.6, 127.0, 126.7, 126.2
(28C, arom. CH), 108.3 (2C, >C =), 95.0 (2C, >C<), 63.5 (2C,
-CH2O-), 48.9 (2C, >CH-), 35.4, 35.3 (4C, -CH2ArCH2), 31.8,
31.2, 31.1, 29.6, 29.0, 28.7, 26.1 (18C, -CH2-), 14.5 (2C, -CH3)
ppm. FAB HRMS (acetone/NBA): calcd for C72H84O6 1044.6268
(M+); found 1044.6274.
Diploid of 9. Rf 0.74 (CHCl3). Colorless amorphous. n 1684
(C O), 1647 (C C) cm-1. 1H NMR (300 MHz, CDCl3): d 7.59–
7.51 (8H, m, arom. H), 7.32–7.12 (32H, m, arom. H), 7.09–6.92
(16H, m, arom. H), 4.31–3.91 (8H, m, -CO2CH2-), 3.80–3.65 (4H,
m, >CH-), 2.69–2.40 (8H, m, -CH2ArCH2-), 2.32–2.23 (8H, m,
-CH2ArCH2-), 2.25 (6H, s, -CH3), 2.23 (6H, s, -CH3), 1.75–1.48
(16H, m, -CH2-), 1.48–1.10 (40H, m, -CH2-), 1.10–0.80 (16H, m,
-CH2-) ppm. 13C NMR (75 MHz, CDCl3): d 166.2 (4C, C O),
166.1 (4C, CO-), 145.4 (8C, arom. C), 140.9 (4C, arom. C), 139.8
(4C, arom. C), 128.7, 128.2, 128.1, 127.7, 127.1, 126.8, 126.2 (56C,
arom. CH), 108.4 (4C, >C =), 95.1 (4C, >C<), 63.5 (4C, -CH2O-),
49.0 (4C, >CH-), 35.4, 35.3 (8C, -CH2ArCH2), 31.8, 31.5, 31.3,
31.1, 29.6, 29.4, 29.1, 28.8, 26.2, 26.1 (36C, -CH2-), 14.5 (4C, -
CH3) ppm. FAB HRMS (acetone/NBA): calcd for C144H168O12
2090.2570 (M+); found 2089.2532.
[18.18]Paracyclophane 7(3)-para. Rf 0.53 (CHCl3–MeOH =
97 : 3 v/v). Colorless amorphous. IR (CHCl3): n 1690 (C O),
1
1647 (C C) cm-1. H NMR (300 MHz, CDCl3): d 7.53–7.51
(4H, m, arom. H), 7.34–7.18 (16H, m, arom. H), 6.94–6.91 (4H,
m, arom. H), 6.81–6.78 (4H, m, arom. H), 4.33–4.17 (4H, m, -
CO2CH2-), 4.02 (4H, t, J = 4.9 Hz, -CH2OArOCH2-), 3.79 (3H,
t, J = 4.8 Hz, -CH2O-), 3.79 (3H, m, >CH-), 3.75–3.60 (12H, m,
-CH2O-), 2.34–2.25 (4H, m, -CH2ArCH2-), 2.28 (6H, s, -CH3),
1.33-1.27 (9H, m, -CH2-), 1.10–0.90 (7H, m, -CH2-) ppm.13C
NMR (75 MHz, CDCl3): d 166.6 (2C, C O), 165.7 (2C, CO-
), 153.0 (2C, arom. C), 145.3 (2C, arom. C), 140.8 (2C, arom.
C), 139.8 (2C, arom. C), 128.1, 127.7, 127.1, 126.7, 126.2 (20C,
arom. CH), 115.6, 115.5 (8C, arom. CH), 108.0 (2C, >C =), 95.1
(2C, >C<), 70.8, 70.6, 69.8, 69.4, 68.1 (10C, -CH2O-), 62.6 (2C,
[12.12]Paracyclophane 5(1)(1)-Cl,para. Rf 0.21 (CHCl3). Color-
less microcrystals (from CHCl3–hexane), m.p. 152–153 ◦C. IR
(CHCl3): n 1699 (C O), 1647 (C C) cm-1. 1H NMR (300 MHz,
CDCl3): d 7.49–7.46 (4H, m, arom. H), 7.38–7.18 (12H, m, arom.
H), 6.71–6.68 (8H, s, arom. H), 4.49–4.44 (2H, m, -CO2CH2-
), 4.35–4.30 (2H, m, -CO2CH2-), 4.06–3.99 (6H, m, >CH-, -
CH2OArOCH2-), 3.76 (4H, t, J = 4.4 Hz, -OCH2-), 3.59 (2H,
dt, J = 9.5, 2.6 Hz, -OCH2-), 3.19–3.13 (2H, m, -OCH2-),
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3.13–2.90 (4H, m, -OCH2-), 2.31 (6H, s, CH3) ppm.13C NMR
(75 MHz, CDCl3): d 168.39 (2C, C O), 168.35 (2C, CO-),
153.0, 152.9 (4C, arom. C), 143.0 (2C, arom. C), 138.6 (2C, arom.
C), 133.9 (2C, arom. C), 133.3 (2C, arom. C), 128.6, 128.4, 127.8,
127.6 (16C, arom. CH), 115.8, 115.7, 115.6 (8C, arom. CH), 103.1
(2C, >C =), 93.9 (2C, >C<), 69.5, 69.0, 67.9, 66.5 (8C, -CH2O-
), 62.1 (2C, -CO2CH2-), 51.2 (2C, >CH-), 14.5 (2C, -CH3) ppm.
FAB HRMS (acetone/NBA): calcd for C58H52O12Cl4 1082.2198
(M+); found 1080.2236.
no unusual trends. The maximum and minimum peaks on the
final difference Fourier map corresponded to 0.86 and -0.77
3
˚
e-/A , respectively. The crystallographic data (excluding structure
factors) for the structure in this paper have been deposited with
the Cambridge Crystallographic Data Centre as CCDC 769197.†
Acknowledgements
This research was supported by Grants-in-Aid for Scientific
Research (C), No. 15550039 and No. 19550046, from the Japan
Society for the Promotion of Science. We gratefully acknowledge
Professor Teruo Shinmyouzu, Institute for Materials Chemistry
and Engineering, Kyushu University, Japan, for the measurement
of the high-resolution FAB mass spectrum.
X-ray analysis of [22]paracyclophane 3(8)(1)-para
A colorless block crystal of C54H56O8 having approximate di-
mensions of 0.90 ¥ 0.80 ¥ 0.70 mm was mounted on a glass
fiber. All measurements were made on a diffractometer with
graphite monochromated Mo-Ka radiation and a rotating anode
generator. Cell constants and an orientation matrix for data
collection, obtained from a least-squares refinement using the
setting angles of 25 carefully centred reflections in the range
30.12 < 2q < 34.17◦ corresponded to a C-centered monoclinic
Notes and references
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(b) M. N. Chatterjee, E. R. Kay and D. A. Leigh, J. Am. Chem. Soc.,
2006, 128, 4058–4073; (c) D. J. Leigh and A. R. Thomson, Org. Lett.,
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˚
˚
cell with dimensions: a = 14.5489(17) A, b = 31.423(9) A, c =
◦
3
˚
˚
11.6090(13) A, b = 118.413(8) , V = 4668.0(14) A , Z = 4, F.W. =
833.03, the calculated density is 1.185 g cm-3, the space group
was determined to be C2/c (#15). The data were collected at a
temperature of 25 1 ◦C using the w scan technique to a maximum
2q value of 55.0◦. Omega scans of several intense reflections, made
prior to data collection, had an average width at half-height of
0.27◦ with a take-off angle of 6.0◦. Scans of (1.73 + 0.30 tan q)◦
were made at a speed of 16.0◦ min-1 (in w). The weak reflections
(I < 10.0s(I)) were rescanned (maximum of 2 scans) and the counts
were accumulated to ensure good counting statistics. Stationary
background counts were recorded on each side of the reflection.
The ratio of peak counting time to background counting time
was 2 : 1. The diameter of the incident beam collimator was
0.5 mm and the crystal to detector distance was 235 mm. The
computer-controlled slits were set to 3.0 mm (horizontal) and
3.0 mm (vertical). Of the 6419 reflections that were collected, 5364
were unique (Rint = 0.124). The intensities of three representative
reflections were measured after every 0 reflections. Over the
course of data collection, the standards decreased by 36.5%. A
polynomial correction factor was applied to the data to account
for this phenomenon. The linear absorption coefficient, m, for Mo-
Ka radiation is 0.784 cm-1. An empirical absorption correction
based on azimuthal scans of several reflections was applied which
resulted in transmission factors ranging from 0.735 to 0.947.
The data were corrected for Lorentz and polarization effects. A
correction for secondary extinction24 was applied (coefficient =
245.440002). The structure was solved by direct methods, SIR9225
and expanded using Fourier techniques, DIRDIF99.26 The non-
hydrogen atoms were refined anisotropically. Hydrogen atoms
were refined using the riding model. The final cycle of full-
matrix least-squares refinement on F2 was based on 2891 observed
reflections and 309 variable parameters and converged (largest
parameter shift was 0.00 times its esd) with unweighted and
weighted agreement factors of R1 = 0.0878 and wR2 = 0.1042.
The standard deviation of an observation of unit weight was
4.75. The weighting scheme was based on counting statistics.
Plots of R (|Fo| - |Fc|)2 versus |Fo|, reflection order in
w
data collection, sin q/l and various classes of indices showed
1506 | Org. Biomol. Chem., 2011, 9, 1491–1507
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