Full text of DOI:10.1002/jhet.5570380601

Nov-Dec 2001
One-Step Syntheses of Macrocyclic Compounds: A Short Review
1239
Krzysztof E. Krakowiak*[a], Reed M. Izatt [b], and Jerald S. Bradshaw [b]
[a] IBC Advanced Technologies, Inc., 856 East Utah Valley Drive, American Fork, UT 84003
[b] Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602
Received June 20, 2001
Macrocyclic ligands have been prepared by various one-step cyclooligomerization processes. This short
review covers one-step cyclization reactions involving the formation of four to twenty or more new covalent
bonds. The new macrocycles reviewed include cyclophanes, biscrown ethers, cryptands, macrolides, cage com-
pounds, calixarenes, homocalixarenes, cucubiturils, and supercryptands all prepared by one-step syntheses.
J. Heterocyclic Chem., 38, 1239 (2001).
Introduction.
macrocyclic ligands that form with 4-20 or more new
bonds (see Scheme 1). Formation of a particular structure
depends on reaction conditions such as template effects,
temperature, concentration of starting materials, and other
unknown factors. Up to now, cryptands, biscrown ethers,
supercryptands, cylindrical polycyclic compounds and
cubic compounds have been prepared by direct one-step
methods. However, nearly every day additional new and
unique structures are added to this list [3,4].
In this review, we show a few one-step cyclization reac-
tions that form specific macrocyclic compounds. The
more bonds that are formed during cyclization starting
with simple starting materials, the more complicated are
the produced macrocyclic products. We hope that this
review will help in the search for new routes for
Synthetic polymer chemistry was developed before syn-
thetic macrocyclic chemistry. Organic polymers cannot be
synthesized without having macrocyclic compounds as
side products and vice versa. The preferential formation of
only one product often depends on the conditions of the
reaction. Cyclic products are usually not wanted in linear
organic polymers because of their deleterious effect on
polymer characteristics. During polymerization reactions,
thousands of new bonds are formed while cyclization reac-
tions result from only a few formed bonds [1,2].
In the synthesis of macrocyclic ligands, different macro-
cyclic compounds can form from the same ratio of starting
materials. For example, starting from a 1:2 ratio of
diamine and dihalide (or ditosylate), it is possible to obtain
"
cyclooligomerization" to form new and unique macro-
cyclic compounds. Also, it provides information for non-
synthetic chemists that will allow them to prepare desired
macrocyclic compounds in order to study their physical
and chemical properties. The main purpose of this review
is to give examples of some of the most important synthe-
ses of macrocyclic compounds and to show the fastest
approach to these complicated molecules. Many reviews
and books are devoted to the synthesis of macrocyclic
compounds [1,5-10], but no review has been published
with an emphasis on one-step syntheses by the formation
of many new bonds.
Scheme 1
NH2
NH2
X
N
o
+
2
N
o
N
or
N
o
4 Bonds
Biscrown
X
4
Bonds
Cryptands
o
o
N
N
N
N
N
or
N
o
N
N
o
or
8 Bonds
Triscrown
or
N
o
N
o
N
N
A special place in the synthesis of macrocyclic com-
pounds belongs to the synthesis of torands, especially one
that is formed from an aromatic ketoaminoaldehyde during
a triple cyclopolymerization reaction (Scheme 2).
N
N
N
o
N
N
N o
8
Bonds
o
8
Bonds
Cylindrical
Molecules
Supercryptands
N
or
o
N
N
N
o
N
N
No
N
o
or
o
o
N
N
N
o
N
N
N
N
N
o
6 Bonds
N
N
N
or
N
1
2
0 Bonds
Pentagonal
Sphere
Cube
o
or
o
o
o
N
N
12 Bonds
Triangular
Prism
N
o
N
or
N
o
N
N
o
N
N
N
N
o
N
N
o
N
1
2 Bonds
Tower
20 Bonds
Scale
Scheme 1.

1
240
K. E. Krakowiak, R. M. Izatt, and J. S. Bradshaw
Vol. 38
Friedlander condensation and cesium hydroxide templated
trimerization gave an expanded torand in 50% yield [9,11].
Another cyclization reaction that is unusual is the so
called "zip" reaction, which causes a ring expansion by the
insertion of a side chain. For example, conversion of a lac-
tam into a cyclic aminoamide with ring enlargement has
been achieved using potassium aminopropylamide in 1,3
propanediamine (Scheme 3). In this way, a 13-membered
lactam has been transformed into a 33-membered cyclic
aminoamide by five successive introductions of a
Macrocyclic Compounds Formed by Three to Six New
Double Bonds.
CH CH CH N unit into the ring (Scheme 3) [12,13].
2
2
2
Some interesting furan-containing macrocycles have
been prepared using the base catalyzed Wittig Reaction as
shown in Scheme 6 [17]. In this case, 5-formylfuran-2-
ylmethyltriphenylphosphonium chloride cyclocondensed
to form the trimer to hexamer products with three to six
double bonds. These products were isolated in low yields.
Macrocyclic Compounds Formed by Two to Twelve New
Bonds.
The reaction of an aromatic diacid dichloride with a
diamine followed by reduction is a common method for
producing 1:1, 2:2, 3:3 and higher-order cyclocondensa-
tion products. The most detailed study of this type of
cyclocondensation reaction was done by Raymond and
coworkers for the reactions of terphthalyl dichloride with
various diamines as shown in Scheme 4 [14]. Where n = 2,
the cyclocondensation products included the trimer (m =
Macrocyclic Compounds Formed by Four New Bonds.
The best example of this reaction type is the 2:2 cycliza-
tion reaction. This reaction is carried out under high dilu-
tion techniques or with a template. The high dilution reac-
tion usually produces a 1:1 cyclization compound as a by-
product. If one of the reactants contains a rigid molecule,
the possibility of producing 1:1 cyclization products is
reduced. The concentration of the reactants also influ-
ences the types of addition products. High concentrations
favor the formation of 2:2 addition products, however,
more linear polymer is also formed. One example of a
rigid difunctional molecule that reacted by 2:2 rather than
1:1 cyclization is catechol, which reacted with 1,5-
dichloro-3-oxapentane to form dibenzo-18-crown-6 exclu-
sively (Scheme 7) [18].
2
) (the product of three diacid dichlorides with three
diamines) to the hexamer. Where n = 4, dimer to pentamer
m = 3) products were isolated; and where n = 6, dimer to
(
pentamer (m = 4) products. The yields of pentamer and
hexamer products were less than 1%. The best yields were
for the dimer (24%), a 28-membered ring, in the reaction
using 1,6-diaminohexane (n = 6) and for the trimer (17%),
a 30-membered ring, in the reaction with ethylenediamine
(n = 2) [14].
An important result of templated synthesis using
polyamines coordinated with metal ions is that it allows
the preparation of peraza macrocycles without the need for
protecting groups on the nitrogen atoms. This reduces the
number of steps needed in a synthetic sequence. The
Vögtle and coworkers studied the cyclocondensation
reactions of terephthalyl dichloride and various derivatives
of ethylenediamine (Scheme 5) [15,16]. Where R = ben-
zyl, the 3:3 cyclo-condensation product (n = 2) was iso-
lated in a 25% yield and the 4:4 adduct in a 3% yield.

Nov-Dec 2001
One-Step Syntheses of Macrocyclic Compounds: A Short Review
1241
appropriate templated cation allows for the formation of
macrocycles by 1:1 or 2:2 cyclo condensations. It is
important to note that even small cations can produce 2:2
cyclization products because two cations can be coordi-
nated inside a large cavity. The reaction between 2,6-
diacetylpyridine or 2,6-diformylpyridine and 3,3'-imino-
bispropylamine are appropriate examples. First, as shown
in Scheme 8, 2,6-diacetylpyridine was treated with bis(3-
aminopropyl)amine in the presence of Ni(II), Cu(II),
Mn(II), Co(II) or Zn(II) salts resulting in the formation of
cyclic complexes of the 1:1 condensation products [19,20].
Templated cyclocondensation of the above compounds in
the presence of Ag(I), Pb(II), Ca(II) or Sr(II) gave the bin-
uclear Ag(I) and Pb(II) and mononuclear Ca(II) and Sr(II)
complexes of the 28-membered ligand resulting from 2:2
cyclization [21-23]. This process is complicated by the
formation of a ring-contracted form when the reaction is
carried out using Ca(II) or Sr(II) salts. The ring contrac-
tion process is evident when diethylenetriamine is used in
the reaction. The contracted 20-membered ring is con-
verted to the 24-membered ring by a transmetallation
process with a transition metal ion [23,24].
ing one mole of available α,ω-diamines with two moles of
available α,ω-diodides as shown in Scheme 9 [26-30].
Often, unexpected by-products are obtained during
cyclization reactions. For example, Krakowiak, et al. pre-
pared the desired cryptand and a biscrown ether by-prod-
uct in the same reaction starting from 1,3-bis(amino-
methyl)benzene and 1,11-diodo-3,6,9-trioxaundecane
(Scheme 10) [26]. In the case of using 1,4-bis(amino-
methyl)benzene, only the bisaza-12-crown-4 was isolated
(Scheme 11). Evidently, in this latter example, the bis-
crown is much easier to form than the [15]paracyclophane
ring leading to the cryptand.
The most important cryptand, [2.2.2], was finally pre-
pared in good yields using the ditosylate starting material
instead of the diiodide (Scheme 12). Other cryptands such
as [2.2.1], [3.3.1], [3.3.2], and [3.3.3] were also prepared
in good yields by this 2:1 bicyclization process using the
appropriate ditosylates [31].
There is large interest in the chemistry of the cryptands
because of their strong complexing properties. A great
number of papers concerning the chemistry of the
cryptands have been published. Only a few cryptands can
be purchased and they are very expensive. The most con-
venient method for preparation of cryptands would be the
one-step reaction of a diamine with two equivalents of an
oligoethylene glycol dichloride first tried by Kulstad and
Malmsten [25]. Although they were unsuccessful, we
repeated their work and found that some [2.2.2] was pro-
duced. However, since there were so many side products
in that reaction, we studied the preparation of many other
cryptands by one-step procedures before we learned how
to make [2.2.2] in one step. It is most convenient in any
synthesis procedure to use starting compounds that are
available from commercial sources such as ditosylates and
diiodides. With that in mind, we discovered a convenient
one-step method to prepare a variety of cryptands by treat-
A number of unsymmetric cryptands have been prepared
in our laboratory by a different one-step ring closure pro-
cedure [32]. Easily formed tetraalcohols were treated with
two equivalents of a dichloride, dibromide, or ditosylate to
produce the new unsymmetric cryptands in yields up to
50% (Scheme 13).

1
242
K. E. Krakowiak, R. M. Izatt, and J. S. Bradshaw
Vol. 38
Self-condensation of o-aminobenzaldehyde in the pres-
given the polymers. 1-Methyl- and 1-phenylaziridine gave
only polymers under the same conditions.
ence of Ni(II) produced a mixture of cyclic trimers and
tetramers [33]. Even though this is not a 2:2 cyclization
reaction because only a single starting material was used,
four new bonds were formed as shown in Scheme 14 for
the tetramer [34-36].
Macrocyclic Compounds Formed by Five to Seven New
Bonds.
The macrolide compounds are important macrocycles
formed from the hydroxycarboxylic acids. Seebach and
coworkers obtained interesting results for the cyclolac-
tolization of (R)- and (S)-3-hydroxybutanoic acid as shown
in Scheme 17 [41]. At room temperature, the cyclic pen-
tamer, hexamer and heptamer were formed in approxi-
mately equal amounts with a total yield of 50%. The ratio
of the products was 59:30:9 in favor of the pentamer over
the heptamer at 110°.
Macrocyclic Compounds Formed by Four to Six New
Bonds.
Small three-membered heterocyclic compounds such as
aziridine and ethylene oxide can open and react to form
larger macrocyclic compounds. For example, cyclooligo-
merization of ethylene oxide gave many new cyclic prod-
ucts. Using the proper conditions, this process gave a
mixture of crown compounds as shown in Scheme 15.
Dale and coworkers [37,38] have shown that product com-
position can be influenced by adding a "templating
cation". Addition of copper or zinc tetrafluoroborate, for
example, gave a product mixture containing greater than
Macrocyclic Compounds Formed by Six New Bonds.
Products of 3:3 cyclization reactions are generally by-
products from high dilution 1:1 or 2:2 cyclizations [42,43].
These large cyclic products can be isolated by careful chro-
matography. Often 3:3 cyclization is the main product
because the 1:1 and 2:2 cyclization products cannot form. An
example of a 3:3 cyclization is the preparation of the piper-
azine-containing cyclic hexamide shown in Scheme 18 [44].
90% of the cyclic pentamer (15-crown-5) [38].
Aziridine molecules readily polymerize and, in some
cases, macrocycles can be isolated from the product mix-
ture [39,40]. For example, 1-benzylaziridine reacted to
give good yields of tetra-N-benzyl-substituted peraza-12-
crown-4 as shown in Scheme 16 [39,40]. These cyclic
tetramers were formed under conditions that should have
Cyclocondensation of 3 molecules of a dihalide (or
diacid dichloride) with 2 molecules of a trialcohol or tri-
amine forms cryptands wherein six C-O or six C-N bonds
are formed. For example, cryptands were formed from tri-
ethanolamine and 2,6-bis(chloromethyl or 2,6-
bis(chloroethyl)pyridine as shown in Scheme 19 [45,46].
The reaction was carried out in xylene or dimethylfor-
mamide in the presence of sodium hydride to give low

Nov-Dec 2001
One-Step Syntheses of Macrocyclic Compounds: A Short Review
1243
yields of the products. A much higher yield was observed
for the 3:2 cyclocondensation of 2-(chloromethyl)-3-
chloropropene with triethanolamine (Scheme 20) [47].
The 3:2 cyclocondensation reaction has also been used
to prepare cryptands containing six Schiff base functions
hexaazacrowns by the templated condensation of ethylene-
diamine, formaldehyde and an alkylamine in the presence
of Cu(II) or Ni(II) (Scheme 23).
[48-53]. In this case, two molecules of tris(2-aminoethyl)-
amine were condensed with three molecules of an aliphatic
or aromatic dialdehyde as shown in Scheme 21. Many of
the hexaimines were then reduced to form the saturated
hexaaza cryptands.
Scheme 21
If rigid subunits are to be incorporated, the various
acyclic intermediates may be pre-organized in the correct
conformation for cyclization. Sometimes these reactions
are quite spectacular. An early example is the reaction of
pyrrole and ketones in the presence of acid, which gave
excellent yields of the macrocycle in a 4+4 cyclization
reaction (Scheme 24) [58,59]. Similar reactions were
observed with furan [60,61].
Kissener and Vögtle prepared a remarkable cage com-
pound composed of two benzene rings connected together
by six aromatic bridges in one step as shown in Scheme 22
[54]. They reacted the two starting materials in very high
dilution using cesium carbonate as the base to give the
product in 0.1% yield. The yield was improved to 0.5% in
a later reaction process. Other cage compounds containing
three decks were also prepared with a total yield of 6% for
a mixture of two isomers [55,56].
Inazu and coworkers developed the synthesis of cyclo-
phanes in one step using a few different approaches [62].
As alternative synthetic methods, they introduced
p-toluenesulfonamide as a reactant (Scheme 25) [63].
During this reaction, the authors isolated products of 2:2,
3:3 and the desired 4:4 cyclization. The use of p-phenyl-
enebistrifluoroacetamide offers a more facile and practical
Macrocyclic Compounds Formed by Eight New Bonds.
Formaldehyde, aldehydes and ketones are often used for
the formation of bonds during the synthesis of macrocyclic
compounds. For example, Suh and Kang [57] prepared

1
244
K. E. Krakowiak, R. M. Izatt, and J. S. Bradshaw
Vol. 38
The base catalyzed condensation of 5,5'-di-t-butyl-2,2'-
dihydroxybiphenyl with formaldehyde gave a calixarene-
like macrocyclic compound as shown in Scheme 28 [75-
77]. Macrocycles with three, four and eight 2,2'-dihydrox-
ybiphenyl units have been prepared.
synthetic method to prepare the cyclophanes and allows
the preparation of these macrocycles in gram quantities
(Scheme 26) [64].
Condensation of resorcinol with aldehydes forms
calix[4]resorcinarenes, but only one member of the family
is known (Scheme 29) [78], although a calix[5]arene with
resorcinol connected in a different position is also known
[79]. It is most likely that resorcinarenes of other ring
sizes can be produced in a manner similar to that used for
the syntheses in the calixarene family. The resorcinarenes
are starting materials for other classes of compounds such
as the cavitands [80,81].
Macrocyclic Compounds Formed by Eight to Forty New
Bonds.
In general, the base catalyzed condensation of p-substi-
tuted phenols and formaldehyde yields a complex mixture
of linear and cyclic oligomers and the outcome of the reac-
tion is difficult to control. There are, however, a few cases
in which the reaction can be controlled. For example, when
the starting phenol bears a bulky substituent at the p-posi-
tion, the condensation reaction can be directed to cyclic
products in excellent yields (Scheme 27). The wide rang-
ing investigations of Gutsche and coworkers [65-69] and
others [70-73] have resulted in both reproducible and high
yield procedures for the synthesis of p-t-butylcalixarenes
The homooxacalixarenes are calixarene analogues in
which some or all of the CH units bridging the aromatic
2
rings in the calixarenes are replaced by CH OCH units.
2
2
Usually, this family of compounds is prepared by the dehy-
dration of phenols. For example, a large homooxacal-
ixarene was isolated after heating a bis(hydroxymethyl)-
bisphenol to a high temperature as shown in Scheme 30
[
82,83].
containing an even number of phenolic rings. The hexamer
was formed when alkali metal cations with large ionic radii
Another group of macrocyclic compounds that was
reported nearly 100 years ago by Behrend et al. [84]
waited until recently for the method of their preparation to
be discovered. These workers isolated the compounds
from an acidic condensation of glycoluril with an excess of
formaldehyde. The structure of the compound was pub-
lished 75 years later by Freeman et al. [85] and it proved to
be cucurbit[6]uril (Scheme 31). It was another 10 years
before another example of this class of compounds, cucur-
+
+
(K , Cs ) were used and the tetramer was formed when a
higher temperature was applied. It is important to empha-
size that a step-by-step synthesis of these compounds is dif-
ficult so that it is more convenient to use the one-step pro-
cedure. Calixarenes containing an odd number of phenolic
rings are less accessible but can be produced with an aver-
age yield by a one-step synthesis [74].

Nov-Dec 2001
One-Step Syntheses of Macrocyclic Compounds: A Short Review
1245
bit[5]uril with 10 methyl groups, was prepared [86].
Cucurbit[6]uril and cucurbit[5]uril have been tested for
different applications [87,88]. The preparation of any
cucurbit[n]uril from n = 4-10 (Scheme 31) was published
only a year ago [89,90]. The authors also detected larger
compounds up to n = 12. The calixarenes have more
proven applications than do the cucurbituril compounds
because the cucurbituril compounds do not have functional
groups that would allow them to be used as building blocks
or platforms to create new supramolecular structures.
five- or six-membered rings, such as morpholine or piper-
azine, will preferentially form. Some aliphatic connecting
group-containing supercryptands shown in Scheme 33 have
been prepared, but in small yields [95-97]. However, reac-
tions of the appropriate starting materials do not always
give the desired supercryptands but often lead to other
macrocyclic compounds as shown in Scheme 34 [96].
Macrocyclic Compounds Formed by Twelve New Bonds.
Recent advances in host-guest chemistry demand more
and more sophisticated artificial host molecules. Step-by-
step synthetic methods are not practical because multi-step
syntheses involve many protecting and deprotecting steps.
A one-step method to the more sophisticated compounds is
a much better approach even with very low yields. Often
purification of the complicated product requires very care-
ful column chromatography. The so-called supercryptands
(
spherical macrotricyclic ligands) can be prepared easily if
rigid aromatic units are present in the starting compounds
Scheme 32) [62,91-94]. Unfortunately, this synthetic
(
approach is not useful for the preparation of small super-
cryptands with aliphatic connecting groups because small
Krakowiak, et al. in the reaction shown in Scheme 35,
produced cryptands, biscrown ethers, and a supercryptand
or a triscrown ether [26]. After reacting the two starting
materials in a 1:2 ratio, they separated two products of a
4:2 cyclocondensation. One product was characterized as

1246
K. E. Krakowiak, R. M. Izatt, and J. S. Bradshaw
Vol. 38
the biscrown ether shown in Scheme 35 [26]. The other is
either the triscrown or the supercryptand. The exact struc-
ture has not yet been determined.
sation of 1,1-bis(aminomethyl)cyclohexane with formalde-
hyde to form a polymer, which upon heating readily isomer-
ized to a cyclic compound (Scheme 38) [102].
Sargeson and coworkers have used an external template
to prepare an octaazacryptate which was obtained in
greater than 95% yield by condensation of the tris(ethyl-
enediamine) cobalt(II) ion with formaldehyde and ammo-
nia as shown in Scheme 36 [98,99].
Summary.
One-step syntheses of macrocyclic compounds are very
convenient methods to prepare many cyclic compounds.
The only drawbacks are that the yields are low and purifi-
cation steps sometimes require repeated column chro-
matography. Some macrocycles can only be prepared by a
one-step synthesis because a multi-step synthesis is not
practical and would take too long (for example for the cal-
ixarenes). On the other hand, unsymmetric macrocyclic
compounds can only be prepared using a multi-step
method.
Macrocyclic Compounds Formed by Sixteen New Bonds.
A square prism (cubic) compound was first prepared by a
multistep synthesis in a 2% yield [100,101]. Later, the same
compound was prepared by a one-step process (Scheme 37)
with a better yield (4.7%). Another example is the conden-
REFERENCES AND NOTES
[
1] J. S. Bradshaw, K. E Krakowiak, and R. M. Izatt, Aza-
Crown Macrocycles, J. Wiley & Sons, New York, 1993, p 83.
2] P. Hodge, H. M. Colquhoun, and D. Williams, Chem. Ind.,
62 (1998).
3] S. V. Shevchuk, J. M. Davis, and J. L. Sessler, Tetrahedron
Lett., 42, 2447 (2001).
[
1
[

Nov-Dec 2001
One-Step Syntheses of Macrocyclic Compounds: A Short Review
1247
[
4] N. Yamasaki, H. Nagahara, and J. Masamoto, Tetrahedron
[37] J. Dale, G. Borgen, and K. Daasvatn, Acta Chem. Scand.,
B28, 378 (1974).
Lett., 42, 271 (2001).
[
5] G. W. Gokel and S. H. Korzeniowski, Macrocyclic
[38] J. Dale and K. Daasvatn, J. Chem. Soc., Chem. Commun.,
295 (1976).
Polyether Synthesis, Springer-Verlag, Berlin, 1982.
[
6] B. Dietrich, P. Viout, and J.-M. Lehn, Macrocyclic
Chemistry, VCH, Weinheim,1993.
7] S. Lindoy, The Chemistry of Macrocyclic Ligand
Complexes, Cambridge University Press, Cambridge, 1989.
8] Comprehensive Supramolecular Chemistry, J. L. Atwood,
[39] G. R. Hansen and T. E. Burg, J. Heterocyclic Chem., 5, 305
(1968).
[40] R. Kossai, J. Simonet, G. Daulphin Tetrahedron Lett., 21,
3575 (1980).
[
[
[41] D. Seebach, V. Brändi, P. Schnurrenberger and M.
Przybylski, Helv. Chim Acta., 71, 155 (1988).
[42] G. R. Newkome, G. E. Kiefer, D. K. Kohli, Y. J. Xia, F. R.
Fronczek, and G. R. Baker, J. Org. Chem., 54, 5105 (1989).
[43] L. Rossa and F. Vögtle, Synthesis of Medio and
Macrocyclic Compounds by High Dilution Principle Techniques, in
Cyclophanes, F.L. Boschlee (editor), Springer-Verlag, Berlin, 1982.
[44] K. E. Krakowiak, J. S. Bradshaw, W. Jiang, N. K. Dalley, G.
Wu, and R. M. Izatt, J. Org. Chem., 56, 2675 (1991).
[45] G. R. Newkome, V. K. Majestic, F. R. Fronczek, and J. L.
Atwood, J. Am. Chem. Soc., 101, 1047 (1979).
[46] G. R. Newkome, V. Majestic, and F. Fronczek, Tetrahedron
Lett., 22, 3035 (1981).
[47] K. E. Krakowiak, J. S. Bradshaw, and R. M. Izatt, J.
Heterocyclic Chem., 27, 1011 (1990).
[48] J. Jazwinski, J.-M. Lehn, D. Lilienbaum, R. Ziessel, J.
Guilheim, and C. Pasccord, J. Chem. Soc., Chem. Commun., 1691
(1987).
[49] D. MacDowell and J. Nelson, Tetrahedron Lett., 29, 385
(1988).
[50] M. G. B. Drew, D. MacDowell and J. Nelson, Polyhedron,
21, 2229 (1988).
J. E. Davies, D. O. McNicol, F. Vögtle, and J.-M. Lehn (editors),
Elsevier, Oxford (1996).
[9] T. W. Bell and J. Liu, Angew. Chem. Int. Ed. Engl., 29, 923
(
(
(
1990).
[
10] Macrocycle Synthesis. A Practical Approach, D. Parker
editor), Oxford University Press, Oxford, 1996.
[
11] T. W. Bell and A. Firestone, J. Am. Chem. Soc., 108, 8109
1986).
12] U. Kramer, A. Guggisberg, M. Hesse, and H. Schmidt,
Angew. Chem. Int. Ed. Eng., 16, 861 (1977).
13] U. Kramer, H. Schmidt, A. Guggisberg, and M. Hesse,
Helv. Chim. Acta, 62, 811 (1979).
14] S. J. Rodgers, C. Y. Ng, and K. N. Raymond, J. Am. Chem.
Soc., 107, 4094 (1985).
15] F. Vögtle and W. M. Müller, Angew. Chem. Int. Ed. Eng.,
1, 147 (1982).
16] F. Vögtle and W. M. Müller, Angew. Chem. Int. Ed. Eng.,
3, 712 (1984).
[
[
[
[
2
2
[
[
[
[
[
17] J. A. Elix, Aust. J. Chem., 22, 1951 (1969).
18] C. J. Pedersen, Org. Synth., Col. Vol. 6, 395 (1988).
19] J. L. Karn and D. H. Busch, Nature, 211, 160 (1966).
20] R. L. Rich and G. L. Stucky, Inorg. Nucl. Chem. Lett., 61
[51] J.-M. Lehn, R. Meric, J. P. Vigrevou, I. Bkouche-Waksman,
and C. J. Pasccord, J. Chem. Soc., Chem. Commun., 63 (1991).
[52] M. P. Ngwenya, A. E. Martell, and J. Reibenspies, J. Chem.
Soc., Chem. Commun., 1207 (1990).
(
1965).
[
21] F. Cabral, B. Murphy, and J. Nelson, Inorg. Chim. Acta, 90,
69 (1984).
1
[
22] M. G. B. Drew, C. P. Waters, S. G. McFall, and S. M.
Nelson, J. Chem. Res., 360 (1979).
23] M. G. B. Drew, B. P. Murphy, J. Nelson, and S. M. Nelson,
J. Chem. Soc., Dalton Trans., 873 (1987).
24] K. E. Krakowiak, J. S. Bradshaw, W. Jiang, N. K. Dalley, G.
Wu, and R. M. Izatt, J. Org. Chem., 56, 2675 (1991).
25] S. Kulstad and L. A. Malmsten, Tetrahedron Lett., 21, 643
1980).
26] K. E. Krakowiak, J. S. Bradshaw, N. K. Dalley, C.-Y. Zhu,
G.-L. Yi, J. C. Curtis, D. Li, and R. M. Izatt, J. Org. Chem., 57, 3166
[53] K. E. Krakowiak, A. V. Bordunov, and J. S. Bradshaw, J.
Heterocyclic Chem., 35, 169 (1998).
[54] W. Kissener and F. Vögtle, Angew. Chem. Ind. Ed. Engl.,
24, 794 (1985).
[55] N. Sendhoff, K.-H. Weissbarth, and F. Vögtle, Angew.
Chem. Int. Ed. Engl., 26, 777 (1987).
[56] N. Sendhoff, W. Kissener, F. Vögtle, S. Franken, and H.
Puff, Chem. Ber., 121, 2179 (1988).
[57] M. P. Suh and S.-G. Kang, Inorg. Chem., 27, 2544 (1988).
[58] A. Baeyer, Chem. Ber., 19, 2184 (1886).
[59] P. Rothemund and C. L. Gage, J. Am. Chem. Soc., 77, 3340
(1955).
[
[
[
(
[
(
1992).
[27] K. E. Krakowiak and J. S. Bradshaw, J. Org. Chem., 56,
3
723 (1991).
[
[60] M. Chastrette and F. Chastrette, J. Chem. Soc., Chem.
Commun., 534(1973).
[61] A. J. Rest, S. A. Smith, and I. D. Tyler, Inorg. Chim. Acta,
16, L1 (1976).
[62] H. Takemura, T. Shinmyozu, and T. Inazu, Coord. Chem.
Rev., 156, 183 (1996).
[63] H. Takamura, M. Suenaga, K. Sakai, H. Kawachi, T.
Shinmyozu, Y. Miyahara, and T. Inazu, J. Incl. Phenom. 2, 207 (1984).
[64] T. Shinmyozu, N. Shibakawa, K. Sugimoto, H. Sakane, H.
Takemura, K. Sako, and T. Inazu, Synthesis, 1257 (1993).
[65] C. D. Gutsche and M. Tqbal, Org. Synth., Col. Vol. VIII, 75
(1993).
28] K. E. Krakowiak, J. S. Bradshaw, H.-Y. An, and R. M. Izatt,
Pure Appl. Chem., 65, 511 (1993).
29] K. E. Krakowiak, P. A. Krakowiak and J. S. Bradshaw,
Tetrahedron Lett., 34, 777 (1993).
30] K. E. Krakowiak, J. S. Bradshaw, and R. M. Izatt, Synlett.,
1 (1993).
31] K. E. Krakowiak, J. S. Bradshaw, X. Kou, and N. K. Dalley,
Tetrahedron, 51, 1599 (1995).
32] J. S. Bradshaw, H.-Y. An, K. E. Krakowiak, T. Wang, C.
Zhu, and R. M. Izatt, J. Org. Chem., 57, 6112 (1992).
[
[
6
[
[
[33] S. G. McGeachin, Can. J. Chem., 44, 2323 (1966).
[
34] G. A. Melson and D. H. Busch, Proc. Chem. Soc., 223
[66] C. D. Gutsche, B. Dhawan, M. Leonis, and D. Stewart, Org.
Synth., Col. Vol VIII, 77 (1993).
(
1963).
[
35] G. A. Melson and D. H. Busch, J. Am. Chem. Soc., 86,
[67] J. H. Munch and C. D. Gutsche, Org. Synth., Col. Vol. VIII,
80 (1993).
4
834 (1964).
[
36] G. A. Melson and D. H. Busch, J. Am. Chem. Soc., 87, 1706
[68] C. D. Gutsche, Calixarenes, Royal Society of Chemistry,
Cambridge, 1989.
(
1965).

1248
K. E. Krakowiak, R. M. Izatt, and J. S. Bradshaw
Vol. 38
[
69] C. D. Gutsche, Calixarenes Revisited, Royal Society of
Chemistry; Cambridge, 1998.
70] J. Vicens and V. Böhmer (editors), Calixarenes: A Versatile
Angew. Chem. Int. Ed. Engl., 31, 1475 (1992).
[87] P. Cintas, J. Incl. Phenom., 17, 205 (1994).
[
[88] W. Mock, Cucurbituril, In Comprehensive Supramolecular
Chemistry, J. L. Atwood, J. E. Davies, D. O. McNicol, F. Vögtle, and
J.-M. Lehn (editors), Elsevier, Oxford (1996).
[89] J. Kim, I.-S. Jung, S.-Y Kim, E. Lee, J.-K. Kang, S.
Sakamoto, K. Yamaguchi, and K. King, J. Am. Chem. Soc., 122, 540
(2000).
Class of Macrocyclic Compounds, Kluwer Academic Press,
Dordrecht, 1991.
[
71] J. Vicens, Z. S. Asfari, and J. M. Harrowfield (editors),
Calixarenes 50th Anniversary Commemorative Issue, Kluwer
Academic Press, 1996.
[
72] Z. Asfari, V. Böhmer, J. M. Harrowfield and J. Vicens (edi-
[90] A. J. Day and A. P. Arnold, WO Patent 68232 (2000);
Chem. Abstr. 133, 362775k (2000).
tors), Calixarenes 2001, Kluwer Academic Press, Doordrecht, 2001.
[
73] A. McKervey and V. Böhmer, Chem. Britain, 724 (1992).
[91] H. Takemura, T. Hirakawa, T. Shinmyozu, and T. Inazu,
Tetrahedron Lett., 25, 5053 (1984).
[74] A. Pochini and R. Ungaro, Calixarenes and Related Hosts
in Supramolecular Chemistry, in Comprehensive Supramolecular
Chemistry, Vol 2, J. L. Atwood, J. E. Davies, D. O. McNicol, F.
Vögtle, and J.-M. Lehn (editors), Elsevier, Oxford (1996).
[92] H. Takemura, T. Shinmyozu, and T. Inazu, Tetrahedron
Lett., 29, 1789 (1988).
[93] H. Takemura, T. Shinmyozu, and T. Inazu, J. Am. Chem.
Soc., 113, 1323 (1991).
[94] H. Takemura, N. Kou, M. Yasutake, H. Kariyazoro, T.
Shinmyozu, and T. Inazu, Angew. Chem. Int. Ed. Engl., 38, 959
(1999).
[95] H. Takemura, H. Kariyazano, M. Kakuta, N. Kou, T.
Shinmyozu, and T. Inazu, J. Chem. Res. S, 372 (1997).
[96] N. Kou, H. Takemura, K. Otsuka, K. Tanoue, S.
Nakashima, M. Yasutake, K. Tani, J. Kimoto, T. Shinmyozu, and T.
Inazu, J. Org. Chem., 65, 3708 (2000).
[
75] T. Yamato, K. Hasegawa, Y. Saruwatari, and L. K.
Doamekpor, Chem. Ber., 126, 1435 (1993).
76] P. O'Sullivan, V. Böhmer, W. Vogt, E. F. Paulus and R. A.
Jakobi, Chem. Ber., 27, 427 (1994).
77] K. Agbaria, S. E. Biali, V. Böhmer, J. Brenn, S. Cohen, M.
[
[
Frings, F. Grynszpan, J. M.. Harrowfield, A. N. Sobolev, and I.
Thondort, J. Org. Chem., 66, 2900 (2001).
[78] A. G. S. Högberg, J. Org. Chem., 45, 4498 (1980).
[79] M. Tabatabai, W. Vogt, V. Böhmer, G. Ferguson, and E. F.
Paulus, Supramol. Chem., 4, 147 (1994).
80] J. C. Sherman, C. B. Knobler, and D. J. Cram, J. Am. Chem.
Soc., 113, 2194 (1991).
81] D. J. Cram, M. E. Tanner, and C. B. Knobler, J. Am. Chem.
Soc., 113, 7717 (1991).
82] S. Felix, J. R. Ascenso, R. Lamartine, and J. L. Pereira,
Tetrahedron, 55, 8539 (1999).
[97] H. Takemura, N. Kou, M. Kotoku, S. Nakashima, K.
Otsuka, M. Yasutake, T. Shinmyozu, and T. Inazu, J. Org. Chem., 66,
2778 (2001).
[98] I. I. Creaser, J. M. Harrowfield, A. J. Herlt, A. M. Sargeson,
J. Springborg, R. J. Geue, and R. M. Snow, J. Am. Chem. Soc., 99,
3181(1977).
[99] A. M. Sargeson, Pure Appl. Chem., 58, 1511 (1986).
[100] Y. Murakami, J. Kikuchi, and T. Hirayama, Chem. Lett.,
161 (1987).
[
[
[
[83] B. Masci, Tetrahedron, 57, 2841 (2001).
[84] R. Behrend, E. Meyer, and F. Rusche, Lieb, Ann. Chem.,
3
39, 1 (1905).
85] W. A. Freeman, W. L. Mock, and N.-Y. Shih, J. Am. Chem.
Soc., 103 7367 (1981).
86] A. Flinn, G. C. Hough, J. F. Stoddart, and D. J. Williams,
[101] Y. Murakami and J. Kikuchi, Pure Appl. Chem., 60, 549
(1988).
[102] M. R. Suissa, C. Romming, and J. Dale, J. Chem. Soc.,
Chem. Commun., 113 (1997).
[
[