One-step Access to Resorcinsalens—Solvent-Dependent Synthesis, Tautomerism, Self-sorting and Supramolecular Architectures of Chiral Polyimine Analogues of Resorcinarene

Article abstract of DOI:10.1002/chem.201800316

Substituted 2,4- and 4,6-dihydroxyisophthalaldehydes were condensed with optically pure and racemic trans-1,2-diaminocyclohexane to form resorcinarene-like polyimine macrocycles (resorcinsalens), the structure and stoichiometry of which were controlled by the choice of the reaction medium. Particularly, the cyclocondensation reactions were driven by the solubility, tautomerization, or by social self-sorting. The resorcinsalens crystallized as inclusion compounds, in which the guest molecules were situated either in channels or in voids. In the highly hydrated crystals of one of the [2+2] macrocycles and chloroform-solvated crystals of a [4+4] product the channels were interconnected, as in zeolites, enabling possible migration of loosely bound solvent molecules in three dimensions. The association mode depended on the structural modification of the host molecule and the type of included solvent molecule(s).

Full text of DOI:10.1002/chem.201800316

A Journal of
Accepted Article
Title: One-step Access to Resorcinsalens - Solvent Dependent
Synthesis, Tautomerism, Self-sorting and Supramolecular
Architectures of Chiral Polyimine Analogues of Resorcinarene
Authors: Marcin Kwit, Joanna Szymkowiak, Beata Warżajtis, and
Urszula Rychlewska
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To be cited as: Chem. Eur. J. 10.1002/chem.201800316
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COMMUNICATION
One-step Access to Resorcinsalens – Solvent Dependent
Synthesis, Tautomerism, Self-sorting and Supramolecular
Architectures of Chiral Polyimine Analogues of Resorcinarene
Joanna Szymkowiak,[a,b] Beata Warżajtis,[a] Urszula Rychlewska,[a] and Marcin Kwit*[a,b]
Abstract: The substituted 2,4- and 4,6-dihydroxyisopthalaldehydes
amine of choice for cycloimination. While the quantitative [3+3]
cyclocondensations between and various aromatic 1,4-
were condensed with optically pure and racemic trans-1,2-
1
diaminecyclohexane
to
form
resorcinarene-like
polyimine
dialdehydes provide triangular macrocycles (trianglimines) of
symmetry and shape depending on the aldehyde structure,[8,9]
the reactions utilizing 1,3-dialdehydes are less selective.
However, the presence of hydroxyl group between two adjacent
CHO groups drives the reaction to the vase-like [3+3] products
(calixsalens) and significantly stabilizes their structure. Both, the
size and electronic properties of a substituent at C5 position of
the arene ring control the abilities to form calixsalen
supramolecular architectures in all states of matter.[10]
To the best of our knowledge, to date there are no reports
on chiral polyimine macrocycles that contain two imine and two
hydroxyl groups in relative 1,3 positions within the same
aromatic unit. These macrocycles, in principle, should exhibit
molecular and supramolecular properties differrent from the
compounds known so far, for instance reversible proton
tautomerism – one of the most important processes in chemistry
and biochemistry.[11] Recently, Lisowski et al. and Banerjee et al.
indicated proton tautomerism as one of the decisive factors that
caused unexpected formation of chiral and achiral [2+3] keto-
enamine organic cages from 1,3,5-triformylphloroglucinol.[12]
MacLachlan et al. proved strong preference of acyclic imines
from 2,4-dihydroxyisopthalaldehyde to form keto-enamine
tautomers (NH form), while imines derived from 4,6-
dihydroxyisopthalaldehyde preserved the enol-imine form.[13]
Thus, it seemed desirable to expand the study into chiral
macrocycles (resorcinsalens) of the structure and stoichiometry
controlled by the choice of the reaction medium. Particularly, the
cyclocondensation reactions are driven by the solubility,
tautomerisation or by social self-sorting. The resorcinsalens
crystallize as inclusion compounds, where the guest molecules are
situated either in channels or in voids. In the highly hydrated crystals
of phase I of 3a and chloroform solvated crystals of meso-5a the
channels are interconnected, as in zeolites, enabling possible
migration of loosely bound solvent molecules in three-dimensions.
The association mode depends on the structural modification of the
host molecule and the type of included solvent molecule(s).
Controlled synthesis of functionalized chiral macrocycles by
means of Dynamic Covalent Chemistry (DCC) concept is
gaining popularity for the development of new supramolecular
receptors, ligands and for designing of porous materials.[1,2]
While most of the macrocyclisation reactions usually require
special reaction conditions or laborious elongation of open-chain
precursor prior macrocyclization,[1] application of the DCC
allowed rational design of molecules, varied in shape and
functionalities, from relatively simple building blocks.[2] The DCC-
based, reversible cycloimination reaction emerges now as
convenient template-free method providing shape-persistent,
optically pure polyimine macrocycles from structurally
predisposed substrates.[3] These polyazamacrocycles are further
applied as chiral catalysts and ligands in stereoselective
synthesis, as molecular receptors or organic porous
materials.[4,5] The use of racemic substrates in cycloimination
reactions often provides complex mixtures of diastereoisomers.
Chiral self-sorting is achieved in those of DCC-based reactions
whose products significantly differ in symmetry, therefore in
polyimine
resorcinarene-like
systems,
being
2,4-
dihydroxyisopthalaldehyde or 4,6-dihydroxyisopthalaldehyde
derivatives. The compounds considered as good candidates for
the synthesis represent members of a new class of highly
functionalized macrocycles (resorcinsalens). We intended to
demonstrate, how the aldehyde structure, reaction conditions
and/or the diamine enantiomeric purity affect the structure of the
product(s). Hydroxyl groups present in the macrocycle skeleton
will be capable of forming hydrogen bonds and controlling, in
this way both, the molecular structure and the assembly in the
solid state. The OH form is generally considered as the most
stable form at room temperature. Consequently, hydroxylated
polyimine chiral macrocycles exist as enol-imine tautomers. So
far none of the macrocycles has been characterized as purely
rotational
entropy.[6,7]
Due to the diequatorial position of amine groups and
skeleton rigidity, trans-1,2-diaminecyclohexane (DACH, 1) is the
NH form by
a
single crystal X-ray diffraction method.[14]
[a]
[b]
J. Szymkowiak, Dr. B. Warżajtis, Prof. Dr. U. Rychlewska, Dr. M.
Kwit
Department of Chemistry, Adam Mickiewicz University
Umultowska 89B, 61 614 Poznan, Poland
E-mail: marcin.kwit@amu.edu.pl
Meanwhile, we anticipated that some of the newly synthesized
macrocycles may appear as the keto-enamine tautomeric forms.
To initiate the work, we synthesized 2,4-dihydroxy- (2a-2c)
or 4,6-dihydroxyisopthalaldehydes (2d, 2e) from respective,
commercially available, resorcinols and through Duff
formylation.[15] The aldehydes were obtained with yields ranging
from 11% to 45% (after chromatography and crystallization) and
were further subjected to reaction with (R,R)-1 or rac-1 (Scheme
J. Szymkowiak, Dr. M. Kwit
Centre for Advanced Technologies, Adam Mickiewicz University
Umultowska 89C, 61 614 Poznan, Poland
Supporting information for this article is given via a link at the end
of the document.
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1). Due to the presence of OH groups at C2 and C4 positions in
aldehydes 2a-2c, we expected the same s-trans conformation of
the imine bonds (see Scheme S1) as in known calixsalens[10c]
and exclusive formation of [3+3] macrocycles 4a-4c.
Indeed, reactions carried out in chloroform, at room
temperature, provided orange colored macrocycles 4a-4c,
formation of which was confirmed by mass spectra. During the
reaction, color of the mixture changed to green with precipitation
of hardly soluble solids (apart from the quantitatively obtained
4c).
The 1H NMR and mass spectra recorded at the time
intervals for the model reaction between (R,R)-1 and 2a, carried
out in CDCl3 (Figure 1), gave an insight into the course of the
cycloimination reaction. Within 15 minutes almost immediate
disappearance of the aldehyde and formation of C3-symmetrical
[3+3] product 4a was observed. The diagnostic CH=N imine
sharp singlets that appeared at δ = 9.39 and 7.72 ppm are
typical for the OH form of the macrocycle. This particular form is
stable in chloroform solution up to 3 hours. After that time, a
step-wise decrease of the diagnostic signals intensity was
observed with simultaneous appearance of new downfield broad
signals at δ = 12.4 and 11.8 ppm, together with a set of signals
in the region between 9÷8 ppm. The MS did not show any
significant changes, which provided compelling evidence of the
ongoing tautomerisation rather than contraction or expansion of
the macrocycle ring. Since neither the appearance nor the
disappearance of already present signals was complete, we
assumed the presence of complex equilibrium involving number
of possible tautomers.
In the UV spectra measured during the cycloimination
reaction between (R,R)-1 and 2a, a shift (ca. 50 nm) of the
absorption maxima of the pure aldehyde into lower energy
region has been observed while the concentration of the cyclic
product 4a increased. The highest intensity absorption band
appeared at 302 nm and its position did not change. However,
as time passed, we observed gradual changes in the shape of
the lower energy regions of the spectra. Well-formed band at
around 400 nm was gradually covered by a wide absorption
band in which characteristic peaks could not be distinguished.
Note that spectrum measured for the [2+2] macrocycle 3a has
similar shape as those of 4a (see Figures S1-S2).
Scheme 1. Reactions of 1 with 2a-2e leading to resorcinsalens 3-5.
Apart from 4c (vide infra), we were unable to fully
characterize the obtained products 4a and 4b, due to their
insolubility. However, the appearance of enamine derived,
broadened NH triplets at δ = 12.25 and 11.49 ppm and =CHN
doublets at δ = 8.41 and 7.15 ppm indicated formation of pure
NH form of 4c. Note that the NH signals disappeared after
addition of
a
drop of D2O to the NMR test tube.
The same reactions carried out in boiling ethanol provided
the contracted [2+2] products 3a and 3b with yields 87% and
45%, respectively. The number and the multiplicity of diagnostic
signals observed in 1H NMR spectra unequivocally confirmed
the presence of 3a-3c solely as the keto-enamine tautomer.
However, the reaction route between (R,R)-1 and the
hydrophobic 2c appeared to be more complex. We observed
precipitation of 4c (yield 40%), which was hardly soluble in polar
solvents and was not subjected to further transformations. The
major product 3c was purified by several crystallizations from
supernatant, which provided analytically pure sample with yield
equal
to
41%.
DFT calculations carried out for the model compounds
being N-methylimine derivatives of 2a (imine 6) and 2c (imine 7)
(Schemes S2-S3, Figures S3-S4) as well as for 3a-3c and 4a-4c
confirmed the preference for the keto-enamine forms.[16] The
calculated energy differences are primarily dependent on the
environment, simulated by the solvent model. The type of the
substituent attached to the aromatic ring had much smaller
impact. The absolute values of energy gaps (in kcal mol-1)
between OH and NH forms of 6 (values for 7 are shown in
Figure 1. a-e) Parts of the 1H NMR spectra [CDCl3] measured during
cycloimination reaction between (R,R)-1 and 2a. Diagnostic regions of 1H
NMR spectra [CDCl3] of f) 3a and g) 4c. On the right are shown pictures taken
during reaction between (R,R)-1 and 2a. Asterisks indicate trace solvent peaks.
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parentheses) increase from 4.4 (3.2) in the gas phase, through
8.9 (7.0) in CHCl3, to 10.6 (8.5) calculated for the ethanol solvent
model. An increase of the environment polarity was associated
with a decrease of the energy barriers of proton transfers from
the OH groups to the imine nitrogen atoms. To sum up these
results, in ethanol, the enamine-imine equilibria reside almost
completely on the side of the respective enamine (NH)
tautomers.
1.247(3) to 1.274(3) Å with the mean value of 1.258(4) Å for 24
observations (Table S4), in agreement with the mean value of
1.285(13) Å calculated for 107 fragments containing the keto-
enamine tautomers of salicylimine deposited in CSD data base
and with results of DFT calculations.[14]
Depending on crystallization conditions, 3a forms two
types of solvated crystals of space group symmetry R32 and P65,
distinguished as phase I and II, respectively. The two phases
differ inter alia in a number of ethanol and water molecules per
one host molecule and in a molecular symmetry (C2 vs. C1,
respectively). In the crystals of phase I, the basic
supramolecular motif comprises a capsule formed by three
macrocyclic molecules related by a three-fold symmetry axis and
two water molecules entrapped inside the capsule (Figure 4a),
and involved in 3-fold hydrogen bonding with the host molecules.
The remaining highly disordered solvent molecules, i.e. ethanol
and water, are located in large channels, bringing about an
impression that the supramolecular aggregates are sailing in the
‘sea’ of solvent molecules, as picturesquely described by
Cooper and co-workers.[20] The total volume of unit cell occupied
Regardless of the macrocycle size, the imine or enamine
groups adopt the s-trans orientation (see Scheme S1). This
allows formation of intramolecular hydrogen bonds, each closing
a
six-membered ring, and thus significantly stabilizes the
macrocycle structure.[10c] While the linkers in 4a-4c are planar,
the C=C(-N) bonds in 3a-3c are placed out of the plane of the
1,3-quinone
ring
(Figure
S3).
The reactions between equimolar amounts of rac-1 and
respective aldehydes 2d and 2e carried out in chloroform led, at
first, to the formation of the [2+2] products 3d, 3e that
precipitated from the reaction mixtures. The [4+4] products 5a
and 5b, which retained in their respective reaction mixtures,
were purified by crystallization from the respective supernatants.
While this procedure provided a pure sample of 5a with yield
equal to 40%, we were unable to obtain a pure sample of 5b in
the same way, despite many attempts. MS and NMR data
confirmed formation of [2+2] and [4+4] macrocycles 3d, 3e and
5a, respectively, as enol-imine tautomers. The number of
by these molecules equals to 30% (probe radius of 1.4 Å)[21]
.
Meanwhile, out of 22 [2+2] imine macrocycles deposited in the
CSD[14] only 10 are solvated and only one of them contains
included water molecules. In these 10 crystal structures the
volume of the voids occupied by solvent molecules ranges from
2% to 32% with the mean value of 18(9)%. Hence, the crystal
structure of phase I of 3a is exceptional in both the content of
included guest molecules and the percentage of space available
to them. The effect of inducing the aggregation of larger
components by smaller components is known in the colloid
science. The mechanism underlying this phenomenon is claimed
to be entropic, i.e. the ordering of larger components allows for
increasing disorder among the smaller components and
ultimately in the entire system.[22]
1
diagnostic signals observed in H NMR spectra corresponds to
the C2h symmetry of a given [2+2] macrocycle having two
diamine subunits of the opposite helicity and to the S4 symmetry
of 5a. The formation of meso diastereomers represents an
example of social self-sorting, unusual for polyimine compounds.
Similar self-sorting phenomenon has been reported to occur
during the dynamic formation of
macrocyclic
a
disulfide containing
tetramer.[17]
The 1H NMR and MS spectra measured at the time
intervals for the model reaction between rac-1 and 2d, show
complete disappearance of the aldehyde just within 15 minutes
with formation of a mixture of [4+4], [3+3] and [2+2] products in
70:15:15 ratio as indicated by 1H NMR (see Figure 2) and MS
measurements. Prolongation of the reaction time up to 3 days
did not alter the shape of the spectrum. Due to the same
symmetry number (σ = 2) we did not expect any difference in
rotational entropy between the [2+2] and [4+4] products.
However, DFT calculations indicated non-symmetrical,
heteorochiral [3+3] macrocycle as thermodynamically the most
stable over all possible structures (Table S1, Figure S5). Thus,
the formation of dominant [4+4] product can not be explained on
the basis of the entropy of symmetry rule postulated for, inter
alia, reversible, thermodynamically controlled cycloimination
reactions.[18,19] On the other hand, the formation of [2+2]
products is driven by their lower solubility in the reaction medium.
As in the above mentioned case of 4c, the precipitated products
were
not
subjected
to
further
transformations.
The single crystal X-ray diffraction study provided tangible
structural evidence for keto-enamine or enol-imine tautomers of
respective resorcinsalens. Resorcinsalens 3a-3b crystallize as
NH tautomers stabilized by intramolecular NH∙∙∙O hydrogen
bonds supplemented by intramolecular π-π stacking interactions
(Figure 3a). The X-ray determined C=O bond lengths vary from
Figure 2. a) Traces of 1H NMR spectra [CDCl3] measured for the pure
aldehyde 2d. b-e) Traces of 1H NMR spectra [CDCl3] measured during
reaction between 2d and rac-1. f, g) Traces of 1H NMR spectra [CDCl3]
measured for meso-3d and meso-5a. Asterisks indicate trace solvent peaks.
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Figure 3. Perspective views of the molecules 3a a) and 5a b) as present in
crystals at 130K. Displacement ellipsoids for non-H atoms are drawn at 40%
probability. Intramolecular hydrogen bonds stabilizing the tautomeric forms are
represented by dashed lines. Shaded areas mark π-π stacking interactions.
Figure 5. 3D system of interconnecting channels forming possible migration
paths for guest molecules in the crystal of meso-5a.
In crystals of phase II, the molecules situated around the
65 screw axis form a helical channel (Figure 4c) with water and
ethanol molecules all entrapped inside it. The percentage of the
unit cell volume occupied by the solvent molecules is lower than
in phase I and amounts to 20% (Figure 4d).
Close similarity of macrocycles 3a and 3b contrasts with their
packing arrangements. Macrocycle 3b crystallizes with four
symmetry independent, but structurally very similar molecules in
a triclinic unit cell. The structure contains two types of isolated
0D voids (Figure 4e) occupied by solvent molecules and the
contribution of these voids to the unit cell volume equals to only
9%.
In the accessible volume of 267.8 Å3 there are two
molecules of ethanol and six and a half molecules of water
involved in multiple hydrogen bonds, so the packing of solvent
molecules is much more compact than in the two crystal phases
of 3a as well as in the crystal structure of meso-5a.
Unlike 3a and 3b, the molecules of meso-5a preserve in the
crystal the enol-imine form (Figure 3b). The mean value of the
X-ray determined C–OH bond length amounts to 1.339(2) Å,
(Table S4), in agreement with the mean value of 1.345(10) Å
calculated for 1194 salicylimine fragments being the OH
tautomers deposited in CSD data base.[14] The meso-5a
crystallizes as chloroform solvate in space group I41/a. Like in
the crystals of phase I of 3a, solvent molecules occupy channels
of varying cross-sections that extend in three dimensions. The
set of interconnecting channels (compare Figs. 4b and 5) forms
possible 3D migration paths for entrapped solvent molecules.
The volume of unit cell occupied by these channels in the
crystals of meso-5a equals to 30%. For comparison, in the three
crystal structures of [4+4] imine macrocycles available in the
CSD the contribution of voids to the unit cell volume does not
Figure 4. 3D, 1D and 0D solvent compartments in the crystal structures of 3a
and 3b. Hydrogen atoms are omitted for clarity. a) Higher-order aggregate
present in crystal phase I of 3a having the water mediated hydrogen-bonded
cyclic trimer as the basic supramolecular motif. The three units generated by a
three-fold symmetry axis are distinguished by colors. b) Intersecting solvent
channels in crystal phase I of 3a. c) Side view of the helical arrangement of
molecules 3a (represented as sticks) around the 65 screw axis in crystal phase
II. Solvent molecules entrapped inside the channel are represented as
spheres of the van der Waals radii; d) top view of the same channels deprived
of solvent molecules. e) Capsules (shaded in yellow) with included solvent
molecules (space-fill representation) formed by molecules 3b (represented as
sticks). Green dashed lines indicate intermolecular hydrogen bonds.
exceed
16%.
In summary, in a single step we have successfully
synthesized representative members of new class of highly
functionalized macrocycles. The control of the structure and
stoichiometry was achieved by the proper choice of reaction
conditions, propensity of reaction products for tautomerisation
and their solubility. Formation of meso heterochiral
diastereomers by hydroxylated polyimine macrocycles has not
been previously reported. Such macrocycles constitute
examples of social self-sorting, unique for this type of
compounds. Due to the stability of meso-5a crystals as
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related compounds give a chance for obtaining new organic,
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progress in our laboratory.
Experimental Section
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For synthetic procedures, full characterization of all new compounds,
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Supporting Information. CCDC 1588862-1588865 contain the
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10.1002/chem.201800316
Chemistry - A European Journal
COMMUNICATION
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COMMUNICATION
A combination of 1H/13C NMR and MS
spectra as well as SCXRD and DFT
studies provided compelling evidence
for a one step synthesis of a new
class of highly functionalized
Joanna Szymkowiak, Beata Warżajtis,
Urszula Rychlewska, Marcin Kwit*
Page No. – Page No.
One-step Access to Resorcinsalens –
Solvent Dependent Synthesis,
Tautomerism, Self-sorting and
Supramolecular Architectures of
Chiral Polyimine Analogues of
Resorcinarene
polyimine macrocycles. Selectivity in
macrocyclization reactions was
achieved by functionalization of the
substrate, change of solvent and
susceptibility to tautomerism. Highly
solvated crystals show 3D system of
interconnecting channels containing
loosely bound guest molecules.
This article is protected by copyright. All rights reserved.