Functionalization at Will of Rim-Differentiated Pillar[5]arenes

Article abstract of DOI:10.1021/acs.orglett.9b01123

The development of an efficient synthetic route toward rim-differentiated C₅-symmetric pillar[5]arenes (P[5]s), whose two rims are decorated with different chemical functionalities, opens up successive transformations of this macrocyclic scaffo

Full text of DOI:10.1021/acs.orglett.9b01123

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Cite This: Org. Lett. XXXX, XXX, XXX−XXX
Functionalization at Will of Rim-Differentiated Pillar[5]arenes
†
,‡,∇
†,∇
†,‡,∇
,†, X‡ ,i§ntong Wan, Weiwei Yang,†
†
Paul Demay-Drouhard,
Ke Du,
Kushal Samanta,
Rajavel Srinivasan,† Andrew C.-H. Sue,* and Han Zuilhof*
,†
†Institute for Molecular Design and Synthesis, School of Pharmaceutical Science & Technology, Tianjin University, 92 Weijin Road,
Nankai District, Tianjin, 300072, People’s Republic of China
‡
Laboratory of Organic Chemistry, Wageningen University, Stippeneng 4, 6703 WE Wageningen, The Netherlands
§
Department of Chemical and Materials Engineering, King Abdulaziz University, 21589 Jeddah, Saudi Arabia
*
S Supporting Information
ABSTRACT: The development of an efficient synthetic route
toward rim-differentiated C -symmetric pillar[5]arenes (P[5]s),
5
whose two rims are decorated with different chemical
functionalities, opens up successive transformations of this
macrocyclic scaffold. This paper describes a gram-scale synthesis
of a C -symmetric penta-hydroxy P[5] precursor, and a range of
5
highly efficient reactions that allow functionalizing either rim at
will via, e.g., sulfur(VI) fluoride exchange (SuFEx) reactions,
esterifications, or Suzuki−Miyaura coupling. Afterward, BBr
3
demethylation activates another rim for similar functionalizations.
he last decades have witnessed significant developments
routinely be synthesized in gram-scale quantities and are easy
to obtain via various routes. The pillarlike shape, in
1
T
of supramolecular chemistry, largely inspired by Nature’s
highly effective approaches to combine both covalent and
noncovalent interactions. An important class of supramolecules
7
,8
combination with their electron-rich nature,
these attractive platforms for separation applications, and
building blocks for complex supramolecular architectures.
has made
9
−15
16−19
2
are macrocyclic compounds, such as cyclodextrins, calixar-
3
,4
5,6
Most common P[5]s are per-functionalized, with 10
identical substituents, which are appealing for their high
enes, and, more recently, pillarenes, especially those of five
repeating aromatic units (pillar[5]arenes or P[5]s; see Figure
). The latter class has characteristic features that they can
20,21
symmetry and facile synthesis.
However, a wealth of
1
additional structural complexity and functionality can be added
22
by alternative functionalization schemes, including mono-
2
3,24
25−27
substitution,
A1/A2 disubstitution,
phenylene sub-
2
8,29
28,29
stitution,
differentiation.
methylene bridge functionalization,
and rim
30,31
The latter approach, which led to tiara-
P[5]s, have received relatively less attention, since there is no
straightforward pathway capable of converting easily available
D -symmetric per-functionalized P[5]s into their correspond-
5
ing C -symmetric rim-differentiated ones. Cyclization of
5
asymmetrically substituted 1,4-dialkoxybenzene monomers is
feasible, but generates the expected C -symmetric isomer in
5
32−36
low selectivity and poor yields (≤5%).
Recently, this
statistical process was recently greatly improved by employing
37,38
the so-called preoriented strategy
starting from asymmetri-
cally substituted 2,5-dialkoxybenzyl alcohols, thereby optimiz-
ing the syntheses of C -symmetric isomers with selectivity
5
higher than 50% and isolated yields up to 20%. This
development paved the way for more widespread applications
and novel chemistries of rim-differentiated P[5] platforms,
which have already been used as amphiphilic self-assemblies
bearing hydrophilic and hydrophobic groups on opposite
Figure 1. Functionalization at will on both sides of C -symmetric rim-
5
differentiated pillar[5]arenes leads to a series of transformations of
this macrocyclic scaffold.
Received: March 30, 2019
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.orglett.9b01123
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
Scheme 1. A Divergent Synthetic Route, Starting from the Gram-Scale Synthesis of a Common Penta-Hydroxy Rim-
a
Differentiated P[5] Precursor (OH) -P[5]
5
a
This route leads to a variety of C -symmetric P[5] derivatives through alkylation, esterification and SuFEx reactions.
5
3
9−43
rims
grafting.
and as promising candidates for multivalent surface
Although the cyclization step has been made
large-scale synthesis of multiple derivatives starting from this
compound.
4
4,45
more efficient, this preoriented protocol requires the synthesis
of the corresponding dialkoxybenzyl alcohol monomer for each
target compound, and the subsequent purification by column
chromatography can be nontrivial. These limitations clearly
hamper the development of this method. A universal rim-
differentiated P[5] building block that can be produced on a
large scale and freely functionalized at either side is thus highly
desired (Figure 1).
In the current paper, we propose an alternative divergent
synthetic route (see Scheme 1) to overcome these limitations
and widely open the door toward rim-differentiated P[5]s that
can be functionalized at will. Key in this route is the efficient,
gram-scale synthesis of a common intermediate, namely,
As a first step, we thus used our preoriented protocol with
(2-(benzyloxy)-5-methoxyphenyl)methanol, which was easily
synthesized in two steps from commercially available reagents
(82% overall yield; typical scale of product = 13 g). The penta-
cyclization reaction thereof yielded the expected rim-differ-
entiated (OBn) -P[5] in a much improved 20% yield in gram-
5
scale batches (1.2 g product per reaction; see the Supporting
Information for detailed synthetic procedures) after straight-
forward column chromatography, followed by quick recrystal-
lization (both using n-hexane/EtOAc). (OBn) -P[5] was
5
27,46
subsequently hydrogenated
(H over Pd/C), quantitatively
2
yielding the corresponding penta-hydroxy (OH) -P[5].
5
Single-crystal samples of air-unstable (OH) -P[5] were
5
(
OH) -P[5] (the five methoxy groups on the other rim are
obtained by vapor−vapor diffusion (n-hexane/EtOAc) under
Ar protection. X-ray crystallography revealed (Figure 2a) that
5
omitted hereafter, for the sake of clarity), which is a rim-
differentiated P[5] equipped with hydroxyl moieties on one
(OH) -P[5] adopts a distorted pentagonal conformation
5
47
side. As it happens, this (OH) -P[5] was recently reported by
similar to per-hydroxylated P[5], in which two aromatic
units are flipped, relative to the other three, as a result of the
three intramolecular hydrogen bonds formed between OH and
OCH3 groups on neighboring phenylene rings ([O···O]
distances of 2.81, 2.81, and 2.67 Å; see Figure 2a, presented
later in this work). In addition, two intermolecular O−H···O H
bonds can be found between different macrocycles, and
5
4
6
Al-Azemi et al. from the corresponding (OBn) -P[5].
5
However, in their report, this benzyl derivative was obtained
via the statistical method from 4-benzyloxyanisole, followed by
hydrogenation. The laborious separation of different constitu-
tional isomers led to a very low isolated yield (<1%) for the
rim-differentiated (OH) -P[5], which certainly precludes any
5
B
DOI: 10.1021/acs.orglett.9b01123
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
between the P[5] macrocycle and its EtOAc guest in the cavity
All previous routes still vary around the theme of
functionalization of the oxygen atom. However, the function-
ality of P[5]s can be altered drastically if the O atom itself
could be replaced and, in this way, changing the electron
density of the macrocyclic scaffold (see Scheme 1). In order to
achieve this, and directly connect aryl groups on the P[5] core,
(
[O···O] distances of 2.82 and 2.81 Å).
For subsequent syntheses, (OH) -P[5] was typically used
5
immediately after hydrogenation, to avoid air oxidation (see
Scheme 1). As earlier attempts, (OH) -P[5] was realkylated
5
with propargyl bromide and NaH at 60 °C to afford pure
(
propargyloxy) -P[5] in 75% yield (57 mg). (OH) -P[5] was
(OH)
(OTf)
engaged in Suzuki−Miyaura couplings to generate (Ph)
and (p-BiPh)
5
-P[5] was converted to the corresponding penta-triflate,
-P[5], in 85% yield (330 mg). This compound was
-P[5]
-P[5] in excellent isolated yields (86%−100%
5
5
also reacted with bromoacetonitrile to generate (OCH CN) -
5
2
5
P[5], also in 75% yield, whose nitrile moiety could easily be
reduced to the corresponding amine later on. While this
divergent synthetic route seems to afford merely rim-
differentiated products already obtainable via our preoriented
route, this procedure is advantageous: the involvement of a C5-
symmetric P[5] that can be synthesized and purified with high
efficiency as the common precursor leads to isomerically pure
final products in the subsequent reactions. In addition, this
5
5
on a 50−150 mg scale) after straightforward column
chromatography with n-hexane/ethyl acetate. The use of
XPhos coupled to a third-generation Buchwald precatalyst
52
(
XPhos-Pd-G3) proved essential to the success of these
couplings, since conventional Pd-based catalysts, e.g., Pd-
PPh ) , failed to give complete conversion. The compounds
(
3 4
shown possess an extended aromatic cavity, where biphenyl
and even terphenyl moieties are the 5-fold repeating units.
Since they are devoid of oxygen atoms on one rim, this should
route uniquely enables the synthesis of C -symmetric P[5]s
5
whose isolation from the corresponding constitutional isomers
3
8
is nontrivial (e.g., (propargyloxy) -P[5])
or simply
5
53
greatly modify the electronic properties of the cage.
The last series of reactions we undertook involved the
deprotection of the methoxy groups on the other rim, and, in
that way, provided access to full and independent control of
the functionalities present on both rims (see Scheme 2).
(
near-)impossible. A clear case of minute differences, down
to only isotopic substitution between the two rims, clearly
demonstrates the strength of this approach. We achieved the
synthesis of CH vs CD rim-differentiated (OCD ) -P[5], an
3
3
3 5
isotopologue of per-methylated P[5], by reacting CD I with
3
(
OH) -P[5] (80% yield). Another noteworthy, rim-differ-
5
Scheme 2. Activating the Other Rim for Further
Functionalization: Demethylation of Various Rim-
Differentiated P[5]s
entiated and highly water-soluble pentasulfonate P[5] ((O-
(
with 1,3-propane sultone (85% yield; 150 mg).
CH ) SO Na) -P[5]) was obtained by reacting (OH) -P[5]
2
3
3
5
5
Moreover, this route provides extra functional group
tolerance for moieties that are incompatible with the
Friedel−Crafts cyclization conditions toward P[5], such as
esters. In the current approach, esterification by reacting rim-
differentiated (OH) -P[5] with acyl chlorides is rather easy,
5
providing access to (OCOMe) -P[5] and (OCOPr) -P[5] in
5
5
typically >60% yields (65−80 mg scale) at room temperature
rt). Harsher conditions were required for the less-reactive
benzoyl chloride (KOH in refluxing CH Cl /H O), but the
(
2
2
2
expected (OCOPh) -P[5] could be isolated in 54% yield.
5
While alkylation and esterification reactions generally result
in fair to very good yields, highly efficient chemistry that
converts five reactive handles on rim-differentiated P[5]
simultaneously is still highly desired. An alternative approach
Common P[5]s are decorated with multiple alkoxy groups
on both rims that cannot be removed selectively, and this
grossly limits the design of novel P[5]s. In our work, robust
to functionalization of the −OH moieties of (OH) -P[5] is the
5
48
sulfur(VI) fluoride exchange (SuFEx) reaction. This SuFEx
C−C and OSO O linkages are effected through Suzuki−
2
click chemistry has proven to be especially useful to obtain
Miyaura coupling and SuFEx reactions on one rim of P[5] first,
49
high yields in constrained environments, as present near the
thus opening up the other rim for further reactions via BBr3
rim of P[5]. (OH) -P[5] was cleanly reacted with sulfuryl
5
demethylation. As typical examples, conjugated (Ph) -P[5]
5
fluoride gas in the presence of base to obtain the
and (p-BiPh) -P[5] were reacted with BBr in dry CHCl , to
5
3
3
corresponding fluorosulfate. This (OSO F) -P[5] was allowed
2
5
afford the corresponding penta-hydroxy compounds in 70%−
to react with a range of aromatic tert-butyldimethylsilyl (TBS)
ethers to give rim-differentiated P[5]s with penta-OSO OPh,
9
0% yields. Analogously, the five OCH at the lower rim of
3
2
(OSO Op-BiPh) -P[5] were also cleanly demethylated,
2 5
50,51
OSO Op-BiPh, and photoswitchable
OSO Op-azobenzene
2
2
yielding corresponding penta−OH compounds in 55% isolated
yields. All these compounds are readily available for further
transformations via synthetic strategies described above, thus
obtaining the desired freedom of functionalization on both
rims at will.
(
see the Supporting Information for UV-vis characterization)
moieties on one rim, respectively. All reactions proceeded in
good to excellent isolated yields after simple recrystallization or
precipitation and MeOH washing (see Scheme 1; the amount
of isolated product is typically 100 mg). Given the wide, and
still rapidly expanding, scope and high efficacy of SuFEx
reactions, we would argue that this methodology provides
significant potential to a broad range of P[5]s with different
functionalization patterns and other types of macrocycles and
supramolecules.
The structures of (OH) -P[5], (OCH CN) -P[5], (Ph) -
5
2
5
5
P[5], (Ph) (OH) -P[5], (p-BiPh) -P[5], (p-BiPh) (OH) -
5
5
5
5
5
P[5], (OSO OPh) -P[5], and (OSO Op-azobenzene) -P[5]
2
5
2
5
were all confirmed via X-ray crystallography (Figure 2). The
expected regular pentagonal cavity was observed for each P[5],
except for (OH) -P[5], as discussed earlier.
5
C
DOI: 10.1021/acs.orglett.9b01123
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
crystallographic data for this paper. These data can be obtained
free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by
emailing data_request@ccdc.cam.ac.uk, or by contacting The
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
AUTHOR INFORMATION
Corresponding Authors
■
*
*
E-mail: andrew.sue@tju.edu.cn (A. C.-H. Sue).
E-mail: han.zuilhof@wur.nl (H. Zuilhof).
ORCID
Paul Demay-Drouhard: 0000-0003-2270-1177
Ke Du: 0000-0002-1786-7327
Kushal Samanta: 0000-0002-7414-4475
Xintong Wan: 0000-0002-5792-0030
Weiwei Yang: 0000-0003-3062-6023
Rajavel Srinivasan: 0000-0001-8374-1952
Andrew C.-H. Sue: 0000-0001-9557-2658
Han Zuilhof: 0000-0001-5773-8506
Author Contributions
∇
These authors contributed equally.
Figure 2. X-ray solid-state structures of representative compounds,
depicted in a blend of tubular stick and space-filling representations:
Notes
(
a) side and top views of (OH) -P[5], (b) (OCH CN) -P[5], (c)
Ph) -P[5], (d) (Ph) (OH) -P[5], (e) (p-BiPh) -P[5], (f) (p-
5 2 5
The authors declare no competing financial interest.
(
5 5 5 5
BiPh) (OH) -P[5] (g) (OSO OPh) -P[5], (h) (OSO Op-azoben-
5
5
2
5
2
ACKNOWLEDGMENTS
zene) -P[5]. All these compounds crystallize as racemates, and only
■
5
one enantiomeric conformer is shown. Hydrogen atoms and solvents
are omitted for clarity. Color code: carbon, gray; oxygen, red;
nitrogen, blue, sulfur, yellow.
This work was supported by the 973 National Basic Research
Program of China (No. 2015CB856500, to A.C.-H.S. and
H.Z.), National Science Foundation of China (No. 21871208,
to H.Z.), National Thousand Young Talents Program of China
(to A.C.-H.S.), the Tianjin City Thousand Talents Program
(to A.C.-H.S. and H.Z.), and Wageningen University.
In summary, a series of new C -symmetric macrocycles
5
derived from the pillar[5]arene family was synthesized in good
to excellent yields, starting from a common penta-hydroxy rim-
differentiated P[5] intermediate. Reaction of the −OH
moieties via alkylation, esterification, or SuFEx strategies
allows a broad variety of substituents to be installed. In
addition, conversion of the −OH moieties to triflates, followed
by Suzuki−Miyaura coupling affords removal of the O atoms
and C−C based structures, with altogether different steric and
electronic properties. Finally, subsequent removal of the
methyl groups on the lower rim opens this side up to
analogous functionalization schemes, thus allowing pillar[5]-
arenes to be functionalized fully at will on both sides. This will
further broaden the scope of the chemistry of 5-fold symmetric
macrocycles via additional studies of host−guest interactions,
substitution effects and solid-state properties, and likely yields
wide application, especially via novel building blocks, in
supramolecular architectures, reticular chemistry, and func-
tional π-systems.
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DOI: 10.1021/acs.orglett.9b01123
Org. Lett. XXXX, XXX, XXX−XXX