Solid-phase synthesis of biphenyls and terphenyls by the traceless multifunctional cleavage of polymer-bound arenesulfonates

Article abstract of DOI:10.1002/ejoc.200500279

Nickel-catalyzed reactions between polymer-bound arene-sulfonates and aryl Grignard reagents produce unfunctionalized biphenyls and terphenyls in good yields through reductive cleavage/cross-coupling of the C-S bond. This novel traceless multifunctional cleavage strategy appears to be a powerful tool for the preparation of large oligophenyl libraries, because it allows the introduction of diversity concomitantly with the release of the target compounds. Wiley-VCH Verlag GmbH & Co. KGaA, 2005.

Full text of DOI:10.1002/ejoc.200500279

SHORT COMMUNICATION
Solid-Phase Synthesis of Biphenyls and Terphenyls by the Traceless
Multifunctional Cleavage of Polymer-Bound Arenesulfonates
[a]
[b]
[a]
[a]
[b]
Chul-Hee Cho, Heon Park, Min-Ah Park, Tae-Yong Ryoo, Yoon-Sik Lee, and
Kwangyong Park*[
a]
Keywords: Biaryls / Cross-coupling / Solid-phase synthesis / Sulfonate / Traceless multifunctional cleavage
Nickel-catalyzed reactions between polymer-bound arene-
sulfonates and aryl Grignard reagents produce unfunction-
alized biphenyls and terphenyls in good yields through re-
ductive cleavage/cross-coupling of the C–S bond. This novel
traceless multifunctional cleavage strategy appears to be a
powerful tool for the preparation of large oligophenyl librar-
ies, because it allows the introduction of diversity concomi-
tantly with the release of the target compounds.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2005)
Introduction
though traceless strategies based on the cleavage of C–S
[
7]
bonds have also been investigated. The carbon–sulfur
Since Merrifield’s pioneering work in solid-phase peptide
synthesis in the 1960s,[ solid-phase organic synthesis
[8]
[9]
bonds in polymer-bound thioethers, sulfones, thioes-
1]
[10]
[11]
[12]
ters,
sulfonamides,
and trialkylsulfonium salts
(SPOS) has formed the core of parallel synthesis and com-
could be cleaved without leaving any functional groups un-
der appropriate conditions. Traceless multifunctional cleav-
age linker systems, allowing the introduction of certain
atoms or molecular fragments at the original linking site
during the cleavage step, are of particular interest as they
allow for the additional diversification of the library with
binatorial chemistry, two areas that play an important role
in the discovery and development of new molecules with
predetermined profiles of properties.[ The final step of
SPOS always requires the cleavage of a covalent bond link-
ing the product to the resin, prior to the former’s isolation,
characterization, and biological evaluation. The utilization
of suitable linkers that allow facile attachment, functionali-
zation, and release of the molecules of interest is therefore
vital to all SPOS methodologies.[
2]
[13]
the release of the target compound.
Biphenyl compounds are popular synthetic targets, since
the biphenyl moiety is an important pharmacophore pres-
3]
[14]
ent in many biologically active molecules.
The biphenyl
Almost all linkers are currently designed to unmask a
polar functionality on release of the substrate from the
resin, because linkage to the polymeric support is achieved
through the functionality already present in the target mole-
cule. However, this polar functionality eventually limits the
structure/activity relationships derived from these com-
pounds, so the development of traceless linker strategies
that will enable the release of unfunctionalized hydro-
carbons from the polymer support represents an important
unit is also represented in a variety of other valuable com-
pounds including liquid crystals and chiral reagents. Ter-
[15]
phenyl derivatives are also known to exhibit interesting op-
[16]
[17]
tical
and electrical
properties, and are of particular
[18]
interest in the area of liquid crystals. Moreover, naturally
isolated p-terphenyl metabolites are known to possess po-
[19]
tent biological activities.
There are numerous methods for the preparation of un-
symmetrical biphenyls and terphenyls, many of which have
been known for several decades. Among these, the use of
the palladium- and nickel-catalyzed coupling reactions[
[4]
challenge in SPOS. To this end, the traceless cleavage of
[
5]
[6]
C–Si and C–N bonds has been extensively studied, al-
20]
[
21]
of aryl halides and pseudohalides with arylboronic acids,
[
22]
[23]
arylstannanes,
lides
arylzincs,
and arylmagnesium ha-
to produce unsymmetrical oligophenyls has been
extensively studied. Since Pd -mediated C–C bond-forming
[
[
a] School of Chemical and Materials Engineering, Chung-Ang
[24]
University,
0
Heukseok-Dong 221, Dongjak-Ku, Seoul 156-756, South Ko-
rea
reactions were first explored on solid supports in the early
Fax: +82-2-815-5476
E-mail: kypark@cau.ac.kr
[25]
1
990s, the repertoire of these reactions in the area of so-
b] School of Chemical and Biological Engineering, Seoul National lid-phase parallel synthesis/combinatorial chemistry has
University,
Seoul 151-744, South Korea
[26]
steadily increased.
Amongst these solid-phase reactions,
the preparation of biphenyl libraries is one of the most fa-
Supporting information for this article is available on the
WWW under http://www.eurjoc.org or from the author.
[
27]
vored applications of these catalysts. However, there are
Eur. J. Org. Chem. 2005, 3177–3181
DOI: 10.1002/ejoc.200500279
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3177

C.-H. Cho, H. Park, M.-A. Park, T.-Y. Ryoo, Y.-S. Lee, K. Park
SHORT COMMUNICATION
few synthetic strategies for the solid-phase preparation of Results and Discussion
unfunctionalized biphenyls and terphenyls, due to the ab-
sence of efficient traceless linker systems.
Recently, we demonstrated that the nickel-catalyzed
cross-coupling reactions of neopentyl arenesulfonates with
arylmagnesium bromides, involving the ipso-nucleophilic
aromatic substitution of alkyloxysulfonyl groups by aryl nu-
Polymer-bound arenesulfonates 3a–d were prepared by
[
31]
treatment of hydroxyethylmethyl resin 1
with the corre-
sponding arenesulfonyl chlorides 2 in the presence of Et N
3
(
Table 1). After the reaction had been allowed to proceed
for 48 h at room temperature, the resulting arenesulfonate
resin 3 was recovered by filtration after standard workup.
The isolated yields of 3 were 78–85% based on the loading
levels of the resins, which were determined by elemental
analysis. The efficient sulfonylation was confirmed by IR
analysis, which showed the disappearance of the IR bands
at 3583 (sharp) and 3452 cm–1 (broad) corresponding to the
hydroxy group of 1, as well as the appearance of new IR
bands corresponding to the sulfate group at 1363 and
cleophiles, efficiently produce unsymmetrical biphenyls and
terphenyls (Scheme 1).[
28]
On the basis of these results, it
was anticipated that the aryl moieties of the arenesulfonates
attached to the solid support could be liberated without
leaving a polar “trace” by use of appropriate nucleophiles.
1
–1
–1
1
1
177 cm– (3a), 1358 and 1175 cm
(3b), 1358 and
172 cm–1 (3c), and 1364 and 1186 cm (3d) (see the Sup-
porting Information). The remaining hydroxy group of 3
Scheme 1. Nickel-catalyzed cross-coupling of arenesulfonates with was converted into the methoxy group by treatment with
aryl Grignard reagents.
excess CH I, before the next step was carried out.
3
Table 1. Preparation of polymer-bound arenesulfonates 3.[a]
In this paper we report on our attempts to develop a
novel sulfonate-based traceless multifunctional linker sys-
tem through nickel-catalyzed reductive cleavage/cross-coup-
ling of the C–S bond. Under our conditions, reactions be-
tween polymer-bound arenesulfonates and aryl Grignard
reagents produced unfunctionalized biphenyls and terphen-
yls in good yields (Scheme 2). While traceless strategies
using the famous catalytic cleavage of the C–O bonds of
resin-bound arylsulfonates[
nates
29]
and perfluoroalkylsulfo-
[
30]
have been extensively investigated, the cleavage of
the C–S bonds of polymer-bound sulfonates has not, to the
best of our knowledge, previously been reported. The re-
sults of this study are presented and discussed below.
[
a] The reactions between resin 1 (4.6 mmol) and the sulfonyl chlo-
rides (18.2 mmol) were carried out in CH Cl (75 mL) in the pres-
ence of Et N (22.8 mmol). [b] Yields of the isolated products based
2
2
3
on the loading level of polymer-bound sulfonate 3 determined by
elemental analysis.
The traceless multifunctional cleavage of 3 with aryl
Grignard reagents 4 was carried out under the optimized
conditions for the corresponding solution-phase reac-
[
28b]
tions.
used in reactions with polymer-bound aldehydes, ketones,
While organomagnesium reagents have often been
[
32]
and esters,
solid supports,
reaction with polymer-bound substrates has not been exten-
sively studied. Arenesulfonates 3a–c underwent cleavage/
cross-coupling reactions with 15 equivalents of 4 in the
presence of [1,1Ј-bis(diphenylphosphanyl)ferrocene]dichlo-
as well as in the cleavage of products from
[
33]
their nickel-catalyzed Kumada coupling
[
34]
ronickel (dppfNiCl ) to produce the desired unfunction-
2
alized biphenyls 5 in good isolated yields within 48 h
(Table 2). The crude products 5 could be purified either by
Scheme 2. Preparation of unfunctionalized terphenyls by the trace-
less multifunctional cleavage strategy.
3178
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2005, 3177–3181

Solid-Phase Synthesis of Biphenyls and Terphenyls
SHORT COMMUNICATION
column chromatography or by preparative HPLC, even has been consistently observed in corresponding solution-
[
28]
though the purification was complicated by the existence of phase reactions.
The relatively easier separation of the
undesired biaryls derived from the homocoupling of 4. The naphthalene derivatives 5e–h from the biphenyl side pro-
famous nucleophilic substitution of arenesulfonates by the duct also played an important role in improving their iso-
catalytic cleavage of the C–O bond was not observed by lated yields, as compared to those of the simple biphenyls
1
[35]
GC or H NMR analysis. Additional confirmation of the 5a–d. Aminonaphthalenesulfonates 3c also showed compet-
efficient cleavage of the C–S bond was provided by the IR itive reactivity, generating the biaryl compounds 5i and 5j
spectrum of the recovered resin 1, in which the absorption in good yields under the standard reaction conditions (En-
band corresponding to the hydroxy group was clearly de- tries 9 and 10).
tected.
We further explored the generality of this traceless cleav-
age/cross-coupling strategy by synthesizing a small library
of unfunctionalized terphenyls 8 (Table 3). Thus, resin-
bound 4-bromobenzenesulfonate (3d) was split into two ali-
quots, which were separately subjected to the Suzuki coup-
ling reaction with phenylborinic acid (6a) and 4-tolylbo-
ronic acid (6b) in the presence of Pd(PPh ) and aqueous
Table 2. Solid-phase preparation of unfunctionalized biphenyls 5.[a]
3
4
Na CO in DME. These palladium-catalyzed coupling re-
2
3
actions produced the biphenylsulfonates 7a and 7b, respec-
tively. The liberation of arenesulfonate derivatives via the
cleavage of the C–O bond by the Pd catalyst was not de-
tected under our standard reaction conditions.
Table 3. Solid-phase preparation of unfunctionalized terphenyls
[a]
8.
[
1
(
a] The reactions between resin 3 (0.261 mmol) and 4 (2.61 +
.31 mmol) were carried out at the reflux temperature of THF
8.0 mL) in the presence of dppfNiCl (0.0781 mmol). [b] Yields of
2
isolated products purified by column chromatography on silica gel
and based on the loading level of 3. [c] The yields refer to the iso-
lated products by preparative HPLC and based on the loading level
of 3.
4
-Methoxyphenylmagnesium bromide (4c) showed
slightly diminished efficiency due to the secondary cross-
coupling reaction of the initially formed methoxybiphenyls 1.31 mmol) were carried out at the reflux temperature of THF
[a] The reactions between resin 7 (0.261 mmol) and 4 (2.61 +
5
c and 5g with excess 4c through the cleavage of the car- (8.0 mL) in the presence of dppfNiCl
2
(0.0781 mmol). [b] The reac-
tions between resin 3d (1.60 mmol) and 6 (5.28 mmol) were carried
out in DME (38.0 mL) in the presence of Pd(PPh (0.144 mmol)
[36]
bon–oxygen bonds (Entries 3 and 7).
Naphthalenesulfo-
3 4
)
nate 3b (Entries 5–8) showed better reactivity than benzene-
sulfonate 3a (Entries 1–4), as would be expected given that
1
1
and aqueous Na
2 3
CO (3.2 mmol); 7a: R = H, 7b: R = 4-Me. [c] 4e
=
p-tert-butylphenylmagnesium bromide. [d] Overall yields of the
the faster reaction of the more conjugated arenesulfonates isolated products based on the loading level of 3d.
Eur. J. Org. Chem. 2005, 3177–3181
www.eurjoc.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3179

C.-H. Cho, H. Park, M.-A. Park, T.-Y. Ryoo, Y.-S. Lee, K. Park
SHORT COMMUNICATION
Polymer-bound biphenylsulfonates 7 were allowed to un-
dergo the nickel-catalyzed coupling reaction with 4 to pro-
duce unsymmetrical terphenyl derivatives 8. The more con-
jugated biphenylsulfonates 7 showed better reactivity
towards the nickel catalyst than the benzenesulfonates 3a
and 3b, as would be expected. Treatment of the polymer-
supported biphenylsulfonates 7 with 15 equivalents of 4 in
[
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