D-Glucosamine based-phosphine for Suzuki-Miyaura cross-coupling reactions in the supported aqueous phase catalysis system

Article abstract of DOI:10.1016/j.tetlet.2012.07.138

A d-glucosamine-based phosphine/Pd(OAc)₂ complex has been applied to the Suzuki-Miyaura coupling reaction of aryl bromides with arylboronic acids using the supported aqueous phase catalysis, SAPC, concept. The recyclability of the catalyst was investigated and revealed a very high activity during the 4 runs.

Full text of DOI:10.1016/j.tetlet.2012.07.138

Tetrahedron Letters 53 (2012) 5602–5604
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Tetrahedron Letters
journal homepage: www.elsevier.com/locate/tetlet
D-Glucosamine based-phosphine for Suzuki-Miyaura cross-coupling reactions
in the supported aqueous phase catalysis system
Karolina Wójcik a,b, ,à, Catherine Goux-Henry a, , Bruno Andrioletti a, , K. Michał Pietrusiewicz b,à
Eric Framery
,
a,
⇑
a
Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (Equipe CASYEN), UMR-CNRS 5246, Université Claude Bernard Lyon 1, Bâtiment Curien (CPE),
3 Boulevard du 11 novembre 1918, F-69622 Villeurbanne Cedex, France
Department of Organic Chemistry, Maria Curie-Sklodowska University, ul. Gliniana 33, 20-614 Lublin, Poland
4
b
a r t i c l e i n f o
a b s t r a c t
Article history:
A D-glucosamine-based phosphine/Pd(OAc)2 complex has been applied to the Suzuki-Miyaura coupling
Received 21 June 2012
Revised 23 July 2012
Accepted 31 July 2012
Available online 7 August 2012
reaction of aryl bromides with arylboronic acids using the supported aqueous phase catalysis, SAPC, con-
cept. The recyclability of the catalyst was investigated and revealed a very high activity during the 4 runs.
Ó 2012 Elsevier Ltd. All rights reserved.
Keywords:
Suzuki-Miyaura reaction
D-Glucosamine
Heterogenous catalysis
SAPC system
Due to the importance of the biaryl compounds in a wide range
of industrial applications including the preparation of pharmaceu-
ticals, herbicides, polymers, the Suzuki-Miyaura cross-coupling
reaction1 is probably one of the most studied Pd-catalyzed reac-
tions by the organic chemistry community. Its catalytic system
provides simple and practical method for creating carbon–carbon
and carbon-nitrogen bonds under sustainable conditions with
excellent yields. Due to the mild conditions, the reactions are
highly tolerant for many functional groups.
immobilization of the catalyst has been also considerably devel-
oped. In the case of Pd catalysts derived from mono- or diphos-
5
phine ligands used in the Suzuki-Miyaura reaction, numerous
6,7
7,8
uses of organic
or inorganic
supports have been described.
An elegant immobilization method is the supported aqueous phase
9
catalysis (SAPC), where the catalyst system is in a liquid phase and
not at the solid-liquid interface as for other supported catalysts.
Although, rhodium complexes are the most extensively used in
SAPC, mainly for the hydroformylation reaction, the first reaction
1
0
Because of its excellent performance, economic and environ-
mental concerns, numerous efforts have been devoted to the devel-
opment of Suzuki-Miyaura reaction under benign conditions.
using this system. A few SAPC examples involving Pd-complexes
11
were described mainly in allylic substitution of allyl acetates and
1
2
in alkoxycarbonylation of alkenes. To the best of our knowledge,
no example of Suzuki-Miyaura cross-coupling reaction using SAPC
methodology has been described in the literature so far.
2
Among them, the use of water as solvent is one possibility. Water
is an attractive solvent for performing chemical reactions, because
of its low cost, non-flammability, non-toxicity, and environmental
concerns. Except in the case of ligand-free methodology,3 the use
of water as solvent requires the preparation of water soluble
In 2002, two of us described the synthesis of a
based phosphine, called 2-deoxy-2-{[4-(diphenylphosphino)
benzoyl]amino}- -glucopyranose (Fig. 1) and its use in the
cross-coupling reaction of aryl iodides or bromides with arylbo-
D-glucosamine-
D
4
ligand, introducing a polar group such as carboxylate, sulfonate,
1
3
ammonium. Many protocols using water as solvent require an
excessive amount of toxic organic solvents for workup (e.g.,
product extraction from water medium), and therefore become
uneconomic and less environmentally. For this reason, the
ronic acids. It has been demonstrated that a medium conversion
is obtained when water is used as solvent. Conversely, when a mix-
ture of toluene/ethanol/water (3/2/2) is used as solvent, where eth-
anol plays the role of transfer agent, excellent yields were
obtained, with TON up to 97,000. Unfortunately, no catalyst recov-
ery has been possible. In this context, we decided to immobilize
⇑
Corresponding author. Tel.: +33 (0) 472 446 263; fax: +33 (0) 472 448 160.
E-mail addresses: kazimierz.pietrusiewicz@poczta.umcs.lublin.pl (K. Michał
the Pd-complex obtained from the same
phosphine, L, and Pd(OAc) in aqueous layer of the SAPC system
in order to recycle the catalyst.
D-glucosamine-based
Pietrusiewicz), eric.framery@univ-lyon1.fr (E. Framery).
Tel.: +33 472 446 263; fax: +33 472 448 160.
2
à
Tel./fax: +48 81 524 22 51x134.
0
040-4039/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tetlet.2012.07.138

K. Wójcik et al. / Tetrahedron Letters 53 (2012) 5602–5604
5603
Table 2
OH
Suzuki-Miyaura cross-coupling of arylbromides and arylboronic acids16
O
HO
OH
O
Z1
[
Pd]
HO HN
Z1
Z2
+
Z2
Br
B(OH)2
PPh2
0
Conv.a (%)
Yieldb (%)
Figure 1.
D
-Glucosamine-based phosphine.
N°
ArBr
4-NO
Ar B(OH)
2
1
2
3
4
5
6
7
8
9
0
2
C
6
H
4
C
6
H
5
100
92
97
50
99
96
76
30
100
93
99
75
95
45
88
95
65
/
96
85
83
75
3-MeCOC
3-MeC
2,6-Me
6 4
H
Table 1
6
H
4
Suzuki-Miyaura cross-coupling of 4-bromonitrobenzene and phenylboronic acid16
2
C
6
H
3
4-MeCOC
4-MeCO
4-VinylC
4-MeOC
2-MeC
4-MeC
6
H
4
C
6
H
5
O2N
2
C
6
H
4
O2N
[Pd]
6
H
4
+
6
H
4
Br
B(OH)2
H
H
6
4
1
6
4
Yielda (%)
11
2-Bromonaphtalene
2-Bromopyridine
85
100
N°
Pd (%mol)
L (%mol)
Run
12
1
2
3
4
5
6
7
8
9
0
1
2
3
4
0.0
1.0
0.0
0.0
1
1
2
1
2
3
4
5
6
1
2
3
4
5
0
74
15
99
95
91
85
40
22
93
86
44
32
18
a
Conversion determined by GC.
Isolated chemical yield after column chromatography.
b
1.0
3.0
4
0% and 20%, respectively (Table 1, entries 4–9). We also tried to
reduce the Pd loading to 0.1% molar (Table 1, entries 10–14). The
yields of the two first runs (93% and 86%) were almost similar to
the two first runs with a Pd loading ten times higher. However
from the third cycle, the yield decreased drastically from 88% to
1
1
1
1
1
0.1
0.3
4
4%, 32%, and 18%. These decreases of yields from the fifth and
the third runs, for 1.0% or 0.1% molar Pd loading respectively, could
be due to some accumulation of salts in the mixture, saturating
aqueous film. However, the excellent yields obtained in the first
runs for the two Pd loadings, demonstrated the positive effect of
a
Isolated chemical yield after column chromatography.
the
catalyst.
After showing the efficiency of the SAPC in the cross-coupling of
D-glucosamine-based phosphine to prevent leaching of the
Before evaluating our SAPC system, we tested first the effect of
bare silica, dried before use under vacuum at 150 °C during 4 h. The
1
4
reaction was carried out in toluene in the presence of SiO
2
,
4-bromonitrobenzene with phenylboronic acid, we studied its effi-
cacy in the coupling reaction of activated or deactivated aryl bro-
mides with various arylboronic acids (Table 2). The reactions
were carried out under the same conditions as described above
with 1% molar of Pd. The yields of coupling of aryl bromides bear-
ing electron withdrawing group with phenylboronic acid were
good, lying between 88% and 99% (Table 2, entries 1, 5 and 6), ex-
cept in the case of 4-vinylbromobenzene where the yield was 65%
with a conversion of 76% (Table 2, entry 7).
In the case of coupling of aryl bromides bearing electron donat-
ing group with phenylboronic acid, the conversions exceeded 90%
(Table 2, entries 9 and 10), except in the case of 4-bromomethoxy-
benzene where a poor conversion of 30% was observed (Table 2, en-
try 8). Biaryl coupling of 4-bromonitrobenzene with 4 arylboronic
acids was also studied (Table 2, entries 1–4). 4-Bromonitrobenzene
reacted efficiently with phenylboronic-, 3-acetylphenylboronic-, or
4-tolylboronic acids giving the corresponding biaryl compounds in
good yields (Table 2, entries 1–3). The sterically hindered 2,6-dim-
ethylphenylboronic acid reacted also (Table 2, entry 4) and afforded
the coupling product in 45% yield.
Na CO (3 equiv) as the base, with a 4-bromonitrobenzene/phenyl-
2
3
boronic acid ratio of 1–1.1, for 24 h at 80 °C (Table 1, entry 1). No
reaction took place. Similarly to explain the role of our ligand in
the SAPC, a catalyst (Pd SAPC) was prepared by impregnating dried
1
4
2
silica with a solution of Pd(OAc) in a mixture of ethanol and
water (ratio 2/1), followed by concentration and drying under vac-
uum at room temperature for 16 h. Indeed, it is well known that
ligand-free Pd(OAc)
aryl iodides and activated or deactivated aryl bromides.
Using the conditions reported before and changing SiO alone by
2
is able to catalyze the coupling reaction of
1
b,1e,15
2
Pd SAPC (1% molar of Pd loading), after the first run, the Pd SAPC
was filtered off, washed with toluene, and dried under vacuum at
room temperature for 16 h, before being used in a second run with-
2
out any addition of Pd(OAc) (Table 1, entries 2 and 3). The yield of
the coupling product of 4-bromonitrobenzene and phenylboronic
acid decreased from 74% to 15%. This drop in performance was ex-
plained by the leaching of the metal when the catalyst was filtered
and washed with toluene between the two cycles of reaction.
Then, we evaluated the recycling of the catalyst (L/Pd SAPC)
prepared by impregnating dried silica14 with a solution of
samine-based phosphine and Pd(OAc)
D
-gluco-
While 2-bromonaphthalene gave very low conversion (20%) of
coupling product with phenylboronic acid with the same Pd load-
ing in a mixture of toluene/ethanol/water as solvent,1 the same
cross-coupling reaction performed under SAPC conditions gave
the biaryl compound with a conversion of 85% (Table 2, entry
11). Finally, the condensation of the heterocyclic 2-bromopyridine
with phenylboronic acid occurred with a total conversion and 75%
isolated chemical yield (Table 2, entry 12).
2
(ratio L/Pd = 3/1) in a mix-
3b
ture of ethanol and water (ratio 2/1), followed by concentration
and drying under vacuum at room temperature for 16 h. Under
the same conditions, with the same Pd loading (1% molar) and
without any addition of catalyst, the chemical yield remained sta-
ble (99–91%) during three runs, and decreased slightly in the
fourth run (85%), before decreasing in the fifth and sixth runs to

5
604
K. Wójcik et al. / Tetrahedron Letters 53 (2012) 5602–5604
In conclusion, the complexes obtained from palladium acetate
and -glucosamine-based phosphines have been already known
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1
1
K.W. thanks the French Ministry of Superior Education and Re-
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2
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l
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2 3
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3