Green Catalysis: Hydroxycarbonylation of Aryl Halides in Water Catalyzed by an Amphiphilic Resin-Supported Phosphine-Palladium Complex

Full text of DOI:10.1021/jo990631f

J . Org. Chem. 1999, 64, 6921-6923
6921
Gr een Ca ta lysis: Hyd r oxyca r bon yla tion of
Sch em e 1
Ar yl Ha lid es in Wa ter Ca ta lyzed by a n
Am p h ip h ilic Resin -Su p p or ted
P h osp h in e-P a lla d iu m Com p lex
Yasuhiro Uozumi*,† and Toshihiro Watanabe
Faculty of Pharmaceutical Sciences, Nagoya City University,
Mizuho-ku, Nagoya 467-8603, J apan
Received April 14, 1999
The development of environmentally friendly catalysts
for organic transformation is becoming an area of growing
1
importance. Our research interests, recently, lie in the
development of solid-supported transition metal com-
2
,3
plexes
realizing high catalytic activity in aqueous
performed in water in the presence of an amphiphilic
solid-supported phosphine-palladium complex under an
atmospheric pressure of carbon monoxide to give the
corresponding carboxylic acids in high yields under mild
reaction conditions.
media4 which would provide a safe, resource-saving, and
environmentally benign process. Solid-phase catalytic
reactions are also useful means of high-throughput
organic syntheses as well as industrial production of fine
,5
6
chemicals. We have previously reported the design and
The amphiphilic resin-supported palladium catalyst
was prepared according to the procedures previously
preparation of amphiphilic palladium-phosphine com-
plexes bound to PEG-PS resin which exhibit high
catalytic activity in the Tsuji-Trost reaction and Su-
zuki-Miyaura cross-coupling.2 Here we report a four-
2c
reported. Thus, the palladium-triarylphosphine com-
11
plex, Pd-PEP (2), bound to amphiphilic solid supports
,7,8
was prepared on poly(ethylene glycol)-polystyrene graft
phase protocol of the palladium-catalyzed hydroxycar-
2
copolymer (PEG-PS) resin, ArgoGel NH , which has
bonylation9
,10
of aryl or alkenyl halides which was
been well-documented to exhibit good swelling properties
in water (Scheme 1).12 The Pd-PEP complex 2 catalyzed
the hydroxycarbonylation of aryl iodides 3 in water under
very mild reaction conditions to give benzoic acids 4
(Scheme 2). A mixture of iodobenzene (0.4 mmol) and
potassium carbonate (3.6 mmol) in 2 mL of water was
agitated vigorously with shaking on a wrist-action shaker
under an atmospheric pressure of carbon monoxide in the
presence of 3 mol % palladium of the Pd-PEP at 25 °C
for 20 h. A small amount of metal leaching was observed
during the reaction. The reaction mixture was filtered,
and the resin was rinsed twice with a small amount of
aqueous sodium bicarbonate. The combined filtrate was
acidified (pH = 1) with concentrated hydrochloric acid
to make a precipitate of benzoic acid and extracted with
ether. Concentration of the extract gave 97% yield of
benzoic acid (4a ), and the purity of 4a was assessed by
†
E-mail: uo@phar.nagoya-cu.ac.jp.
1) For a review, see: Anastas, P. T., Williamson, T. C., Eds. Green
(
Chemistry; ACS Symposium Series 626; American Chemical Society:
Washington, DC, 1996; and references therein.
(2) (a) Uozumi, Y.; Danjo, H.; Hayashi, T. Tetrahedron Lett. 1997,
3
3
6
8, 3557. (b) Uozumi, Y.; Danjo, H.; Hayashi, T. Tetrahedron Lett. 1998,
9, 8303. (c) Uozumi, Y.; Danjo, H.; Hayashi, T. J . Org. Chem. 1999,
4, 3384.
(3) For recent reviews, see: (a) Bunin, B. A. Combinatorial Index;
Academic Press: London, 1998; p 262. (b) Obrecht, D.; Villalgordo, J .
M. Solid-Supported Combinatorial and Parallel Synthesis of Small-
Molecular-Weight Compound Libraries, Tetrahedron Organic Chem-
istry Series Vol. 17; Elsevier: Oxford, U.K., 1998; p. 44.
(4) For reviews, see: (a) Li, C.-J .; Chan, T.-H. Organic Reactions in
Aqueous Media; Wiley: New York, 1997. (b) Grieco, P. A., Ed. Organic
Synthesis in Water; Kluwer Academic Publishers: Dordrecht, The
Netherlands, 1997.
(
5) For a review, see: Herrmann W. A.; Kohlpaintner, C. W. Angew.
Chem., Int. Ed. Engl. 1993, 32, 1524.
6) Examples of solid-supported reagents, see: (a) Nagayama, S.;
(
Endo, M.; Kobayashi, S. J . Org. Chem. 1998, 63, 6094. (b) Kobayashi,
S.; Nagayama, S. J . Am. Chem. Soc. 1996, 118, 8977. (c) Kobayashi,
S.; Nagayama, S.; Busujima, T. Tetrahedron Lett. 1996, 37, 9221. (d)
Pop, I. E.; D e´ prez, B. P.; Tartar, A. L. J . Org. Chem. 1997, 62, 2594.
e) Flynn, D. L.; Crich, J . Z.; Devraj, R. V.; Hockerman, S. L.; Parlow,
J . J .; Southand, M. SD.; Woodard, S. S. J . Am. Chem. Soc. 1997, 119,
(9) (a) Kiji, J .; Okano, T.; Nishiumi, N.; Konishi, H. Chem. Lett. 1988,
957. (b) Okano, T.; Uchida, I.; Nakagaki, T.; Konishi, H.; Kiji, J . J .
Mol. Catal. 1989, 54, 65. (c) Okano, T. Okabe, N.; Kiji, J . Bull. Chem.
Soc. J pn. 1992, 65, 2589. (d) Goux, C.; Lhoste, P.; Sinou, D.; Masdeu,
A. J . Organomet. Chem. 1996, 511, 139.
(
4
1
7
874. (f) Kulkarni, B. A.; Ganesan, A. Angew. Chem., Int. Ed. Engl.
997, 36, 2454. (g) Kulkarni, B. A.; Ganesan, A. Chem. Commun. 1998,
(10) (a) Cassar, L.; Foa, M.; Gardano, A. J . Organomet. Chem. 1976,
121, C55. (b) Valentine, D., J r.; Tilley, J . W.; LeMahieu, R. A. J . Org.
Chem. 1981, 46, 4650. (c) Bumagin, N. A.; Nikitin, K. V.; Beletskaya,
I. P. J . Organomet. Chem. 1988, 358, 563.
85.
(7) Recent examples of reactions catalyzed by palladium-phosphine
complexes performed in aqueous organic solvents: (a) Gen eˆ t, J . P.;
Blart, E.; Savignac, M. Synlett 1992, 715. (b) Gen eˆ t, J . P.; Blart, E.;
Savignac, M.; Lemeune, S.; Paris, J .-M. Tetrahedron Lett. 1993, 34,
1
3
31
(11) Gel-phase C and P NMR studies on Pd-PEP (2) have been
2
c
3
3 5
reported in which an η -C H group and a phosphorus atom coordi-
4
189. (c) Lemaire-Audoire, S.; Savignac, M.; Blart, E.; Pourcelot, G.;
nated to palladium were observed, respectively. In addition, elemental
analysis and ICP-atomic emission spectroscopy of 2 showed the ratio
of palladium, phosphorus, and chlorine to be 1.1/1.0/1.0 (Pd/P/Cl). These
Gen eˆ t, J . P. Tetrahedron Lett. 1994, 35, 8783. (d) Gen eˆ t, J . P.; Blart,
E.; Savignac, M.; Lemeune, S.; Lemaire-Audoire, S.; Paris, J .-M.;
Bernard, J .-M. Tetrahedron 1994, 50, 497. (e) Blart, E.; Gen eˆ t, J . P.;
Safi, M.; Savignac, M.; Sinou, D. Tetrahedron 1994, 50, 505. (f)
Amatore, C.; Blart, E.; Gen eˆ t, J . P.; J utand, A.; Lemaire-Audoire, S.;
Savignac, M. J . Org. Chem. 1995, 60, 6829. (g) Lemaire-Audoire, S.;
Savignac, M.; Dupuis, C.; Gen eˆ t, J . P. Tetrahedron Lett. 1996, 37, 2003.
results demonstrate that the structure of the palladium complex moiety
3
at the terminus of PEG chain is PdCl(η -C
3
H
5
)(Ph
2
PC
6
H
4
-resin).
(12) (a) Bayer, E.; Rapp, W. In Chemistry of Peptides and Proteins;
Voelter, W., Bayer, E., Ovchinikov, Y. A., Iwanov, V. T., Eds.; Walter
de Gruter: Berlin, 1986, Vol. 3, p 3. (b) Rapp, W. in Combinatorial
Peptide and Nonpeptide Libraries; J ung, G., Ed.; VCH: Weinheim,
Germany,1996; p 425. (c) Du, X.; Armstrong, R. W. J . Org. Chem. 1997,
62, 5678. (d) Gooding, O. W.; Baudert, S.; Deegan, T. L.; Heisler, K.;
Labadie, J . W.; Newcomb, W. S.; Porco, J . A., J r.; Eikeren, P. J . Comb.
Chem. 1999, 1, 113.
(
h) Bumagin, N. A.; Bykov, V. V.; Sukhomlinova, L. I.; Tolstaya, T. P.;
Beletskaya, I. P. J . Organomet. Chem. 1995, 486, 259.
8) Very recently, Bergbreiter and Liu have reported water-soluble
(
polymer-bound, recyclable palladium(0)-phosphine catalysts; see:
Bergbreiter, D. E.; Liu, Y.-S. Tetrahedron Lett. 1997, 38, 7843.
1
0.1021/jo990631f CCC: $18.00 © 1999 American Chemical Society
Published on Web 08/12/1999

6
922 J . Org. Chem., Vol. 64, No. 18, 1999
Ta ble 1. Hyd r oxyca r bon yla tion of Ar yl Ha lid es in Wa ter Ca ta lyzed by P d -P EP (2)a
Notes
entry
aryl halide
base
product
yield (%)b
entry
10c
aryl halide
base
product
yield (%)b
1
2
3
4
5
6
3a (X ) H)
K2CO3
K2CO3
KOH
K2CO3
K2CO3
KOH
K2CO3
KOH
K2CO3
4a
4b
4b
4c
4d
4d
4e
4e
4f
97
55
96
99
55
100
53
96
3g (X ) 4-Br)
3h (X ) 4-NO2)
3i (X ) 4-CF3)
3j (X ) 3-COOEt)
3k (X ) 3-I)
3l (X ) 4-I)
K2CO3
K2CO3
K2CO3
K2CO3
KOH
KOH
K2CO3
KOH
4g
4h
4i
4j
6
7
9
4a
100
100
96
c
3b (X ) 2-CH3)
3b (X ) 2-CH3)
3c (X ) 3-CH3)
3d (X ) 4-CH3)
3d (X ) 4-CH3)
3e (X ) 4-OCH3)
3e (X ) 4-OCH3)
3f (X ) 4-Cl)
11
12
13
14
93
92
c
c
e
c
c
15
93
78
45
c
7
8
16
8
c
17f
bromobenzene
c,d
9
99
a
All reactions were carried out with shaking in water under carbon monoxide (1 atm) at 25 °C for 12-20 h, unless otherwise noted:
b
1
aryl halide (0.4 mmol), H2O (2.0 mL), K2CO3 (3.6 mmol), 2 (3 mol % Pd). Isolated yield. Purities of all products were assessed by
H
NMR study (400 MHz) to be >98%. 200 µL of benzene was used as a cosolvent. d Reaction for 40 h. e A mixture with a small amount of
c
f
3
-iodobenzoic acid. 10 mol % palladium of PEP-Pd catalyst was used.
Sch em e 2
Sch em e 3
1
H NMR study (400 MHz) to be >98%. The carbonylation
using water-soluble phosphine ligand TPPTS13 and poly-
styrene-supported triphenylphosphine showed much lower
catalytic activity under the reaction conditions giving
2
0% and 13% yield of 4a , respectively. A number of
commercially available phosphine ligands (e.g., tri-
phenylphosphine) are unsuitable for use in water owing
to their insolubility. The resin-supported complex 2 also
catalyzed the carbonylation of iodobenzene in methanol
or ethanol under the same conditions to give an 81% yield
of methyl or ethyl benzoate (5 or 5′).
The hydroxycarbonylation is comprised of four phases,
gas, solid, organic, and aqueous phases. By using this
four-phase protocol, carbon monoxide (gas phase) and the
starting halide (organic phase) should diffuse into the
catalyst resin (solid phase) during the reaction, and the
resulting carboxylic acid is immediately extracted with
alkaline solution (aqueous phase). They are readily
separated each other, and subsequent reapplication of
the catalyst is made facile (Scheme 3). Thus, after the
workup, the recovered catalyst resin was subjected to a
second series of the reaction to give 96% yield of 4a under
otherwise the same reaction conditions. The chemical
yield observed in the 30 continuous runs ranged between
4, 9-13). o-Tolyl iodide (3b), p-tolyl iodide (3d ), and
p-anisyl iodide (3e) showed a little lower reactivity under
the reaction conditions, presumably because of steric
bulkiness and/or electron-donating character of the sub-
stituents. A significant improvement of the catalytic
activity of Pd-PEP was observed in the carbonylation
of 3b,d ,e when potassium hydroxide was used as a base
(entries 2, 3, 5-8). Thus, for example, the hydroxycar-
bonylation of 3e in aqueous potassium hydroxide gave
4e in 96% under otherwise the same reaction conditions,
while that in aqueous potassium carbonate gave only 53%
yield of the desired acid. The hydroxycarbonylation took
place successively on the two iodides of 1,3- and 1,4-
diiodobenzenes (3k ,l), which gave quantitative yields of
isophthalic acid 6 and terephthalic acid 7, respectively
(entries 14 and 15). All these products were obtained
without chromatographical purification, the workup con-
sisting of only filtration and extraction.
This simple protocol for the preparation of carboxylic
acids was also successfully applied to alkenyl and aryl
bromides under the same reaction conditions. Bromosty-
rene 8 underwent hydroxycarbonylation to give a 78%
yield of cinnamic acid (9) (Scheme 4) (Table 1, entry 16).
It is noteworthy that bromobenzene undergoes pal-
ladium-catalyzed hydroxycarbonylation at 25 °C in water
9
4 and 100%, the average being 97% yield (Scheme 3).
Table 1 summarizes the representative results of the
hydroxycarbonylation. The hydroxycarbonylation of m-
tolyl iodide (3c), 4-chlorophenyl iodide (3f), 4-bromo-
phenyl iodide (3g), 4-nitrophenyl iodide (3h ), 4-(trifluo-
romethyl)phenyl iodide (3i), and m-ethyl iodobenzoate
(3j) gave 4c,f-j in 96-100% yield, respectively (entries
(entry 17), though the oxidative addition of aryl bromides
to palladium(0) species requires 80 °C or higher reaction
temperature in general.14 A mixture of bromobenzene and
10 mol % palladium of resin-supported complex 2 in 2.0
(
13) TPPTS ) triphenylphosphinetrisulfonate sodium salt. (a) Kuntz,
E. G. German Patent No. 2627354, 1976. (b) Sinou, D. Bull. Soc. Chim.
Fr. 1987, 3, 480. See also refs 7a-g.

Notes
J . Org. Chem., Vol. 64, No. 18, 1999 6923
Sch em e 4
performed on a wrist-action shaker (Burrel Scientific, Inc.). All
products shown in Table 1 are known compounds.
Gen er a l P r oced u r e for Hyd r oxyca r bon yla tion of Ar yl
Iod id e Ca ta lyzed by P d -P EP . A Merrifield vessel was
charged with aryl iodide (3) (0.4 mmol), potassium carbonate
(
2
498 mg, 3.6 mmol), Pd-PEP (2) (29 mg, 12 µmol of Pd), and
.0 mL of water. The reaction mixture was shaken on a wrist-
action shaker under an atmospheric pressure of carbon monoxide
at 25 °C for 12 h. The reaction mixture was filtered, and the
mL of 1.8 M solution of potassium hydroxide was agitated
under an atmospheric pressure of carbon monoxide to
give 45% yield of benzoic acid.
Pd-PEP was an effective catalyst for the Heck reac-
tion. Thus, the preparation of cinnamic acid 9 was
examined by the Heck reaction of iodobenzene with
acrylic acid (5.0 equiv) in aqueous potassium carbonate
in the presence of 3 mol % palladium of Pd-PEP 2 to
give 92% yield of 9 (Scheme 4).
resin was rinsed with saturated NaHCO
combined filtrate was acidified (pH = 1) with concentrated
hydrochloric acid and extracted with ether. The extract was dried
3
(3 × 1.5 mL). The
2 4
over Na SO and concentrated under reduced pressure to give
benzoic acid (4).
Heck Rea ction of Iod oben zen e (2a ) w ith Acr ylic Acid .
A Merrifield vessel was charged with 3a (41 mg, 0.2 mmol),
acrylic acid (144 mg, 2.0 mmol), potassium carbonate (124 mg,
0.9 mmol), 2 (29 mg, 12 µmol of Pd), and 500 µL of water. The
reaction mixture was shaken on a wrist-action shaker at 25 °C
for 20 h. The reaction mixture was filtered, and the resin was
rinsed with saturated NaHCO
filtrate was washed with chloroform, acidified (pH = 1) with
concentrated hydrochloric acid, and extracted with ether. The
3
(3 × 1.5 mL). The combined
Exp er im en ta l Section
Gen er a l Meth od s. The amphiphilic resin-supported pal-
ladium-triarylphosphine 2 was prepared on commercially avail-
able poly(ethylene glycol)-polystyrene graft copolymer beads,
2 4
extract was dried over Na SO and concentrated under reduced
pressure to give 55 mg of cinnamic acid (7) (92%).
ArgoGel NH
2
(Argonaut Technologies, CA), according to the
Ack n ow led gm en t. The authors are grateful to Dr.
J ohn A. Porco, J r., at Argonaut Technologies for provi-
sion of the PEG-PS resin. This work was supported by
a Grant-in-Aid for Scientific Research from the Ministry
of Education of J apan. Y.U. thanks the Shorai Founda-
tion for Science and Technology and the ASPRONC
Foundation for partial financial support of this work.
reported procedure. All starting substrates 3a -l, 8, and bromo-
benzene are commercially available. TPPTS and polystyrene-
supported triphenylphosphine were purchased from Aldrich
Chemical Inc. Water was deionized and distilled prior to each
catalytic reaction. The agitation of the reaction mixture was
(
14) For a recent review, see: J . Tsuji, Palladium Reagents and
Catalysts; J ohn Wiley and Sons: Chichester, U.K., 1995.
J O990631F