Palladium-catalyzed hydroxycarbonylation of aryl and vinyl bromides by mixed acetic formic anhydride

Article abstract of DOI:10.1055/s-2006-950195

The palladium-catalyzed hydroxycarbonylation of aryl and vinyl bromides in the presence of acetic anhydride and lithium formate as a carbon monoxide source has been developed. The combination of palladium(II) acetate with 1,1′-bis(diphenylphosphino)ferrocene (dppf) is an efficient catalytic system when the reaction is carried out at 120 °C. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2006-950195

3106
PAPER
Palladium-Catalyzed Hydroxycarbonylation of Aryl and Vinyl Bromides by
Mixed Acetic Formic Anhydride
Palladium-Cat
h
alyze
d
H
ydr
i
oxycarb
l
onylat
i
ion of
A
p
ryl and Vin
p
yl Bromide
s
e Berger, Alla Bessmernykh,*1 Jean-Claude Caille,*2 Sylviane Mignonac
FINORGA S.A., 497 route de Givors, BP 9, 38670 Chasse-sur-Rhône, France
Fax +33(3)896138; fax +33(2)41427919; E-mail: Alla.Lemeune@u-bourgogne.fr; E-mail: caille@ppg.com
Received 20 April 2006; revised 1 June 2006
[1,3-bis(diphenylphosphino)propane]dichloropalladium
Abstract: The palladium-catalyzed hydroxycarbonylation of aryl
and vinyl bromides in the presence of acetic anhydride and lithium
formate as a carbon monoxide source has been developed. The com-
bination of palladium(II) acetate with 1,1¢-bis(diphenylphosphi-
[PdCl2(dppp)] was an efficient precatalyst but the reaction
was very slow (64 h) and led to moderate yields of the de-
sired products. Here we report a convenient protocol for
no)ferrocene (dppf) is an efficient catalytic system when the the palladium-catalyzed hydroxycarbonylation of aryl
reaction is carried out at 120 °C.
bromides using Cacchi’s source of carbon monoxide
(Equation 1).
Key words: hydroxycarbonylation, palladium, catalysis, aryl bro-
mides, carboxylic acids
Br
COOH
Ac2O, HCO2Li
Pd(OAc)2, ligand,
i-Pr2EtN
The transition-metal-catalyzed carbonylation of various
organic substrates is important in industrial organic syn-
thesis.3 Hydroxycarbonylation of aryl and vinyl halides or
triflates has received considerable attention.4 Carbon
monoxide is used as a substrate in such reactions. This in-
expensive and readily available gas is highly toxic and
must be stored in stainless steel containers.5 The use of
carbon monoxide in chemistry plants demands special
equipment and expensive safety control. Thus, a new and
safe technique where carbon monoxide is not introduced
into the reaction mixtures, but instead is generated in situ,
is highly desirable. There is additional interest in such
techniques in the pharmaceutical industry. The wide use
of automated combinatorial chemistry for the discovery of
new drugs has led to a demand for the replacement of gas-
eous substrates by liquid and solid materials that are easier
to handle.
R
R
Equation 1
Our first attempt to carry out the hydroxycarbonylation of
4-bromobiphenyl under the conditions reported by Cacchi
were disappointing. According to the reported procedure,
lithium formate (2 equiv), acetic anhydride (3 equiv), and
N,N-diisopropylethylamine (2 equiv) were reacted in
N,N-dimethylformamide at room temperature for one
hour, then 4-bromobiphenyl, lithium chloride, and the pal-
ladium catalyst were introduced; the reaction was per-
formed at 80 °C. Even a simple replacement of the
reported palladium catalyst [1,3-bis(diphenylphosphi-
no)propane]dichloropalladium by
a
more readily
available catalytic system such as tris(dibenzylidene-
acetone)dipalladium/1,3-bis(diphenylphosphino)propane
and palladium(II) chloride/1,3-bis(diphenylphosphi-
no)propane led to no production of the desired acid
(Table 1, entries 1 and 2).
In recent years, a few sources of carbon monoxide have
been reported.6 For example, carbonylation has been real-
ized by the use of methyl formate.7 Alper and Grushin per-
formed the catalytic hydroxycarbonylation of aryl iodides
and vinyl and benzyl halides by carbon monoxide gener-
ated in situ from chloroform and aqueous alkali.8 Recent-
ly, Cacchi et al. reported on the use of acetic anhydride
and lithium formate as precursors of carbon monoxide.9
The mixed anhydride acetic formic anhydride was pro-
posed as the source of carbon monoxide under these con-
ditions. The hydroxycarboxylation of aryl iodides was
carried out under mild conditions (palladium catalyst,
i-Pr2EtN, LiCl, DMF, 80 °C). However, aryl bromides,
which are more interesting substrates for industrial
applications, were sluggish to react under the re-
ported conditions. In a limited number of examples
These results prompted us to search for a more efficient
catalytic system for the hydroxycarbonylation reaction of
aryl and vinyl bromides. A variety of phosphine ligands
was examined using 4-bromobiphenyl (1) as a model sub-
strate (Table 1). In this ligand screening, only 1,1¢-
bis(diphenylphosphino)ferrocene (dppf) (Table 1, entry
9) gave the desired product in good yield, where as tri-
tert-butylphosphine, tri-2-tolylphosphine, triphenylphos-
phine, and 2,2¢-bis(diphenylphosphino)-1,1¢-binaphthyl
(BINAP) were less efficient or ineffective. Unfortunately,
under these conditions 1-(4-bromophenyl)-N-(tert-but-
oxycarbonyl)ethylamine (2) provided the corresponding
acid in only 35% yield (Table 2, entry 1). So we continued
optimization using this less reactive substrate and varying
the temperature, the palladium source, the solvent, and the
amount of lithium chloride additive. The results are sum-
marized in Table 2.
SYNTHESIS 2006, No. 18, pp 3106–3110
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x.
x
x
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0
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Advanced online publication: 15.08.2006
DOI: 10.1055/s-2006-950195; Art ID: P04906SS
© Georg Thieme Verlag Stuttgart · New York

PAPER
Palladium-Catalyzed Hydroxycarbonylation of Aryl and Vinyl Bromides
3107
Table 1 Evaluation of Ligands for Hydroxycarbonylation of 4-Bro-
Table 2 Optimization of Hydroxycarbonylation of Bromide 2a
mobiphenyla
Br
COOH
Ac2O, HCO2Li
Ac2O, HCO2Li
Br
COOH
[Pd], ligand,
i-Pr2EtN
[Pd], dppf, i-Pr2EtN
1
Entry
Palladium precatalyst Ligand (mol%)
(mol%)
Yieldb (%)
NHBoc
NHBoc
2
Entry Palladium pre-
catalyst (mol%)
dppf
(mol%) (°C)
Temp
Time
(h)
Yield
1
2
3
4
5
6
7
8
9
Pd2(dba)3 (5)
PdCl2 (10)
dppp (10)
0
0
(%)
35c
45c
15c
dppp (10)
1b
2
Pd2(dba)3 (5)
Pd2(dba)3 (5)
Pd2(dba)3 (5)
Pd2(dba)3 (5)
20
20
20
20
80
80
20
20
20
Pd2(dba)3 (5)
Pd2(dba)3 (5)
Pd2(dba)3 (5)
Pd2(dba)3 (5)
Pd2(dba)3 (5)
Pd2(dba)3 (5)
Pd2(dba)3 (5)
(t-Bu)3P (10)
(t-Bu)3P (20)
(o-Tol)3P (30)
(o-Tol)3P (60)
Ph3P (30)
10
5
3b
4b
60
10
5
120
2
3
83d
86d (70)e
0
5b
6
Pd2(dba)3 (2.5)
Pd2(dba)3 (2.5)
PdCl2 (5)
10
10
10
10
5
120
120
120
120
120
120
120
120
120
120
5
61d
81d
77d
81d
93d
86d
96d
64d
97d
92d
BINAP (20)
dppf (20)
25
70
5
7
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
a Reactions conditions: 4-bromobiphenyl (2 mmol), Ac2O (2 equiv),
HCO2Li (3 equiv), i-Pr2EtN (2 equiv), LiCl (3 equiv), DMF (9 mL),
80 °C, 24 h. After cooling, the mixture was diluted with EtOAc,
washed with 2 M HCl, dried (Na2SO4) and concentrated under re-
duced pressure. The residue was analyzed by 1H and 13C NMR.
b By NMR.
8
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (2.5)
Pd(OAc)2 (1)
9
10
15
5
11f
12g
13
5
We speculated that the temperature could be the crucial
parameter for a successful hydroxycarbonylation reaction
since both oxidative addition of bromide and thermal de-
composition of intermediate acetic formic anhydride are
determined by this factor. Indeed, dramatic improvement
was observed by increasing the temperature (compare
Table 2, entries 1, 3, and 4). When the reaction was car-
ried out at 120 °C, a significant increase in the reaction
rate was observed (86% HPLC yield after 3 h; Table 2, en-
try 4) and good conversion was achieved with a decreased
amount of catalyst (Table 2, entries 5, 13 and 14). Con-
trary to Cacchi’s data, no beneficial effect of lithium
chloride was observed when 1,1¢-bis(diphenylphosphi-
no)ferrocene was used as a ligand at 80 °C or 120 °C
(Table 2, entries 2 and 6 vs. 1 and 5). Changing the palla-
dium source showed only a moderate effect, tris(diben-
zylideneacetone)dipalladium, palladium(II) acetate, and
palladium(II) chloride were effective precatalysts
(Table 2, entries 4, 7 and 8). When the precatalyst/ligand
ratio was changed, slightly better yields were obtained us-
ing an equimolar ratio of palladium(II) acetate and 1,1¢-
bis(diphenylphosphino)ferrocene (Table 2, entries 8–10).
The choice of solvents was limited due to the high reactiv-
ity of the anhydrides. The reaction proceeded well in polar
solvents, such as N,N-dimethylformamide and N-meth-
ylpyrrolidin-2-one (Table 2, entries 9 and 11). The yields
decreased in dimethyl sulfoxide (Table 2, entry 12). Note-
worthy was that the yield of the product was dramatically
dependent on the aryl bromide concentration. The hy-
2.5
14
1
a Reactions conditions: bromide 2 [1 (or 2) mmol], Ac2O (2 equiv),
HCO2Li (3 equiv), i-Pr2EtN (2 equiv), DMF [5 (or 10) mL].
b The reaction was run in the presence of LiCl (3 equiv).
c NMR yield. After cooling, the mixture was diluted with EtOAc,
washed with 2 M HCl, dried (Na2SO4), and concentrated under re-
duced pressure. The residue was analyzed by 1H and 13C NMR.
d HPLC yield.
e Isolated yield.
f NMP was used as the solvent.
g DMSO was used as the solvent.
droxycarbonylation reaction proceeds smoothly only in
dilute solutions of aryl bromide in N,N-dimethylform-
amide (Table 3). The hydrodebromination of bromide 2
plays a significant role when more concentrated solutions
are used under these conditions.
Finally, among the formic acid salts and bases, a combi-
nation of lithium formate and N,N-diisopropylethylamine
was the most efficient (Table 4).
To examine the scope of this reaction, a variety of bro-
mides was then subjected to hydroxycarbonylation. In
practice, the conditions we used when the procedure was
applied to other aryl bromides are as follows: aryl bro-
mide (1 equiv, 0.18 M), Pd(OAc)2/dppf (3–5 mol%),
i-Pr2EtN (2 equiv), HCO2Li (3 equiv), Ac2O (2 equiv),
Synthesis 2006, No. 18, 3106–3110 © Thieme Stuttgart · New York

3108
P. Berger et al.
PAPER
Table 5 Substrate Scope for Hydroxycarbonylation Reactiona
Table 3 Evaluation of Substrate Concentration for Hydroxycarbon-
ylation of Bromide 2a
Entry
1
Substrate
Pd(OAc)2 Time (h) Yield (%)b
(mol%)
Entry
Concentration of ArBr (M) Isolated yield (%)
Br
3
5
74c
1
2
3
4
0.18
0.22
0.66
0.80
75
79
44
38
2
3
5
5
2
1
89
79
Br
Br
a Reactions conditions: bromide 2 (0.01–0.75 mol), Ac2O (2 equiv),
HCO2Li (3 equiv), i-Pr2EtN (2 equiv), 1 mol% Pd(OAc)2, 1 mol%
dppf, 120 °C, 7 h.
DMF, 120 °C. The results are summarized in Table 5. The
amount of catalytic system was not optimized and 3–5
mol% was employed to achieve a full conversion of start-
ing bromide.
O
O
OEt
4
5
1
71
Br
The hydroxycarbonylation reaction shows broad substrate
generality and afforded the expected acids with good
yields starting from neutral, electron-poor, and electron-
rich aryl bromides (Table 5, entries 1–8). For example, 4-
(trifluoromethyl)benzoic acid, which has found a number
of industrial applications,10 was obtained in 74% yield
(Table 5, entry 7). Of particular note is the tolerance of
different functional groups, including ketones, esters, and
ethers, to these conditions. Bromonaphthalenes were also
transformed to the corresponding acids with good yields
(Table 5, entry 9). This protocol can be used for the syn-
thesis of dicarboxylic acids. Indeed, terephthalic acid was
obtained from 1,4-dibromobenzene in 75% yield together
with a 20% yield of benzoic acid (Table 5, entry 10). The
methodology was further extended to vinylic bromides. 2-
Bromo-1H-indene gave the corresponding acid in 83%
yield under standard conditions (Table 5, entry 11).
5
6
7
5
5
5
3
1
1
76
Br
Cl
Br
82
F
74d
Br
CF3
Br
8
5
5
82
In summary, we have developed a general procedure for
synthesis of carboxylic acids from aryl bromides using
Cachi’s source of carbon monoxide. Investigations are un-
derway to utilize these conditions for gram- and kilogram-
scale synthesis of pharmaceutical intermediates.
OMe
9
5
5
4
2
61
Br
10
75e
Table 4 Evaluation of Formate Counter Cation and Base for Hy-
droxycarbonylation of Bromide 2a
Br
Br
Entry
M+
K+
Base
Time (h)
15
Yieldb (%)
1
2
3
4
i-Pr2EtN
i-Pr2EtN
i-Pr2EtN
Et3N
9
2
11
5
1
83
Br
Na+
Li+
Li+
15
a Reactions conditions: bromide (2–10 mmol), Ac2O (2 equiv),
HCO2Li (3 equiv), i-Pr2EtN (2 equiv), Pd(OAc)2/dppf (1:1), DMF (5
mL/1 mmol of bromide), 120 °C.
2.5
92
2.5
15
56
68
b Isolated yield.
c 33% in the presence of 1 mol% Pd(OAc)2.
d 36% in the presence of 3 mol% Pd(OAc)2.
e Using Ac2O (4 equiv), HCO2Li (6 equiv), and i-Pr2EtN (4 equiv),
benzoic acid (20%) was also obtained.
a Reactions conditions: bromide 2 (1 mmol), Ac2O (2 equiv), HCO2M
(3 equiv), base (2 equiv), 1 mol% Pd(OAc)2, 1 mol% dppf, 120 °C.
b By HPLC.
Synthesis 2006, No. 18, 3106–3110 © Thieme Stuttgart · New York

PAPER
Palladium-Catalyzed Hydroxycarbonylation of Aryl and Vinyl Bromides
3109
Arenecarboxylic Acids; General Procedure
4-Chlorobenzoic Acid (Table 5, Entry 5)
A soln of HCO2Li (312 mg, 6 mmol), i-Pr2EtN (697 mL, 4 mmol),
and Ac2O (377 mL, 4 mmol) in anhyd DMF (9 mL) was stirred at r.t.
for 1 h under an inert atmosphere. Then, aryl bromide (2 mmol),
Pd(OAc)2 (22.5 mg, 0.10 mmol), and dppf (55.4 mg, 0.10 mmol)
were added. The mixture was stirred at 120 °C until complete con-
version of the bromide (by HPLC). After cooling, EtOAc (20 mL)
and H2O (20 mL) were added and the mixture was acidified to pH 1
with concd HCl. Two phases were separated and the aqueous layer
was extracted with EtOAc (2 × 10 mL). Isolation of pure acid was
achieved by extraction of the combined organic phase with 10% aq
NaOH (3 × 10 mL), acidification of the aqueous phase to pH 1 with
concd HCl, followed by reextraction with EtOAc (3 × 15 mL). The
combined organic layers were dried (Na2SO4) and evaporate under
reduced pressure at 80 °C. In a few cases (Table 5, entries 3, 4, 11)
the pure acids were isolated by chromatography (silica gel, n-hep-
tane–EtOAc, 50:50). The 1H and 13C NMR spectra of isolated acids
(Table 5) were in accord with that reported in the literature.11
Prepared from 1-bromo-4-chlorobenzene (383 mg, 2 mmol) follow-
ing the general procedure; mp 238–240 °C; Lit.12 mp 239–241 °C.
1H NMR (DMSO-d6): d = 7.54 (d, J = 8.4 Hz, 2 H), 7.92 (d, J = 8.4
Hz, 2 H), 7.93 (br s, 1 H).
13C NMR (DMSO-d6): d = 129.37, 130.38, 130.65, 144.29, 168.66.
4-Fluorobenzoic Acid (Table 5, Entry 6)
Prepared from 1-bromo-4-fluorobenzene (875 mg, 5 mmol) follow-
ing the general procedure; mp 183–184 °C; Lit.12 mp 182–184 °C.
1H NMR (DMSO-d6): d = 7.54 (d, J = 8.4 Hz, 2 H), 7.92 (d, J = 8.4
Hz, 2 H), 7.93 (br s, 1 H).
13C NMR (DMSO-d6): d = 116.95 (d, J = 22.6 Hz), 129.10, 133.65
(d, J = 10.3 Hz), 166.65 (d, J = 250.6 Hz), 168.14.
4-(Trifluoromethyl)benzoic Acid (Table 5, Entry 7)
Prepared from 1-bromo-4-(trifluoromethyl)benzene (900 mg, 4
mmol) following the general procedure; mp 218–220 °C; Lit.12 mp
219–220 °C.
1H NMR (DMSO-d6): d = 7.85 (d, J = 8.2 Hz, 2 H), 8.12 (d, J = 8.2
Hz, 2 H), 12.3 (br s, 1 H).
4-Biphenylcarboxylic Acid (Table 5, Entry 1)
Prepared from 4-bromobiphenyl (466 mg, 2 mmol) following the
general procedure; mp 224–225 °C; Lit.12 mp 225–226 °C.
1H NMR (DMSO-d6): d = 7.45 (m, 3 H), 7.71 (d, J = 6.6 Hz, 2 H),
7.78 (d, J = 8.2 Hz, 2 H), 8.01 (d, J = 8.2 Hz, 2 H), 11.5 (br s, 1 H).
13C NMR (DMSO-d6): d = 127.76, 127.90, 129.23, 130.02, 130.57,
130.92, 139.97, 145.25, 168.08.
13C NMR (DMSO-d6): d = 124.97 (q, J = 270.5 Hz), 126.69 (q,
J = 3.2 Hz), 131.25, 133.34 (q, J = 31.5 Hz), 135.82, 167.35.
p-Anisic Acid (Table 5, Entry 8)
Prepared from 4-bromoanisole (748 mg, 4 mmol) following the
4-[2-(tert-Butoxycarbonyl)ethyl]benzoic Acid (Table 3, Entry 2)
Prepared from 1-(4-bromophenyl)-N-(tert-butoxycarbonyl)ethyl-
amine (3.00 g, 10 mmol) following the general procedure; mp 146–
147 °C.
general procedure; mp 183–184 °C; Lit.12 mp 182–185 °C.
1H NMR (DMSO-d6): d = 3.81 (s, 3 H), 7.01 (d, J = 8.1 Hz, 2 H),
7.88 (d, J = 8.1 Hz, 2 H), 12.61 (br s, 1 H).
13C NMR (DMSO-d6): d = 56.60, 114.98, 124.17, 132.50, 164.03,
168.15.
1H NMR (CDCl3): d = 1.28 (t, J = 7.9 Hz, 3 H), 1.35 (s, 9 H), 4.56
(q, J = 7.9 Hz, 1 H), 4.81 (d, J = 7.5 Hz, 1 H), 7.39 (d, J = 7.8 Hz, 2
H), 7.89 (d, J = 7.8 Hz, 2 H), 10.5 (br s, 1 H).
4-Methyl-1-naphthoic Acid (Table 5, Entry 9)
Prepared from 1-bromo-4-methylnaphthalene (442 mg, 2 mmol)
following the general procedure; mp 179–181 °C; Lit.12 mp 179–
180 °C.
1H NMR (DMSO-d6): d = 2.71 (s, 3 H), 7.45 (d, J = 8.1 Hz, 1 H),
7.65 (m, 2 H), 8.06 (d, J = 8.1 Hz, 1 H), 8.09 (m, 1 H), 8.94 (m, 1
H), 12.9 (br s, 1 H).
13C NMR (CDCl3): d = 23.09, 28.70, 50.00, 78.30, 126.39, 129.56,
129.84, 151.10, 155.29, 167.68.
p-Toluic Acid (Table 5, Entry 2)
Prepared from 4-bromotoluene (855 mg, 5 mmol) following the
general procedure; mp 180–181 °C; Lit.12 mp 180–182 °C.
1H NMR (DMSO-d6): d = 2.18 (s, 3 H), 7.25 (d, J = 8.1 Hz, 2 H),
7.82 (d, J = 8.1 Hz, 2 H), 11.5 (br s, 1 H).
13C NMR (DMSO-d6): d = 22.37, 129.93, 131.37, 132.36, 138.80,
168.85.
13C NMR (DMSO-d6): d = 22.82, 125.85, 126.88, 127.31, 128.38,
131.05, 132.17, 133.63, 140.98, 170.01.
Terephthalic Acid (Table 5, Entry 11)
Prepared from 1,4-dibromobenzene (472 mg, 2 mmol) following
the general procedure along with benzoic acid (20%); mp >300 °C;
Lit.12 mp >300 °C.
1H NMR (DMSO-d6): d = 8.15 (s, 4 H), 13.41 (s, 2 H).
13C NMR (DMSO-d6): d = 130.76, 135.93, 167.15.
Terephthalic Acid Monoethyl Ester (Table 5, Entry 3)
Prepared from ethyl 4-bromobenzoate (2.29 g, 10 mmol) following
the general procedure; mp 169–170 °C; Lit.13 mp 168–170 °C.
1H NMR (DMSO-d6): d = 1.32 (t, J = 7.9 Hz, 3 H), 4.32 (q, J = 7.9
Hz, 2 H), 8.03 (br s, 4 H), 11.5 (br s, 1 H).
13C NMR (DMSO-d6): d = 19.83, 66.90, 135.02, 135.17, 139.10,
1H-Indene-2-carboxylic Acid (Table 5, Entry 10)
140.60, 170.84, 172.32.
Prepared from 2-bromo-1H-indene (780 mg, 4 mmol) following the
general procedure; mp 233–235 °C; Lit.14 mp 234–235 °C.
4-Acetylbenzoic Acid (Table 5, Entry 4)
1H NMR (DMSO-d6): d = 3.62 (d, J = 1.6 Hz, 2 H), 7.32 (m, 2 H),
7.53 (m, 2 H), 7.68 (m, 1 H), 12.9 (br s, 1 H).
Prepared from 4-bromoacetophenone (796 mg, 4 mmol) following
the general procedure; mp 208–209 °C; Lit.12 mp 208–210 °C.
13C NMR (DMSO-d6): d = 39.06, 122.85, 123.88, 126.49, 126.83,
137.95, 139.69, 142.12, 144.18, 165.23.
1H NMR (DMSO-d6): d = 2.60 (s, 3 H), 8.02 (s, 4 H), 13.2 (br s, 1
H).
13C NMR (DMSO-d6): d = 28.15, 129.47, 130.71, 135.71, 141.04,
167.81, 198.87.
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P. Berger et al.
PAPER
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