Oxalic acid as the: In situ carbon monoxide generator in palladium-catalyzed hydroxycarbonylation of arylhalides

Article abstract of DOI:10.1039/c7ob01052d

An efficient palladium-catalyzed hydroxycarbonylation reaction of arylhalides using oxalic acid as a CO source has been developed. The reaction features high safety, low catalyst loading, and a broad substrate scope, and provides a safe and tractable approach to access a variety of aromatic carboxylic acid compounds. Mechanistic studies revealed the decomposition pattern of oxalic acid.

Full text of DOI:10.1039/c7ob01052d

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DOI: 10.1039/C7OB01052D
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PAPER
Oxalic acid as the in situ carbon monoxide generator in palladium-
catalyzed hydroxycarbonylation of arylhalides†
Received 00th January 20xx,
Accepted 00th January 20xx
Changdong Shao,a,b Ailan Lu,a Xiaoling Wang,a Bo Zhou,a Xiaohong Guan*b,d and Yanghui
Zhang*a,b,c
DOI: 10.1039/x0xx00000x
An efficient palladium-catalyzed hydroxycarbonylation reaction of arylhalides using oxalic acid as CO source has been
developed. The reaction features high safety, low catalyst loading, and broad substrate scope, and provides a safe and
tractable approach to access a variety of aromatic carboxylic acid compounds. Mechanistic studies revealed the
decomposition pattern of oxalic acid.
www.rsc.org/
Introduction
Carboxylic acids and their derivatives, such as esters, amides,
etc. are important intermediates and extensively exist in
pharmaceuticals, perfumes, dyes, and other manufactured
chemicals.1 For instance, acetylsalicylic acid and niacin, with
the trade name of aspirin and vitamin B3 respectively, are
worldwide commercialized medicines. Likewise, terephthalic
acid is one of the synthons in the synthesis of the extremely
famous polymer material Dacron. Carboxylic acids may be
prepared in a simple manner by, for example, the oxidation of
preoxidized substrates, hydrolysis of related derivatives, and
the combination of carbon dioxide into nucleophilic reagents
such as organolithium or organomagnesium halides.2 Despite
the high efficiency and low-cost advantages of these
conventional procedures, harsh reaction conditions or high
reactivity of reagents makes them inadequate in
chemoselectivity or functional group tolerance. Thus, transition
metal-catalyzed carbonylation reactions of halogenated
hydrocarbons with carbon monoxide and various nucleophiles
have been one of the most important methods to acquire
complex carbonyl compounds that bearing various functional
groups.3 The pioneering work in this field was reported by
Heck more than 40 years ago.4
Scheme 1 Examples of generally used CO surrogates.
to use it in laboratory. The reasons for this is no doubt related to
the highly toxic, colorless, flavorless, explosible properties of
carbon monoxide, and in most cases specialized high-pressure
equipment are also needed. To address these problems, lots of
CO surrogates that can generate CO gas in an in situ or ex situ
manner have been developed as the alternative proposal to
avoid direct operation of CO gas (Scheme 1).5 Skrydstrup and
co-workers reported lots of examples by using 9-
methylfluorene-9-carbonylchloride,6 silacarboxylic acid,7 and
tertiary acid chloride8 as the concentrated CO surrogates.
Manabe’s group published the palladium-catalyzed reductive
carbonylation and fluorocarbonylation reactions of aryl halides
using N-formylsaccharin as the CO source.9 Many examples
illustrated that formic acid and their derivatives can be treated
Although a plethora of carbonylation reactions in industry
demonstrated the utility of CO gas, chemists are still reluctant
as
CO
producers.10
Metal
carbonyl
complexes,11
formaldehyde,12 chloroform,13 or even some alcohols14 and
carbohydrates15 also can be regarded as CO succedaneums.
Based on these CO surrogates, the ―CO-free‖ carbonylation
chemistry has made great breakthrough in the past few decades.
However, drawbacks related to toxicity, price, stability, and
atom efficiency still exist in front of chemists.
Oxalic acid and their derivatives are inexpensive, nontoxic,
and abundant chemicals. Few examples have demonstrated that
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Table 1 Conditions screening.
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DOI: 10.1039/C7OB01052D
Entry
1
Variations from condition Xa
Yield (%)b
conditions A
4 h instead of 6 h
94
85
2
3
80 °C instead of 100 °C
conditions B
89
4
94
5
conditions C
94
6
1 mol % Pd(OAc)2 was used
0.5 mol % Pd(OAc)2 was used
94 (90)c
89
7
8
Pd(PPh3)4 instead of Pd(OAc)2/PPh3
(CO2H)2 instead of (CO2H∙H2O)2
without (CO2H∙H2O)2
without Ac2O
92
84
—
—
12
—
—
9
10
11
12
13
14
without DIPEA
without Ac2O and DIPEA
without Pd(OAc)2
Scheme 2 Examples of using oxalic acid derivatives in carbonylation reactions.
a
Conditions A: PhI (0.2 mmol), (CO2H∙H2O)2 (3.0 equiv.), Ac2O (3.0 equiv.),
DIPEA (3.0 equiv.). Conditions B: PhI (0.2 mmol), (CO2H∙H2O)2 (2.5 equiv.),
Ac2O (1.5 equiv.), DIPEA (1.5 equiv.). Conditions C: PhI (0.4 mmol),
oxalic acid and their derivatives have the potential to be CO
surrogates. Liu, Ge, and Gu reported several palladium-
catalyzed decarboxylative cross-coupling reactions of
potassium oxalate monoesters or oxamic acids with arylhalides,
arylborates, and C−H bonds (Scheme 2, a-d).16 However, high
reaction temperature or strong oxidizing agents are needed.
Recently, Ulven and co-workers reported an example of using
oxalyl chloride and NaOH aqueous solution to generate CO
gas.17 Almost simultaneously, Gracza et al. described a protocol
for the generation of CO gas by the reduction of oxalyl chloride
with zinc powder (e).18 Oxalyl chloride is known as a
deliquescent and amyctic liquid and should be operated with
carefulness. Furthermore, the operation of CO gas balloon or
two-chamber apparatus still can not be avoided in these two
reports. Das and co-workers reported a palladium nanoparticle-
catalyzed carboxylation of arylhalides. Despite the novelty of
palladium nanoparticle catalyst, the reaction was carried out
under microwave irradiation with high temperature, pressure,
excessive oxalic acid, and moderate yields (f).19 Hence,
developing facile and efficient carbonylation reactions using
oxalic acid is still of great interests. Herein, we present an
example of palladium-catalyzed hydroxycarbonylation reaction
of arylhalides using oxalic acid as the operable concentrated
carbonyl reagent.
b
(CO2H∙H2O)2 (1.5 equiv.), Ac2O (1.5 equiv.), DIPEA (1.5 equiv.). Yields were
determined by 1H NMR analysis of crude products using C2H2Cl4 as the internal
standard. c Isolated yield. DIPEA = N,N-Diisopropylethylamine.
(Table 1, entry 1). The yield of 3a decreased to 85% when the
reaction time was reduced to 4 hours (entry 2). The decrease of
reaction temperature also resulted in a slightly lower yield
(entry 3). The impact of the ratios of the reagents on the
reaction was investigated and the optimal conditions were
summarized in Table 1 (entries 4-5, for details see SI). Based
on conditions C, further screening experiments were carried out,
and the results illustrated the catalyst loading can be lowered to
1 mol % (entry 6). Surprisingly, 3a can also be generated with a
satisfactory yield (89%) even when 0.5 mol % Pd(OAc)2 was
used (entry 7). Other palladium catalysts such as Pd(PPh3)4
(entry 8), Pd(dba)2 and Pd(PPh3)2Cl2 were also tested, and the
results revealed that Pd(OAc)2 was the optimal one (for details
see SI). The yield of 3a decreased when anhydrous (CO2H)2
was used instead of (CO2H∙H2O)2 (entry 9). Control
experiments illustrated that (CO2H∙H2O)2 and Ac2O were
indispensable components and DIPEA promotes the reaction
tremendously (entries 10-13). No product was detected in the
absence of Pd(OAc)2 catalyst (entry 14).
With the optimal conditions in hand (entry 6), we next
investigated the substrate scope of this hydroxycarbonylation
Results and Discussion
protocol. Gratifyingly, various substituted iodobenzenes (1b-1v
underwent the hydroxycarbonylation reaction efficiently,
providing aromatic carboxylic acids esters (3b-3v) in moderate
to excellent yields (Table 2). Both electron-withdrawing groups,
such as cyano (1c), carbonyl (1g, 1h), nitro (1i), ester (1j), and
)
We
initiated
our
research
by
investigating
the
hydroxycarbonylation of iodobenzene (1a). (CO2H∙H2O)2,
Ac2O, and DIPEA were selected as the CO generator system
(CO gen). Surprisingly, methyl benzoate (3a) was obtained in
94% yield when 1a was treated with 5 mol % Pd(OAc)2, 15
mol % PPh3, and 3.0 equivalent CO gen in DMF under 100 C
for 6 hours followed by sequential esterification operation
trifluoromethyl
(1o), and electron-donating groups like
o
methanoyl (1e), methyl (1n), and methoxyl (1p) were well-
tolerated in the reaction. It should be noted that the halo groups,
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Table 2 Substrate scope of aryliodides.a, b, c, d
Table 3 Substrate scope of arylbromides.a, b, c
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DOI: 10.1039/C7OB01052D
a
Reaction conditions: Arylbromides (0.4 mmol), (CO2H•H2O)2 (1.5 equiv.),
Pd(OAc)2 (1 mol %), xantphos (1 mol %), Ac2O (1.5 equiv.), DIPEA (1.5 equiv.),
o
b
c
d
DMF (2.0 mL), 100 C, 6 h. Treated with method A. Isolated yield. Treated
with method B. 1H NMR yield. xantphos = 4,5-bis(diphenylphosphino)-9,9-
e
dimethylxanthene.
for the treatment of cerebral ischemia).21 The reactivities of
iodothiophenes (1r and 1t) were also examined. Interestingly,
methyl 3-thiophenecarboxylate product
(3t) was obtained in
78% yield when using 3-iodothiophene as the substrate while 2-
iodothiophene gave dithiopheneylketone (3s) as the main
product together with only 22% methyl 2-thiophenecarboxylate
(
3r). However, iodopyridines (1u, 1v) were incompatible with
the reaction.
To disclose the reactivity of arylbromides, further screenings
were carried out (for details see SI). Bromobenzene (4a
)
a
Reaction conditions: Aryliodides (0.4 mmol), (CO2H∙H2O)2 (1.5 equiv.),
underwent the hydroxycarbonylation reaction under nitrogen
atmosphere successfully by using xantphos as the ligand (Table
3). Arylbromides containing both electron-withdrawing groups
Pd(OAc)2 (1 mol %), PPh3 (3 mol %), Ac2O (1.5 equiv.), DIPEA (1.5 equiv.),
DMF (2.0 mL), 100 oC, 6 h. b Treated with method A. c Isolated yield. d 3xo/m/p =
ortho/meta/para-position. Treated with method B. f 0.2 mmol 1,4-diiodobenzene
e
(
4b-f) and electron-donating groups (4h-k) exhibited high
reactivity and the reactions were high yielding. The substrates
bearing ortho-substituents such as chloro (4g) and methyl (4ho
was used.
including F (1k), Cl (1l), and Br (1m), survived the reaction
conditions. The protocol was applicable for disubstituted
substrate (1d), and 1-iodonaphthalene was also compatible (1f).
To explore the applicability of the method in dual
hydroxycarbonylation reactions, 1,4-diiodobenzene was
selected as the reagent and dimethyl terephthalate (3jp) was
observed in 66% yield. Surprisingly, when o-iodoacetophenone
)
group gave the carboxylated products in lower yields. Bromo-
substituted thiophenes (4l and 4m) were also compatible and
the desired products were formed in excellent yields. It should
be noted that pyridine substrates (4n and 4o) also underwent the
(
1q
)
was used, methylphthalide (3q) rather than the
corresponding carboxylate product was observed.20 Notably,
phthalide is the core framework of a series of chemical
compounds (e.g. butylphthalide soft capsules, a useful medicine
Scheme 3 Mechanistic study.
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spectra were recorded in CDCl3 referenced to residual CHCl3 at
View Article Online
13
7.26 ppm, and C NMR spectra were reDfeOrIe:n10c.e1d03t9o/Ct7hOeBc0e1n05tr2aDl
peak of CDCl3 at 77.00 ppm. Chemical shifts (δ) are reported in
ppm, and coupling constants (J) are in Hertz (Hz).
Multiplicities are reported using the following abbreviations: s
= singlet, d = doublet, t = triplet, q = quartet, m = multiplet, dd
= doublet of doublets, dt = doublet of triplets, td = triplet of
doublets. All the products were purified by flash column
chromatography on silica gel (300-400 mesh) to give the
corresponding compounds. All the reagents were used directly
without further purification.
General Procedures for Hydroxycarbonylation
General procedures for the reactions of aryliodides: A 35
mL sealed tube equipped with a stir bar was charged with
(CO2H∙H2O)2 (1.5 equiv.), Pd(OAc)2 (1 mol %), PPh3 (3
mol %), ArI (0.4 mmol), Ac2O (1.5 equiv.), DIPEA (1.5 equiv.),
DMF (2.0 mL) under air. The tube was quickly sealed with a
Teflon® high pressure valve. After the reaction mixture was
stirred in a preheated oil bath (100 °C) for 6 h, it was allowed to
cool down to room temperature.
General procedures for the reactions of arylbromides: A 35
mL Schlenk tube equipped with a stir bar was charged with
(CO2H∙H2O)2 (1.5 equiv.), Pd(OAc)2 (1 mol %), xantphos (1
mol %), ArBr (0.4 mmol), Ac2O (1.5 equiv.), DIPEA (1.5
equiv.), DMF (2.0 mL) under air. The tube was quickly sealed
with a Teflon® high pressure valve, frozen in liquid nitrogen,
evacuated and backfilled with N2 (5 times). After the reaction
mixture was stirred in a preheated oil bath (100 °C) for 6 h, it
was allowed to cool down to room temperature.
Scheme 4 Plausible mechanism.
carboxylation reaction, albeit in low yields.
To gain a better understanding of the reaction, a series of
mechanistic studies were carried out. First of all, CO and CO2
gas were detected by GC-TCD in approximate 1:1 molar ratio
after heating the CO generator system in DMF for 1 hour (for
details see SI). Secondly, several reports demonstrated that CO2
was effective carboxylation reagent in Pd-, Ni-, and Cu-
catalyzed carboxylation of aryl halides; however, no
carboxylated product was detected in our catalytic system under
CO2 atmosphere in the absence of (CO2H∙H2O)2 (Scheme 3).22
These results illustrated that CO, but not CO2, was the carbon
source in this hydroxycarbonylation reaction. Based on the
mechanistic studies mentioned above and literatures,23
plausible mechanism pathway was suggested. As shown in
Scheme 4, the oxidative addition of Pd(0) to aryl iodide gave
a
Method A: The reaction mixture was diluted with EA (10 mL),
acidified with 2 M HCl (5 mL, once), and washed with brine (5
mL, twice). The organic phase was dried over anhydrous
Na2SO4 and concentrated in vacuo. The carboxylic acid product
was then esterified with CH2N2 ether solution. The final ester
products were purified by flash column chromatography on
silica gel (300-400 mesh) to give the corresponding carboxylic
acid ester compounds.
arylpalladium complex
of CO, which was generated by the decomposition of CO gen,
acylpalladium intermediate was formed. An acylpalladium
complex was subsequently generated after the ligand
exchange with H2O or HOAc. The final aromatic carboxylic
acid was obtained after reductive elimination and meanwhile
gave Pd(0) for the next catalyst cycle.
A, after the coordination and insertion
C
D
Method B: After cooled down to room temperature, K2CO3
(4.0 equiv.) and CH3I (4.0 equiv.) were added to the reaction
mixture and stirred for another 6 h, then the mixture was diluted
with EA (10 mL) and washed with brine (5 mL, twice). The
organic phase was dried over anhydrous Na2SO4 and
concentrated in vacuo. The final ester products were purified by
flash column chromatography on silica gel (300-400 mesh) to
give the corresponding carboxylic acid ester compounds.
Methyl benzoate 3a. 49.1 mg, 90% (for 1a); 50.6 mg, 93%
(for 4a). 1H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 7.2 Hz, 2H),
7.55 (t, J = 7.4 Hz, 1H), 7.44 (t, J = 7.6 Hz, 2H), 3.92 (s, 3H).
13C NMR (101 MHz, CDCl3) δ 167.10, 132.88, 130.13, 129.54,
Conclusions
In conclusion, we have demonstrated that oxalic acid could be
an inexpensive, nontoxic, abundant, and operable concentrated
CO surrogate in palladium-catalyzed hydroxycarbonylation
reactions of arylhalides. The protocol tolerates multiple
functional groups and gave corresponding aromatic carboxylic
acid products in moderate to excellent yields. This method
could also be applicable to the hydroxycarbonylation of
heteroarylhalides.
+
128.32, 52.07. HRMS (ESI-TOF) m/z: calcd for C8H8NaO2 :
159.0417 (M + Na)+, found: 159.0416.
Experimental Section
Methyl [1,1'-biphenyl]-4-carboxylate 3b. 73.0 mg, 86%
(for 1b); 82.3 mg, 97% (for 4j). 1H NMR (400 MHz, CDCl3) δ
8.11 (d, J = 8.4 Hz, 2H), 7.65 (dd, J = 14.9, 7.9 Hz, 4H), 7.47 (t,
J = 7.4 Hz, 2H), 7.40 (t, J = 7.3 Hz, 1H), 3.94 (s, 3H). 13C
NMR (101 MHz, CDCl3) δ 166.98, 145.60, 139.96, 130.07,
General Information
High resolution mass spectra were measured on Bruker
MicroTOF II ESI-TOF mass spectrometer. H NMR and 13C
1
NMR spectra were recorded on Bruker ARX400. 1H NMR
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128.89, 128.86, 128.11, 127.24, 127.01, 52.09. HRMS (ESI- 2H), 3.98 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 165.16,
View Article Online
TOF) m/z: calcd for C14H12NaO2 : 235.0730 (M + Na)+, found: 150.50, 135.47, 130.69, 123.52, 52.81. HRMS (ESI-TOF) m/z:
+
DOI: 10.1039/C7OB01052D
+
235.0733.
Methyl 4-cyanobenzoate 3c. 47.0 mg, 73%. H NMR (400
calcd for C8H7NNaO4 : 204.0267 (M + Na)+, found: 204.0277.
Dimethyl phthalate 3jo. 39.6 mg, 51%. 1H NMR (400 MHz,
1
MHz, CDCl3) δ 8.14 (d, J = 8.2 Hz, 2H), 7.74 (d, J = 8.2 Hz, CDCl3) δ 7.71 (dd, J = 5.7, 3.3 Hz, 2H), 7.52 (dd, J = 5.7, 3.3
2H), 3.96 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 165.41, Hz, 2H), 3.89 (s, 6H). 13C NMR (101 MHz, CDCl3) δ 167.95,
133.90, 132.20, 130.07, 117.93, 116.38, 52.70. HRMS (ESI- 131.81, 131.02, 128.76, 52.53. HRMS (ESI-TOF) m/z: calcd
+
+
TOF) m/z: calcd for C9H7NNaO2 : 184.0369 (M + Na)+, found: for C10H10NaO4 : 217.0471 (M + Na)+, found: 217.0475.
184.0370.
1
Dimethyl isophthalate 3jm. 68.3 mg, 88%. H NMR (400
Methyl 3,5-dimethylbenzoate 3d. 64.3 mg, 98% (for 1d); MHz, CDCl3) δ 8.67 (s, 1H), 8.21 (dd, J = 7.8, 1.6 Hz, 2H),
1
63.0 mg, 96% (for 4i). H NMR (400 MHz, CDCl3) δ 7.66 (s, 7.52 (t, J = 7.8 Hz, 1H), 3.94 (s, 6H). 13C NMR (101 MHz,
2H), 7.18 (s, 1H), 3.89 (s, 3H), 2.35 (s, 6H). 13C NMR (101 CDCl3) δ 166.18, 133.74, 130.65, 130.53, 128.57, 52.30.
+
MHz, CDCl3) δ 167.40, 137.95, 134.50, 129.96, 127.24, 51.92, HRMS (ESI-TOF) m/z: calcd for C10H10NaO4 : 217.0471 (M +
+
21.08. HRMS (ESI-TOF) m/z: calcd for C10H12NaO2 : Na)+, found: 217.0473.
187.0730 (M + Na)+, found: 187.0732.
Dimethyl terephthalate 3jp. 73.7 mg, 95% (for 1jp); 25.6
1
Methyl 4-acetoxybenzoate 3e. 67.5 mg, 87%. 1H NMR (400 mg, 66% (for 1,4-diiodobenzene); 76.8 mg, 99% (for 4e). H
MHz, CDCl3) δ 8.06 (d, J = 8.8 Hz, 2H), 7.16 (d, J = 8.8 Hz, NMR (400 MHz, CDCl3) δ 8.10 (s, 4H), 3.94 (s, 6H). 13C NMR
2H), 3.91 (s, 3H), 2.31 (s, 3H). 13C NMR (101 MHz, CDCl3) δ (101 MHz, CDCl3) δ 166.29, 133.90, 129.54, 52.42. HRMS
168.82, 166.26, 154.24, 131.12, 127.67, 121.56, 52.16, 21.11. (ESI-TOF) m/z: calcd for C10H10NaO4 : 217.0471 (M + Na)+,
HRMS (ESI-TOF) m/z: calcd for C10H10NaO4 : 217.0471 (M + found: 217.0469.
Na)+, found: 217.0469.
+
+
Methyl 2-fluorobenzoate 3ko. 47.4 mg, 77%. 1H NMR (400
Methyl 1-naphthoate 3f. 57.3 mg, 77% (for 1f); 70.7 mg, 95% MHz, CDCl3) δ 7.92 (td, J = 7.6, 1.6 Hz, 1H), 7.53 – 7.46 (m,
(for 4k). 1H NMR (400 MHz, CDCl3) δ 8.91 (d, J = 8.6 Hz, 1H), 1H), 7.18 (t, J = 7.2 Hz, 1H), 7.15 – 7.09 (m, 1H), 3.91 (s, 3H).
8.19 (d, J = 6.4 Hz, 1H), 8.02 (d, J = 8.2 Hz, 1H), 7.89 (d, J = 13C NMR (101 MHz, CDCl3) δ 164.80 (d, J = 3.6 Hz), 161.82
8.1 Hz, 1H), 7.62 (t, J = 7.2 Hz, 1H), 7.58 – 7.45 (m, 2H), 4.01 (d, J = 259.8 Hz), 134.39 (d, J = 9.0 Hz), 132.02, 123.85 (d, J =
(s, 3H). 13C NMR (101 MHz, CDCl3) δ 168.02, 133.81, 133.33, 3.9 Hz), 118.52 (d, J = 9.6 Hz), 116.86 (d, J = 22.4 Hz), 52.19.
+
131.30, 130.18, 128.51, 127.72, 127.06, 126.17, 125.78, 124.45, HRMS (ESI-TOF) m/z: calcd for C8H7FNaO2 : 177.0322 (M +
+
52.11. HRMS (ESI-TOF) m/z: calcd for C12H10NaO2 : Na)+, found: 177.0323.
209.0573 (M + Na)+, found: 209.0578.
Methyl 3-fluorobenzoate 3km. 49.3 mg, 80% (for 1km);
1
Methyl 4-acetylbenzoate 3g. 63.4 mg, 89% (for 1g); 67.7 60.4 mg, 98% (for 4b). H NMR (400 MHz, CDCl3) δ 7.83 (d,
1
mg, 95% (for 4d). H NMR (400 MHz, CDCl3) δ 8.12 (d, J = J = 7.7 Hz, 1H), 7.75 – 7.69 (m, 1H), 7.45 – 7.37 (m, 1H), 7.29
8.4 Hz, 2H), 8.00 (d, J = 8.4 Hz, 2H), 3.94 (s, 3H), 2.64 (s, 3H). – 7.22 (m, 1H), 3.92 (s, 3H). 13C NMR (101 MHz, CDCl3) δ
13C NMR (101 MHz, CDCl3) δ 197.50, 166.19, 140.21, 133.87, 165.95 (d, J = 2.7 Hz), 162.52 (d, J = 246.9 Hz), 132.28 (d, J =
129.80, 128.17, 52.43, 26.84. HRMS (ESI-TOF) m/z: calcd for 7.6 Hz), 129.97 (d, J = 7.8 Hz), 125.28 (d, J = 3.1 Hz), 119.96
+
C10H10NaO3 : 201.0522 (M + Na)+, found: 201.0519.
(d, J = 21.2 Hz), 116.47 (d, J = 23.1 Hz), 52.35. HRMS (ESI-
Methyl 3-acetylbenzoate 3h. 61.2 mg, 86%. H NMR (400 TOF) m/z: calcd for C8H7FNaO2 : 177.0322 (M + Na)+, found:
1
+
MHz, CDCl3) δ 8.58 (s, 1H), 8.21 (d, J = 7.7 Hz, 1H), 8.14 (d, J 177.0318.
= 7.8 Hz, 1H), 7.54 (t, J = 7.8 Hz, 1H), 3.94 (s, 3H), 2.64 (s,
Methyl 4-fluorobenzoate 3kp. 54.2 mg, 88%. 1H NMR (400
3H). 13C NMR (101 MHz, CDCl3) δ 197.23, 166.28, 137.26, MHz, CDCl3) δ 8.01 (dd, J = 8.7, 5.6 Hz, 2H), 7.06 (t, J = 8.6
133.88, 132.28, 130.66, 129.53, 128.84, 52.38, 26.68. HRMS Hz, 2H), 3.87 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 165.95,
+
(ESI-TOF) m/z: calcd for C10H10NaO3 : 201.0522 (M + Na)+, 165.61 (d, J = 253.7 Hz), 131.97 (d, J = 9.3 Hz), 126.29 (d, J =
found: 201.0523.
2.9 Hz), 115.34 (d, J = 22.0 Hz), 51.99. HRMS (ESI-TOF) m/z:
1
+
Methyl 2-nitrobenzoate 3io. 59.4 mg, 82%. H NMR (400 calcd for C8H7FNaO2 : 177.0322 (M + Na)+, found: 177.0319.
MHz, CDCl3) δ 7.90 (dd, J = 7.8, 1.0 Hz, 1H), 7.73 (dd, J = 7.5,
Methyl 2-chlorobenzoate 3lo. 57.1 mg, 84% (for 1lo); 42.8
1
1.5 Hz, 1H), 7.70 – 7.59 (m, 2H), 3.91 (s, 3H). 13C NMR (101 mg, 63% (for 4g). H NMR (400 MHz, CDCl3) δ 7.81 (dd, J =
MHz, CDCl3) δ 165.76, 148.12, 132.86, 131.73, 129.74, 127.39, 7.7, 1.3 Hz, 1H), 7.46 – 7.37 (m, 2H), 7.33 – 7.27 (m, 1H), 3.92
+
123.80, 53.14. HRMS (ESI-TOF) m/z: calcd for C8H7NNaO4 : (s, 3H). 13C NMR (101 MHz, CDCl3) δ 166.06, 133.58, 132.46,
204.0267 (M + Na)+, found: 204.0273.
131.29, 130.97, 129.97, 126.48, 52.33. HRMS (ESI-TOF) m/z:
Methyl 3-nitrobenzoate 3im. 62.3 mg, 86% (for 1im); 61.6 calcd for C8H7ClNaO2 : 193.0027 (M + Na)+, found: 193.0029.
+
1
mg, 85% (for 4c). H NMR (400 MHz, CDCl3) δ 8.83 (s, 1H),
Methyl 3-chlorobenzoate 3lm. 59.8 mg, 88%. 1H NMR
8.39 (d, J = 7.1 Hz, 1H), 8.35 (d, J = 7.8 Hz, 1H), 7.64 (t, J = (400 MHz, CDCl3) δ 8.00 (s, 1H), 7.90 (d, J = 7.8 Hz, 1H),
8.0 Hz, 1H), 3.97 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 7.51 (d, J = 7.1 Hz, 1H), 7.36 (t, J = 7.9 Hz, 1H), 3.91 (s, 3H).
164.85, 148.18, 135.18, 131.78, 129.58, 127.30, 124.47, 52.71. 13C NMR (101 MHz, CDCl3) δ 165.80, 134.44, 132.87, 131.79,
+
HRMS (ESI-TOF) m/z: calcd for C8H7NNaO4 : 204.0267 (M + 129.62, 129.60, 127.63, 52.32. HRMS (ESI-TOF) m/z: calcd
+
Na)+, found: 204.0265.
Methyl 4-nitrobenzoate 3ip. 60.1 mg, 83%. H NMR (400
for C8H7ClNaO2 : 193.0027 (M + Na)+, found: 193.0025.
Methyl 4-chlorobenzoate 3lp. 59.8 mg, 88%. 1H NMR (400
1
MHz, CDCl3) δ 8.29 (d, J = 8.9 Hz, 2H), 8.21 (d, J = 8.9 Hz, MHz, CDCl3) δ 7.94 (d, J = 8.4 Hz, 2H), 7.38 (d, J = 8.4 Hz,
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J. Name., 2017, 00, 1-8 | 5
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Journal Name
2H), 3.89 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 165.98, 8.14 (d, J = 8.2 Hz, 2H), 7.70 (d, J = 8.2 Hz, 2H),V3ie.w9A5rt(icsle, O3nHlin)e.
13
DOI: 10.1039/C7OB01052D
139.16, 130.80, 128.52, 128.42, 52.06. HRMS (ESI-TOF) m/z:
C NMR (100Z MHz, CDCl3) δ 165.86, 134.41 (q, J = 32.6
calcd for C8H7ClNaO2 : 193.0027 (M + Na)+, found: 193.0028. Hz), 133.31, 129.96, 125.38 (q, J = 3.7 Hz), 123.61 (q, J =
Methyl 2-bromobenzoate 3mo. 77.4 mg, 90%. H NMR 272.6 Hz), 52.49. HRMS (ESI-TOF) m/z: calcd for
(400 MHz, CDCl3) δ 7.76 (dd, J = 7.5, 1.9 Hz, 1H), 7.63 (dd, J C9H7F3NaO2 : 227.0290 (M + Na)+, found: 227.0293.
+
1
+
1
= 7.7, 1.2 Hz, 1H), 7.37 – 7.27 (m, 2H), 3.91 (s, 3H). 13C NMR
Methyl 2-methoxybenzoate 3po. 37.8 mg, 57%. H NMR
(101 MHz, CDCl3) δ 166.48, 134.20, 132.44, 132.00, 131.16, (400 MHz, CDCl3) δ 7.78 (dd, J = 7.9, 1.7 Hz, 1H), 7.59 – 7.30
127.03, 121.50, 52.33. HRMS (ESI-TOF) m/z: calcd for (m, 1H), 7.07 – 6.78 (m, 2H), 3.88 (s, 3H), 3.87(s, 3H). 13C
+
C8H7BrNaO2 : 236.9522 (M + Na)+, found: 236.9523.
NMR (101 MHz, CDCl3) δ 166.60, 158.97, 133.40, 131.51,
1
Methyl 3-bromobenzoate 3mm. 78.3 mg, 91%. H NMR 119.99, 119.89, 111.89, 55.83, 51.86. HRMS (ESI-TOF) m/z:
(400 MHz, CDCl3) δ 8.17 (s, 1H), 7.96 (d, J = 7.8 Hz, 1H), calcd for C9H10NaO3 : 189.0522 (M + Na)+, found: 189.0525.
7.67 (d, J = 8.0 Hz, 1H), 7.31 (t, J = 7.9 Hz, 1H), 3.92 (s, 3H).
13C NMR (101 MHz, CDCl3) δ 165.71, 135.82, 132.56, 132.01, (400 MHz, CDCl3) δ 7.63 (d, J = 7.6 Hz, 1H), 7.56 (s, 1H),
+
1
Methyl 3-methoxybenzoate 3pm. 57.8 mg, 87%. H NMR
129.90, 128.11, 122.41, 52.37. HRMS (ESI-TOF) m/z: calcd 7.34 (t, J = 7.9 Hz, 1H), 7.10 (dd, J = 8.2, 1.8 Hz, 1H), 3.91 (s,
+
for C8H7BrNaO2 : 236.9522 (M + Na)+, found: 236.9519.
3H), 3.85 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 166.95,
1
Methyl 4-bromobenzoate 3mp. 77.6 mg, 90%. H NMR 159.51, 131.40, 129.34, 121.94, 119.47, 113.91, 55.38, 52.13.
(400 MHz, CDCl3) δ 7.89 (d, J = 8.6 Hz, 2H), 7.57 (d, J = 8.6 HRMS (ESI-TOF) m/z: calcd for C9H10NaO3 : 189.0522 (M +
Hz, 2H), 3.91 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 166.36, Na)+, found: 189.0522.
+
1
131.70, 131.10, 129.02, 128.02, 52.28. HRMS (ESI-TOF) m/z:
Methyl 4-methoxybenzoate 3pp. 55.8 mg, 84%. H NMR
calcd for C8H7BrNaO2 : 236.9522 (M + Na)+, found: 236.9523. (400 MHz, CDCl3) δ 7.98 (d, J = 9.0 Hz, 2H), 6.90 (d, J = 8.9
Methyl 2-methylbenzoate 3no. 52.8 mg, 88% (for 1no); Hz, 2H), 3.87 (s, 3H), 3.84 (s, 3H). 13C NMR (101 MHz,
45.0 mg, 75% (for 4ho). 1H NMR (400 MHz, CDCl3) δ 7.91 (d, CDCl3) δ 166.80, 163.28, 131.52, 122.53, 113.54, 55.33, 51.77.
+
+
J = 7.4 Hz, 1H), 7.40 (t, J = 7.1 Hz, 1H), 7.26 – 7.22 (m, 2H), HRMS (ESI-TOF) m/z: calcd for C9H10NaO3 : 189.0522 (M +
3.89 (s, 3H), 2.60 (s, 3H). 13C NMR (101 MHz, CDCl3) δ Na)+, found: 189.0524.
168.08, 140.15, 131.93, 131.65, 130.53, 129.53, 125.66, 51.78,
3-Methyleneisobenzofuran-1(3H)-one 3q. 41.5 mg, 71%.
21.69. HRMS (ESI-TOF) m/z: calcd for C9H10NaO2 : 173.0573 1H NMR (400 MHz, CDCl3) δ 7.90 (d, J = 7.7 Hz, 1H), 7.72 (d,
(M + Na)+, found: 173.0575. J = 4.1 Hz, 2H), 7.62 – 7.52 (m, 1H), 5.27 – 5.19 (m, 2H). 13C
+
Methyl 3-methylbenzoate 3nm. 57.6 mg, 96% (for 1nm); NMR (101 MHz, CDCl3) δ 166.82, 151.79, 138.95, 134.44,
1
58.8 mg, 98% (for 4hm). H NMR (400 MHz, CDCl3) δ 7.86 130.43, 125.23, 125.06, 120.57, 91.23. HRMS (ESI-TOF) m/z:
+
(s, 1H), 7.84 (d, J = 7.7 Hz, 1H), 7.36 (d, J = 7.5 Hz, 1H), 7.32 calcd for C9H6NaOS2 : 169.0260 (M + Na)+, found: 169.0262.
(t, J = 7.5 Hz, 1H), 3.91 (s, 3H), 2.40 (s, 3H). 13C NMR (101
Methyl thiophene-2-carboxylate 3r. 12.5 mg, 22% (for 1r);
MHz, CDCl3) δ 167.26, 138.10, 133.63, 130.08, 130.04, 55.1 mg, 97% (for 4l). 1H NMR (400 MHz, CDCl3) δ 7.77 (dd,
128.21, 126.66, 52.00, 21.21. HRMS (ESI-TOF) m/z: calcd for J = 3.7, 1.2 Hz, 1H), 7.52 (dd, J = 5.0, 1.2 Hz, 1H), 7.06 (dd, J
+
C9H10NaO2 : 173.0573 (M + Na)+, found: 173.0569.
= 5.0, 3.8 Hz, 1H), 3.85 (s, 3H). 13C NMR (101 MHz, CDCl3)
Methyl 4-methylbenzoate 3np. 58.8 mg, 98%. 1H NMR δ 162.56, 133.45, 133.34, 132.25, 127.63, 52.02. HRMS (ESI-
(400 MHz, CDCl3) δ 7.93 (d, J = 8.2 Hz, 2H), 7.23 (d, J = 8.0 TOF) m/z: calcd for C6H6NaO2S+: 164.9981 (M + Na)+, found:
Hz, 2H), 3.90 (s, 3H), 2.40 (s, 3H). 13C NMR (101 MHz, 164.9985.
1
CDCl3) δ 167.18, 143.53, 129.56, 129.04, 127.39, 51.91, 21.61.
Di(thiophen-2-yl)methanone 3s. 24.8 mg, 64%. H NMR
+
HRMS (ESI-TOF) m/z: calcd for C9H10NaO2 : 173.0573 (M + (400 MHz, CDCl3) δ 7.90 (dd, J = 3.7, 1.0 Hz, 2H), 7.69 (dd, J
Na)+, found: 173.0572.
= 4.9, 1.0 Hz, 2H), 7.18 (dd, J = 4.9, 3.9 Hz, 2H). 13C NMR
Methyl 2-(trifluoromethyl)benzoate 3oo. 43.2 mg, 53%. 1H (101 MHz, CDCl3) δ 178.75, 142.85, 133.48, 133.13, 127.95.
+
NMR (400 MHz, CDCl3) δ 7.83 – 7.70 (m, 2H), 7.66 – 7.54 (m, HRMS (ESI-TOF) m/z: calcd for C9H6NaOS2 : 216.9752 (M +
2H), 3.93 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 167.25, Na)+, found: 216.9753.
131.69, 131.14, 131.02, 130.04, 128.73 (q, J = 32.5 Hz), 126.64
Methyl thiophene-3-carboxylate 3t. 44.3 mg, 78% (for 1t);
1
(q, J = 5.4 Hz), 123.31 (q, J = 273.3 Hz), 52.77. HRMS (ESI- 53.4 mg, 94% (for 4m). H NMR (400 MHz, CDCl3) δ 8.08
+
TOF) m/z: calcd for C9H7F3NaO2 : 227.0290 (M + Na)+, found: (dd, J = 2.9, 0.9 Hz, 1H), 7.50 (dd, J = 5.0, 0.9 Hz, 1H), 7.28
227.0286.
(dd, J = 5.0, 3.1 Hz, 1H), 3.85 (s, 3H). 13C NMR (101 MHz,
Methyl 3-(trifluoromethyl)benzoate 3om. 47.3 mg, 58%. CDCl3) δ 163.12, 133.42, 132.56, 127.77, 125.92, 51.68.
1H NMR (400 MHz, CDCl3) δ 8.30 (s, 1H), 8.22 (d, J = 7.8 Hz, HRMS (ESI-TOF) m/z: calcd for C6H6NaO2S+: 164.9981 (M +
1H), 7.81 (d, J = 7.8 Hz, 1H), 7.58 (t, J = 7.8 Hz, 1H), 3.95 (s, Na)+, found: 164.9983.
3H). 13C NMR (101 MHz, CDCl3) δ 165.75, 132.77, 131.04 (q,
Methyl picolinate 3u. 15.4 mg, 28% (for 4n). 1H NMR (400
J = 32.9 Hz), 130.97, 129.42 (q, J = 3.5 Hz), 129.03, 126.51 (q, MHz, CDCl3) δ 8.74 (d, J = 4.0 Hz, 1H), 8.13 (d, J = 7.8 Hz,
J = 3.9 Hz), 123.64 (q, J = 272.4 Hz), 52.48. HRMS (ESI-TOF) 1H), 7.84 (ddd, J = 7.8, 7.8, 1.7 Hz, 1H), 7.48 (ddd, J = 7.6, 4.7,
+
m/z: calcd for C9H7F3NaO2 : 227.0290 (M + Na)+, found: 1.0 Hz, 1H), 4.00 (s, 3H). 13C NMR (101 MHz, CDCl3) δ
227.0287.
165.68, 149.78, 147.89, 137.03, 126.94, 125.12, 52.88. HRMS
+
Methyl 4-(trifluoromethyl)benzoate 3op. 69.4 mg, 85% (ESI-TOF) m/z: calcd for C7H7NNaO2 : 160.0369 (M + Na)+,
(for 1op); 76.7 mg, 94% (for 4f). 1H NMR (400 MHz, CDCl3) δ found: 160.0366.
6 | J. Name., 2017, 00, 1-8
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Org. Lett., 2013, 15, 2794; (c) C.-L. Li, X. Qi and X.-F. Wu,
Acknowledgements
View Article Online
ChemistrySelect, 2016, 1, 1702; (d) J. DHOoIu: 1,0J.1.-0H39./XC7iOe Ba0n1d05Q2D.-
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This work was supported by the National Natural Science
Foundation of China (No. 21372176) and Shanghai Science and
Technology Commission (14DZ2261100). We thank Dr. Yuji
Gao with the Technical Institute of Physics and Chemistry,
CAS for his generous assistance in mechanistic studies.
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DOI: 10.1039/C7OB01052D
Oxalic acid as the in situ carbon monoxide generator in
palladium-catalyzed hydroxycarbonylation of arylhalides
Changdong Shao,a,b Ailan Lu,a Xiaoling Wang,a Bo Zhou,a Xiaohong Guan*b,d and Yanghui
Zhang*a,b,c
Br/I
CO2H
Pd
Het
Het
R
R
CO generator system
(CO2H•H2O)2
Ac2O/DIPEA
low catalyst loading 1 mol %
50 examples, yields up to 99%
Oxalic acid as a high efficient, safe and tractable concentrated carbon monoxide surrogate was
successfully introduced into the palladium-catalyzed hydroxycarbonylation of arylhalides.