Palladium-Catalyzed Carbonylative Transformation of Organic Halides with Formic Acid as the Coupling Partner and CO Source: Synthesis of Carboxylic Acids

Article abstract of DOI:10.1021/acs.joc.7b01808

A palladium-catalyzed carbonylative transformation of organic halides with formic acid as the coupling partner to produce carboxylic acids has been developed. With a catalytic amount of DCC as the activator of formic acid, the process can be realized successfully through benzoic formic anhydride as the intermediate. Both vinyl and aryl (pseudo)halides were conveniently transformed into the corresponding acids in good yields.

Full text of DOI:10.1021/acs.joc.7b01808

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Article
Palladium-Catalyzed Carbonylative Transformation
of Organic Halides with Formic Acid as the Coupling
Partner and CO Source: Synthesis of Carboxylic Acids
Fu-Peng Wu, Jin-Bao Peng, Xinxin Qi, and Xiao-Feng Wu
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.7b01808 • Publication Date (Web): 18 Aug 2017
Downloaded from http://pubs.acs.org on August 18, 2017
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PalladiumꢀCatalyzed Carbonylative Transformation of Organic Halides with Formic Acid as the
Coupling Partner and CO Source: Synthesis of Carboxylic Acids
,
, ,‡
†
†
†
†
FuꢀPeng Wu, JinꢀBao Peng,* Xinxin Qi, and XiaoꢀFeng Wu*
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†Department of Chemistry, Zhejiang SciꢀTech University, Hangzhou, Zhejiang 310018, People’s
Republic of China
‡
LeibnizꢀInstitut für Katalyse e.V. an der, Institution Universität Rostock, AlbertꢀEinsteinꢀStraße
29a, Rostock 18059, Germany
Abstract: A palladiumꢀcatalyzed carbonylative transformation of organic halides with formic acid
as the coupling partner to produce carboxylic acids has been developed. With catalytic amount of
DCC as the activator of formic acid, the process can be realized successfully through benzoic
formic anhydride as the intermediate. Both vinyl and aryl(pseudo)halides were conveniently
transformed into the corresponding acids in good yields.
Introduction
Carboxylic acids represent a large family of important structure units that exist in many natural
1
products, pharmaceuticals, agrochemicals, and materials. Several efficient methods have been
developed for the synthesis of these structures, oxidation of primary alcohols, aldehydes or
hydrolysis of the corresponding nitriles have been considered as the traditional procedures for
2
their preparation. The reaction of organic reagents with CO , such as KolbeꢀSchmitt reaction and
the Grignard reaction provide good efficiency and regionꢀselectivity, but the functional group
2
compatibility was limited. Thus, palladium catalyzed hydroxycarbonylation of aryl halides
provides an efficient and straightforward alternative for preparing such compounds. Despite many
advantages, the main drawback for this method is the requirement of highly toxic CO gas and the
corresponding high pressure equipment. To circumvent this problem, several CO gasꢀfree
carbonylation protocols have been developed based on CO surrogates during the past decades.
Metalꢀcarbonyl complexes, formamides, aldehyde, formic acid, and oxalyl chloride were all
3
investigated and successively used as CO sources. Among them, formic acid attracted much
2
attention since it can generate one molecule of CO after releasing one molecule of H O. Many
research groups including our group have developed a series of efficient carbonylation reactions
4
employing formic acid as the CO source. However, there are two major disadvantages for this
2 2 4
method: 1) (over)stoichiometric amounts of activator such as Ac O and H SO were needed to
react with formic acid to release CO; 2) (over)stoichiometric byꢀproduct such as AcOH was
generated which might influence the subsequent carbonylation reaction or need equal amount of
base to neutralize. Hydroxycarbonylation reaction with catalytic amount of activator using formic
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acid as the CO source was rarely studied.
Among the seldom reports, Skrydstrup and coꢀworkers elaborated an elegant palladiumꢀcatalyzed
hydroxycarbonylation of aryl halides with potassium formate as a mildly basic nucleophile and
4
c
CO source in 2013 (Scheme 1, a). A special acylꢀPd(II) precatalyst, which delivered
substoichiometric CO to initiate the reaction and also acted as the catalyst, was prepared and used
in this reaction. Another catalytic hydroxycarbonylation reaction with formic acid was reported by
Zhou and coꢀworkers (Scheme 1, b). Using catalytic amount of acetic anhydride as the initiator,
acrylic acids were synthesized by a palladiumꢀcatalyzed hydrocarboxylation reaction of alkynes
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with formic acid.
Recently, we have developed a novel palladiumꢀcatalyzed hydroxycarbonylation of aryl halides
with the inꢀsitu generation of CO and H
2
O, benzoic acid could be synthesized without the addition
5
of CO gas. However, stoichiometric acetic anhydride and aliphatic alcohol were needed for this
transformation. Lately, we found that benzoic acid could be generated via a decarbonylation of the
4h
benzoic formic anhydride, where the property of ligand played a determinative role. From the
point of the reaction mechanism, we assume that catalytic amount of DCC would be possible as
well. As the CO from the decomposed benzoic formic anhydride would be applicable for the next
catalytic cycle. Furthermore, the carboxylation of vinyl (pseudo)halides provides a direct method
for the preparation of acrylic acid, which is versatile material in industry. With these
considerations above, herein, we wish to report a new developed palladium catalyzed
hydroxycarbonylation procedure with formic acid using catalytic amount of DCC as the activator
(
Scheme 1, c).
Scheme 1. Formic Acid Based Hydroxycarbonylation Reaction with Catalytic Activator.
Results and Discussion
The initial investigation was performed with 2ꢀphenylvinyl iodide as the starting material. We
chose Xantphos as the ligand because the large bite angle bidentate phosphine ligand facilitates
the formation of anhydride and subsequent provide the acid product. To our delight, heating a
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solution of vinyl iodide and formic acid in the presence of Pd(OAc) with only 0.2 equivalent of
DCC as the activator in DMF for 20 hours, the carboxylation product cinnamic acid was produced
in 92% yield (Table 1, entry 2). Reducing the loading of DCC to 0.1 equivalent gave a decreased
yield of 75% (Table 1, entry 1). However, further increasing of the amount of DCC didn’t improve
the reaction yield (Table 1, entries 3ꢀ5). It should be mentioned that all the reactions were
conducted in a 20 mL sealed tube, which give a theoretical CO partial pressure of 0.1 bar when 0.2
equivalent DCC was used. This is also agreeable to the previous report of Skrydstrup’s
observation that a minimum of 0.1 bar carbon monoxide partial pressure was essential for
effective convention. This is explainable since the coordination and releasing of CO to vinyl
palladium complex is a reversible process, lower CO partial pressure would facilitate the release
of the CO from the palladium and thus decrease the hydroxycarboxylation yield. Additionally, no
desired acid product can be obtained in the absence of DCC, but some 1,4ꢀdiphenylbutaꢀ1,3ꢀdiene
can be detected as the homoꢀcoupling product (Table 1, entry 6). Some other bidentate phosphine
ligands were tested as well; decreased yield was obtained (Table 1, entryies 7ꢀ11). And only 6% of
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cinnamic acid could be detected with PPh
3
as the ligand (Table 1, entry 12).
a
Table 1. Optimizing the reaction condition.
O
Pd(OAc)2
Ligand
I
OH
+
HCOOH
Et N, DMF
3
1a
2a
DCC
Entry
Ligand
Yield (%)
(
equiv.)
0.1
0.2
0.4
0.6
1.0
0
1
2
3
4
5
6
7
8
9
Xantphos
Xantphos
Xantphos
Xantphos
Xantphos
Xantphos
DPPE
75
92
84
81
84
0
0.2
0.2
0.2
0.2
0.2
0.2
30
27
35
48
81
6
DPPP
DPPPe
10
DPPF
11
DPEphos
12
PPh
3
a
2
Reaction conditions: vinyl iodide (0.5 mmol), formic acid (3.5 mmol), Pd(OAc) (3 mol%),
Ligand (3 mol%), Et N (1.0 mmol), 100 ℃ , 20 h. DPPE = 1,2ꢀbis(diphenylphosphino)ethane.
3
DPPP = 1,3ꢀbis(diphenylphosphino)propane. DPPPe = 1,5ꢀbis(diphenylphosphino)pentane. DPPF
=
1,1’ꢀbis(diphenylphosphino)ferrocene. DPEphos = bis(2ꢀdiphenylphosphino)diphenyl ether.
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Xantphos = 4,5ꢀbis(diphenylphosphino)ꢀ9,9ꢀdimethylxanthene.
With the optimized reaction condition in hand (Table 1, entry 2), we began to investigate the
generality of the carboxylation reaction with a series of substituted vinyl iodides. As shown in
Table 2, various substituted 2ꢀphenylvinyl iodides were subjected to the optimized reaction
condition, the carboxylation reaction proceeded smoothly and the corresponding cinnamic acids
were generated in high to excellent yields (Scheme 2, 2aꢀ2h). The electronic property and position
of the substituent group on the benzene ring showed little influences on the yields.
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Table 2. Substrate scope of vinyl iodides
a
Reaction condition: vinyl iodides (0.5 mmol), Pd(OAc)
2
(3 mol%), Xantphos (3 mol %),
o
HCOOH (3.5 mmol), DCC (0.1 mmol), Et
3
N (1.0 mmol), DMF (1 mL), 100 C, 20 h, isolated
yields.
Then various aryl iodides were studied under our standard conditions. As summarized in Table 3, a
series of aryl iodides were tested in this reaction and the corresponding carboxylic acid were
isolated in good yields in general. Both electronꢀdonating groups (Table 3, 4bꢀ4f) and
electronꢀwithdrawing groups (Table 3, 4gꢀ4j) substitution at different position were well tolerated
and produced the corresponding acids in good yields. Generally, substrates with
electronꢀwithdrawing groups gave slightly higher yield than that of electronꢀdonating groups.
Notably, aryl iodides with fluoroꢀ and chloroꢀsubstitutions were also tolerated in this reaction and
delivered the corresponding product in 82% yields (Table 3, 4g and 4h). However,
pꢀbromoiodobenzene gave an nonꢀseparatable mixture of benzoic acid, 4ꢀbromobenzoic acid and
terephthalic acid (1:0.06:0.1; Scheme 2). This phenomena implies that aryl bromides are
applicable substrates as well. Furthermore, 2ꢀiodonaphthalene and 3ꢀiodothiophene were also
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amenable to this reaction and provided the desired products in 97% and 46% yields, respectively
(Table 3, 4k and 4l).
a
Table 3. Substrate scope of aryl iodides
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a
Reaction condition: aryl iodides (0.5 mmol), Pd(OAc)
2
(3 mol%), Xantphos (3 mol %), HCOOH
o
(3.5 mmol), DCC (0.1 mmol), Et
3
N (1.0 mmol), DMF (1 mL), 100 C, 20 h, isolated yields.
Scheme 2. Carbonylative transformation of p-bromoiodobenzene.
Aryl bromides, which are more abundant and cheaper than aryl iodides, usually represent more
challenging materials for palladium catalyzed carbonylation owing to their higher activation
barrier for the CꢀBr bond activation. To our delight, various substituted aryl bromides were
conveniently applied in this reaction and the corresponding carboxylic acids were generated in
moderate to good yields (Table 4).
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Table 4. Substrate scope of aryl bromides
Pd(OAc) (3 mol%)
Xantphos (3 mol%)
DCC (20 mol%)
2
O
Br
OH
OH
+
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R
R
Et N (2 equiv.)
3
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O
O
O
OH
OH
MeO
Ac
4a (80%)
4d (65%)
4e (58%)
O
O
O
OH
OH
OH
F
Cl
4g (84%)
4h (67%)
4i (74%)
a
Reaction condition: aryl bromides (0.5 mmol), Pd(OAc) (3 mol%), Xantphos (3 mol %),
2
o
HCOOH (3.5 mmol), DCC (0.1 mmol), Et
3
N (1.0 mmol), DMF (1 mL), 100 C, 20 h, isolated
yields.
In addition to aryl iodides and bromides, when phenyl triflite were subjected to the optimized
conditions, the carboxylation reaction proceeded successfully and the desired benzoic acid was
obtained in 89% yield (Scheme 3, eq. 1). We also conducted a gramꢀscale reaction to demonstrate
the synthetic utility of this method. When the reaction was performed on 20 mmol scale, benzoic
acid was obtained in 68% yield (Scheme 3, eq. 2). However, no conversion of substrate could be
observed when chlorobenzene or 4ꢀchlorobenzotrifluoride was applied.
Scheme 3. The reaction of phenyl triflate and gram-scale synthesis of benzoic acid.
Pd(OAc) (3 mol%)
Xantphos (3 mol%)
DCC (20 mol%)
2
O
OTf
OH
+
HCOOH
(1)
(2)
Et N (2 equiv.)
3
o
DMF, 100 C
4a (89%)
Pd(OAc) (3 mol%)
Xantphos (3 mol%)
DCC (20 mol%)
2
O
I
OH
+
HCOOH
Et N (2 equiv.)
3
o
DMF, 100 C
20 mmol
4a (68%)
Based on these results and precedent reports, a possible reaction mechanism is proposed in
0
Scheme 4. Initially, oxidative addition of the inꢀsitu generated Pd to CꢀX bond give an
arylꢀpalladium complex 6. Then, coordination and insertion of 6 with one molecule of carbon
monoxide, which was generated inꢀsitu from the reaction of formic acid with DCC as the activator,
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forms an acylꢀpalladium intermediate 7. Subsequently, the ligand exchange of the iodide with
formic acid would afford the acylpalladium formic acid complex 8. The steric effect of large bite
1
angle bisphosphine lignated palladium would enforce a η binding mode through one oxygen atom.
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Subsequently, reductive elimination delivered the benzoic formic anhydride 9. Meanwhile, Pd
was regenerated and used for the next catalyst cycle. The benzoic formic anhydride 9 then
decomposed to generate the terminal acid product 4 and release CO at the same time for following
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4
c,6
up reactions.
Scheme 4. Plausible reaction mechanism.
In summary, we have developed a palladium catalyzed carbonylative transformation reaction of
organic halides with formic acid as the CO source and coupling partner. With catalytic amount of
DCC as the activator, the reaction was initiated and CO was generated from the decarbonylation
of the formed benzoic formic anhydride and used in the next catalytic cycle. Vinyl and aryl
(pseudo)halides were all suitable substrates and transformed into the corresponding acids in good
yields.
EXPERIMENTAL SECTION
General Information: Unless otherwise noted, all reactions were carried out under a nitrogen
atmosphere. All chemicals were from commercial sources and used as received without
further purification. All solvents were purified and dried by standard techniques, and distilled
prior to use. Column chromatography was performed on silica gel (200ꢀ300 meshes) using
o
1
13
petroleum ether (bp. 60~90 C) and ethyl acetate as eluent. H and C NMR spectra were
taken on 400 MHz instruments and spectral data were reported in ppm relative to
3
tetramethylsilane (TMS) as internal standard and CDCl as solvent. Mass spectra (MS) were
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measured on spectrometer by direct inlet at 70 eV.
General Procedure. Pd(OAc) (3 mol %), Xantphos (3 mol%) were added into an ovenꢀdried
2
tube which was then vacuumed and refilled with nitrogen for three times. A solution of formic
acid (3.5 mmol) and organic halide (0.5 mmol) in DMF (1.0 mL) was added to the reaction
3
tube. After DCC (0.1 mmol) and Et N (1.0 mmol) were added, the tube was sealed and the
mixture was stirred at 100 °C for 20 h. After the reaction was completed, the reaction mixture
was filtered and concentrated under vacuum. The crude product was purified by column
chromatography on silica gel to afford the corresponding product.
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2.2 Spectroscopic Data of Products
[7]
1
Cinnamic acid : 2a, 92% yield, 68 mg, eluent (petroleum ether/EtOAc: 2:1), H NMR
(
400 MHz, DMSO) δ 12.41 (s, 1H), 7.69 (dd, J = 6.3, 2.6 Hz, 2H), 7.60 (d, J = 16.0 Hz, 1H),
1
3
7.46 – 7.38 (m, 3H), 6.54 (d, J = 16.0 Hz, 1H). C NMR (101 MHz, DMSO) δ 168.07,
144.37, 134.70, 130.68, 129.36, 128.66, 119.72.
[7]
(E)-3-(o-Tolyl)acrylic acid : 2b, 90% yield, 73 mg, eluent (petroleum ether/EtOAc: 2:1),
1
H NMR (400 MHz, DMSO) δ 12.46 (s, 1H), 7.83 (d, J = 15.9 Hz, 1H), 7.68 (d, J = 7.6 Hz,
1
3
1
H), 7.33 – 7.26 (m, 1H), 7.26 – 7.19 (m, 2H), 6.42 (d, J = 15.9 Hz, 1H), 2.37 (s, 3H). C
NMR (101 MHz, DMSO) δ 168.03, 141.59, 137.60, 133.36, 131.14, 130.39, 126.90, 126.86,
20.63, 19.71.
1
[7]
(
E)-3-(m-Tolyl)acrylic acid : 2c, 88% yield, 71 mg, eluent (petroleum ether/EtOAc: 2:1),
1
H NMR (400 MHz, DMSO) δ 12.39 (s, 1H), 7.55 (dd, J = 16.0, 4.8 Hz, 1H), 7.47 (d, J = 8.3
13
Hz, 2H), 7.34 – 7.20 (m, 2H), 6.50 (ddd, J = 16.0, 3.8, 2.3 Hz, 1H), 2.37 – 2.29 (m, 3H). C
NMR (101 MHz, DMSO) δ 168.07, 144.51, 138.60, 134.60, 131.38, 129.24, 129.10, 125.88,
119.45, 21.28.
[7]
(
E)-3-(p-Tolyl)acrylic acid : 2d, 89% yield, 72 mg, eluent (petroleum ether/EtOAc: 2:1),
1
H NMR (400 MHz, DMSO) δ 12.34 (s, 1H), 7.56 (dd, J = 12.1, 5.6 Hz, 3H), 7.21 (d, J = 7.9
13
Hz, 2H), 6.47 (d, J = 16.0 Hz, 1H), 2.31 (s, 3H). C NMR (101 MHz, DMSO) δ 168.17,
144.38, 140.58, 131.96, 129.96, 128.62, 118.55, 21.43.
[7]
(
E)-3-(4-Fluorophenyl)acrylic acid : 2e, 79% yield, 66 mg, eluent (petroleum
1
ether/EtOAc: 2:1), H NMR (400 MHz, DMSO) δ 12.41 (s, 1H), 7.75 (dd, J = 8.4, 5.7 Hz,
1
3
2H), 7.60 (d, J = 16.0 Hz, 1H), 7.23 (t, J = 8.8 Hz, 2H), 6.49 (d, J = 16.0 Hz, 1H). C NMR
(101 MHz, DMSO) δ 168.00, 164.84, 162.37, 143.14, 131.36, 131.33, 130.96, 130.88, 119.54,
116.41, 116.20.
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[7]
(
E)-3-(4-Chlorophenyl)acrylic acid : 2f, 89% yield, 81 mg, eluent (petroleum
1
ether/EtOAc: 2:1), H NMR (400 MHz, DMSO) δ 12.49 (s, 1H), 7.70 (d, J = 8.4 Hz, 2H),
13
7
.58 (d, J = 16.0 Hz, 1H), 7.44 (d, J = 8.4 Hz, 2H), 6.55 (d, J = 16.0 Hz, 1H). C NMR (101
MHz, DMSO) δ 167.90, 142.94, 135.17, 133.64, 130.33, 129.35, 120.53.
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(E)-3-(4-Methoxyphenyl)acrylic acid : 2g, 87% yield, 77 mg, eluent (petroleum
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ether/EtOAc: 3:2), H NMR (400 MHz, DMSO) δ 12.24 (s, 1H), 7.63 (d, J = 8.6 Hz, 2H),
1
3
7
.56 (d, J = 16.0 Hz, 1H), 6.96 (d, J = 8.6 Hz, 2H), 6.38 (d, J = 16.0 Hz, 1H), 3.78 (s, 3H). C
NMR (101 MHz, DMSO) δ 168.32, 161.39, 144.19, 130.37, 127.28, 116.96, 114.79, 55.71.
[7]
(
E)-3-(4-(tert-Butyl)phenyl)acrylic acid : 2h, 78% yield, 80 mg, eluent (petroleum
1
ether/EtOAc: 2:1), H NMR (400 MHz, DMSO) δ 12.38 (s, 1H), 7.62 – 7.54 (m, 3H), 7.41
13
(
d, J = 8.1 Hz, 2H), 6.48 (d, J = 16.0 Hz, 1H), 1.26 (s, 9H). C NMR (101 MHz, DMSO) δ
68.16, 153.51, 144.23, 131.97, 128.46, 126.14, 118.78, 34.98, 31.33.
1
[4h]
1
Benzoic acid : 4a, 84% yield, 51 mg, eluent (petroleum ether/EtOAc: 2:1), H NMR
(400 MHz, DMSO) δ 12.96 (s, 1H), 8.00 – 7.92 (m, 2H), 7.61 (d, J = 7.5 Hz, 1H), 7.50 (t, J =
1
3
7
.6 Hz, 2H). C NMR (101 MHz, DMSO) δ 167.79, 133.31, 131.21, 129.73, 129.02.
[4h]
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-Methylbenzoic acid : 4b, 83% yield, 57 mg, eluent (petroleum ether/EtOAc: 2:1), H
NMR (400 MHz, CDCl
3
) δ 12.23 (s, 1H), 8.14 (t, J = 9.8 Hz, 1H), 7.50 (t, J = 7.5 Hz, 1H),
13
7
1
3
.33 (t, J = 7.6 Hz, 2H), 2.72 (s, 3H). C NMR (101 MHz, CDCl ) δ 173.74, 141.43, 133.02,
3
31.98, 131.66, 128.37, 125.91, 22.20.
[4h]
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-Methylbenzoic acid :4c, 82% yield, 56 mg, eluent (petroleum ether/EtOAc: 2:1), H
NMR (400 MHz, CDCl ) δ 12.49 (s, 1H), 7.98 (d, J = 7.2 Hz, 2H), 7.59 – 7.36 (m, 2H), 2.46
3
1
3
(s, 3H). C NMR (101 MHz, CDCl
3
) δ 172.87, 138.33, 134.65, 130.75, 129.30, 128.42,
127.43, 21.28.
[4h]
1
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-Methylbenzoic acid : 4d, 82% yield, 56 mg, eluent (petroleum ether/EtOAc: 2:1), H
NMR (400 MHz, CDCl ) δ 11.11 (s, 1H), 8.04 (d, J = 8.0 Hz, 2H), 7.30 (d, J = 7.8 Hz, 2H),
3
13
2
.46 (s, 3H). C NMR (101 MHz, CDCl
3
) δ 172.53, 144.68, 130.28, 129.24, 126.63, 21.79.
[4h]
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-Methoxybenzoic acid : 4e, 67% yield, 51 mg, eluent (petroleum ether/EtOAc: 1:1),
1
H NMR (400 MHz, DMSO) δ 12.64 (s, 1H), 7.90 (d, J = 8.8 Hz, 2H), 7.01 (d, J = 8.8 Hz,
13
2
H), 3.82 (s, 3H). C NMR (101 MHz, DMSO) δ 167.48, 163.30, 131.80, 123.43, 114.24,
55.85.
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[
1,1'-Biphenyl]-4-carboxylic acid :4f, 63% yield, 62 mg, eluent (petroleum
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ether/EtOAc: 2:1), H NMR (400 MHz, DMSO) δ 12.99 (s, 1H), 8.04 (d, J = 8.1 Hz, 2H),
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.79 (d, J = 8.2 Hz, 2H), 7.72 (d, J = 7.6 Hz, 2H), 7.50 (t, J = 7.5 Hz, 2H), 7.42 (t, J = 7.3 Hz,
13
1H). C NMR (101 MHz, DMSO) δ 167.63, 144.78, 139.50, 130.44, 130.10, 129.53, 128.74,
127.42, 127.26.
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-Fluorobenzoic acid : 4g, 82% yield, 57 mg, eluent (petroleum ether/EtOAc: 2:1), H
NMR (400 MHz, DMSO) δ 13.04 (s, 1H), 8.08 – 7.97 (m, 2H), 7.31 (dd, J = 12.3, 5.4 Hz,
13
2
1
4
H). C NMR (101 MHz, DMSO) δ 166.83, 166.62, 164.13, 162.17, 132.61, 132.51, 127.81,
16.17, 115.95.
[4h]
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-Chlorobenzoic acid : 4h, 82% yield, 64 mg, eluent (petroleum ether/EtOAc: 2:1), H
NMR (400 MHz, DMSO) δ 13.19 (s, 1H), 7.93 (d, J = 8.4 Hz, 2H), 7.53 (d, J = 8.4 Hz, 2H).
13
C NMR (101 MHz, DMSO) δ 166.93, 138.26, 131.57, 130.08, 129.14.
[4h]
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4-Acetylbenzoic acid : 4i, 71% yield, 58 mg, eluent (petroleum ether/EtOAc: 3:2), H
13
NMR (400 MHz, DMSO) δ 13.29 (s, 1H), 8.04 (s, 4H), 2.62 (s, 3H). C NMR (101 MHz,
DMSO) δ 197.65, 166.61, 139.76, 134.52, 129.50, 128.25, 26.93.
[4h]
4
-(Methoxycarbonyl)benzoic acid : 4j, 81% yield, 73 mg, eluent (petroleum
1
ether/EtOAc: 3:2), H NMR (400 MHz, DMSO) δ 13.29 (s, 1H), 8.03 (d, J = 2.2 Hz, 4H),
13
3
5
1
.87 (s, 3H). C NMR (101 MHz, DMSO) δ 167.01, 166.03, 135.27, 133.56, 129.99, 129.74,
2.83.
[4h]
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-Naphthoic acid : 4k, 97% yield, 84 mg, eluent (petroleum ether/EtOAc: 2:1), H
NMR (400 MHz, DMSO) δ 13.18 (s, 1H), 8.92 (d, J = 8.6 Hz, 1H), 8.24 – 8.16 (m, 1H), 8.14
(d, J = 8.1 Hz, 1H), 8.00 (d, J = 8.1 Hz, 1H), 7.65 (dd, J = 8.3, 7.0 Hz, 1H), 7.58 (dt, J = 7.7,
1
3
4.6 Hz, 2H). C NMR (101 MHz, DMSO) δ 169.18, 133.95, 133.39, 131.20, 130.36, 129.06,
1
28.21, 128.02, 126.64, 126.06, 125.33.
[4h]
Thiophene-3-carboxylic acid : 4l, 46% yield, 30 mg, eluent (petroleum ether/EtOAc:
1
2
3
1
:1), H NMR (400 MHz, DMSO) δ 12.70 (s, 1H), 8.26 (d, J = 2.9 Hz, 1H), 7.61 (dd, J = 4.9,
13
.0 Hz, 1H), 7.45 – 7.42 (m, 1H). C NMR (101 MHz, DMSO) δ 164.03, 134.78, 133.73,
28.20, 127.72.
AUTHOR INFORMATION
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*Eꢀmail: pengjb_05@zstu.edu.cn
Eꢀmail: xiaoꢀfeng.wu@catalysis.de
*
ACKNOWLEDGMENT
The authors thank the financial supports from NSFC (21472174, 21602201, 21602204), education
department of Zhejiang Province (Y201636555), Zhejiang SciꢀTech University (16062095ꢀY) and
Zhejiang Natural Science Fund for Distinguished Young Scholars (LR16B020002).
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Supporting Information
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H and C NMR spectrums of products supplied as Supporting Information.
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