Palladium-catalyzed direct alkoxycarbonylation of aromatic C-H bonds via selective C-C cleavage of a-keto esters

Article abstract of DOI:10.1002/adsc.201300436

A novel palladium-catalyzed direct alkoxycarbonylation of 2-arylpyridines, 2-arylquinolines, benzo[h]quinolines, 2-phenylpyrimidines, N-pyrimidine pyrroles and N-pyrimidine indoles via aromatic C-H bond activation and selective C-C cleavage of a-keto esters has been developed. The method has the advantages of wide functional group tolerance, high selectivity, broad range of substrates and good yields.

Full text of DOI:10.1002/adsc.201300436

FULL PAPERS
DOI: 10.1002/adsc.201300436
Palladium-Catalyzed Direct Alkoxycarbonylation of Aromatic
À
À
C H Bonds via Selective C C Cleavage of a-Keto Esters
Wei Zhou,a Pinhua Li,a Yicheng Zhang,a and Lei Wanga,b,*
a
Department of Chemistry, Huaibei Normal University, Huaibei, Anhui 235000, Peopleꢀs Republic of China
Fax : (+86)-561-309-0518; phone: (+86)-561-380-2069; e-mail: leiwang@chnu.edu.cn
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Shanghai 200032, Peopleꢀs
b
Republic of China
Received: May 18, 2013; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201300436.
Abstract: A novel palladium-catalyzed direct alkoxy- high selectivity, broad range of substrates and good
carbonylation of 2-arylpyridines, 2-arylquinolines, yields.
benzo[h]quinolines, 2-phenylpyrimidines, N-pyrimi-
dine pyrroles and N-pyrimidine indoles via aromatic
C H bond activation and selective C C cleavage of Keywords: alkoxycarbonylation; C C bond cleavage;
a-keto esters has been developed. The method has C H bond activation; a-keto esters; palladium cata-
the advantages of wide functional group tolerance, lysts
À
À
À
À
Introduction
bond with diethyl azodicarboxylate.[8] In 2009, Zhang
and co-workers developed the rhodium-catalyzed
À
Esters are very important in the chemical and phar- direct oxidative carbonylation of the aromatic C H
maceutical industries, and they have been widely used bond with CO and alcohol.[9] In the same year, the
in the production of valuable compounds, such as ruthenium-catalyzed direct alkoxycarbonylation of
polymers, fragrances, fatty acids, etc.[1] There are two the C H bond with carbamoyl chlorides was accom-
À
well-known traditional approaches for the preparation plished by Kakiuchi and co-workers.[10] In 2011, Shi
of esters. One is based on the reaction of activated and co-workers also achieved ethoxycarbonylation of
À
À
acid derivatives (acyl chlorides and anhydrides) with the aromatic C H bond via C C bond cleavage of ox-
alcohols,[2] and the other is the transition metal-cata- aziridine.[11] Most recently, we have developed an effi-
À
lyzed cross-coupling reaction of aryl halides with cient carbo-acylation reaction of the aromatic C H
carbon monoxide.[3] However, the above methods bond with a-diketones via Pd-catalyzed C H activa-
À
À
have the drawbacks of multiple-step reactions, and tion and C C bond cleavage for the synthesis of aryl
necessity to handle a hazardous gas which is often ketones.[12] However, there is hardly any formation of
under high pressure, and pre-functionalized substrates the desired alkoxycarbonylation products in the reac-
are needed in some cases. Therefore, exploiting tions of 2-phenylpyridine with dimethyl oxalate or di-
a simple and efficient strategy to access esters is ethyl oxalate. Very recently, Tan and co-workers re-
highly desirable.
ported a Pd-catalyzed direct alkoxycarbonylation of
Recently, the direct alkoxycarbonylation of simple anilides using glyoxylates for the synthesis of anthra-
[4]
C H bonds, a method involving C H bond activa- nilic esters.[13] Inspired by Tanꢀs work, we envisioned
À
À
tion and functionalization, has received much atten- that a-keto esters could be utilized as the alkoxycar-
tion in the construction of the ester group on account bonylation reagents in the palladium-catalyzed aro-
À
of its atom economy and simplified procedure in com- matic C H bond alkoxycarbonylation. To our delight,
parison with the traditional strategies.[5,6] For the pur- 2-phenylpyridine reacted with ethyl benzoylformate
pose of obtaining selective activation and functionali- smoothly and generated the corresponding (2’-alkoxy-
À
À
zation of the C H bond to a C CO2R group, signifi- carbonyl)-2-phenylpyridines in good yields. To devel-
cant achievements have been made by means of di- op an alternative and concise pathway to the direct al-
À
recting functional groups in the presence of a cata- koxycarbonylation of the aromatic C H bond, herein
lyst.[7] In 2008, Yu reported the palladium-catalyzed we wish to report this novel and efficient Pd-catalyzed
À
À
oxidative ethoxycarbonylation of the aromatic C H direct alkoxycarbonylation of aromatic C H bonds
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Scheme 1. The direct alkoxycarbonylation of the aromatic C H bond.
À
through selective C C cleavage of a-keto esters ence of oxidants on the reaction was explored.
(Scheme 1). As far as we know, this is the first exam- Among the tested organic oxidants, including tert-
ple that utilizes a-keto esters as the alkoxycarbonyla-
Table 1. Optimization of the reaction conditions.[a]
À
tion reagents in the palladium-catalyzed aromatic C
H bond alkoxycarbonylation of 2-arylpyridines, 2-ar-
ylquinolines, benzo[h]quinolines, 2-phenylpyrimidines,
N-pyrimidine pyrroles and N-pyrimidine indoles.
Results and Discussion
Entry Pd catalyst
Solvent Oxidant Yield [%][b]
In order to realize the direct alkoxycarbonylation of
1
2
3
4
5
6
7
8
Pd
PdCl2
G
THF
THF
THF
THF
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
81
73
71
66
59
57
66
53
23
17
0
0
0
71
22
33
39
À
À
the C H bond via selective C C bond cleavage of a-
keto esters, 2-phenylpyridine (1a) and ethyl benzoyl-
formate (2a) were selected as model substrates. At
the beginning, an intensive screening of Pd salts was
investigated under the conditions of THF as solvent
and tert-butyl hydroperoxide (TBHP) as oxidant. To
our delight, PdACHTUNGTRENNUNG(OAc)2 exhibited the highest activity
among the Pd sources tested in Table 1, and the de-
sired product 3a was isolated in 81% yield (Table 1,
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pd
diglyme TBHP
dioxane TBHP
toluene TBHP
NMP
DCE
DMSO
DMF
THF
9
10
11
12
13
14
15
TBHP
TBHP
TBHP
TBHP
DBHP
TBPB
DTBH
PAA
entry 1). Other Pd sources, PdCl2, Pd
ACHTUGNRTNE(NUNG PPh3)2Cl2,
Pd(PCy3)2Cl2, Pd(CH3CN)2Cl2, and Pd(PPh3)4 were
A
R
ACHTUNGTRENNUNG
less effective and 3a was obtained in 57–73% yields
(Table 1, entries 2–6). Then, a variety of solvents were
examined and the results indicated that THF was the 16
best reaction medium. Other solvents, such as di-
glyme, dioxane, toluene and NMP gave the inferior
yields of 3a in 17–66% (Table 1, entries 7–10). How-
ever, when the model reaction was carried out in
DCE, DMSO or DMF, no desired product 3a was de-
tected (Table 1, entries 11–13). In addition, the influ-
THF
THF
THF
17
[a]
Reaction conditions: 2-phenylpyridine (1a, 0.50 mmol), a-
keto ester (ethyl benzoylformate, 2a, 0.75 mmol), Pd cat-
alyst (5.0 mol%), oxidant (0.75 mmol), solvent (anhy-
drous, 2.0 mL), sealed tube, 1108C, 12 h.
[b]
Isolated yields.
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Palladium-Catalyzed Direct Alkoxycarbonylation of Aromatic C H Bonds
Table 2. The scope of 2-arylpyridines and benzoylformates.[a]
Scheme 2. The reactivity of 2a, 2b and 2c with 1a.
butyl hydroperoxide (TBHP), a,a-dimethylbenzyl hy-
droperoxide (DBHP), tert-butyl peroxybenzoate
(TBPB), di-tert-butyl peroxide (DTBP), and peroxy-
acetic acid (PAA), TBHP (anhydrous) was the most
effective one (Table 1, entries 14–17). Further optimi-
zation of the reaction conditions demonstrated that
the model reaction was completed in THF (sealed
tube) at 1108C for 12 h.
À
As a source of the ethyloxycarbonyl group via C C
cleavage of a-keto esters, ethyl 2-oxoacetate (2b)[14]
and ethyl 2-oxopropanoate (2c) were much less reac-
tive compared with ethyl benzoylformate (2a)
(Scheme 2).
Under the optimized reaction parameters
[PdACHTUNGTRENNUNG(OAc)2 (5.0 mol%) as the catalyst, TBHP (anhy-
drous, 1.5 equiv.) in THF at 1108C for 12 h], we
turned our attention to an investigation of the scope
of the alkACHTUNGTRENNUNGoxycarbonylation reactions between arylpyr-
idines and a-keto esters. As can be seen from Table 2,
the reactions of arylpyridines with a-keto esters indi-
cated wide functional group tolerance, broad range of
substrates, high selectivity and good yields of the de-
sired products. 2-Phenylpyridines with an electron-do-
nating group, such as MeO or Me on the phenyl rings
reacted with ethyl benzoylformate (2a) smoothly and
generated the direct alkoxycarbonylation products
3b–f in 55–69% yields. Meanwhile, 2-phenylpyridines
with an electron-withdrawing group, including Cl and
F on the phenyl rings also exhibited high reactivity
and generated 3h and 3i in 72% and 75% yields, re-
spectively. Moreover, a phenyl substituent on 2-phe-
nylpyridine was also well tolerated and the expected
product 3g was obtained in 64% yield. On the other
hand, 2-phenylpyridines with Me on the pyridine
rings also reacted with 2a and gave the corresponding
product 3j–l in 54–78% yields. An obvious ortho-posi-
tion effect was observed in the reactions (3b and 3j).
It was gratifying to find that the special substrates, 6-
methyl-4-phenyl-2-(p-tolyl)quinoline and 2-(naphtha-
len-2-yl)pyridine also participated in the reactions
and afforded the direct alkoxycarbonylation products
3m and 3n in 74% and 67% yields under the opti-
mized reaction conditions. Notably, a series of a-keto
esters, such as methyl benzoylformate, ethyl benzoyl-
[a]
[b]
Reaction conditions: arylpyridine or quinoline (1,
0.50 mmol), a-keto ester (2, 0.75 mmol), Pd(OAc)2
(0.025 mmol), anhydrous TBHP (0.75 mmol), anhydrous
THF (2.0 mL), sealed tube, 1108C, 12 h.
Isolated yields.
ACHTUNGTRENNUNG
formate, propyl benzoylformate and isopropyl ben- products 3o–u were obtained in 50–92% yields, and
zoylformate also reacted with 2-phenylpyridine and ethyl benzoylformate showed the highest reactivity. It
benzo[h]quinoline smoothly and the corresponding should be noted that the reactivity of benzo[h]quino-
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Table 3. The scope of 2-arylpyrimidines and benzoylform-
nylpyrimidines with Me or Cl on the phenyl rings re-
acted with ethyl benzoylformate and afforded the al-
koxycarbonylation products 4e and 4f in 66% and
70% yields, respectively. For the aims of broad sub-
strates scope, we turned our attention to the alkoxy-
carbonylation of heteroarenes, such as pyrrole and
ACHTUNGTRENNUNG
ates.[a]
À
indole through the direct C H bond functionalization.
As shown in Table 3, N-pyrimidinylpyrrole and N-pyr-
imidinylindole also worked efficiently and gave the
corresponding alkoxycarbonylation products 4g, 4h, 4i
and 4j in 41%, 53%, 55% and 69% yields, respective-
ly. This direct alkoxycarbonylation of heteroarenes
methodology was valuable for the further transforma-
tion of the obtained pyrrole and indole derivatives.
À
However, finding a suitable direct C H bond alkoxy-
carbonylation system for those substrates which con-
tain directing groups including ketones, acetamides,
oximes, imines and azobenzenes is a great challenge
up till now.
During the separation of products in the model re-
action, tert-butyl benzoate and benzoic acid were also
isolated as by-products. What is more, when a radical
scavenger, 2,2,6,6-tetramethylpiperidyl 1-oxyl or as-
corbic acid was added to the model reaction,[16] the
À
direct C H bond alkoxycarbonylation was almost
completely shut down, suggesting that this reaction
may involve a radical process. Although the exact
mechanism is still not clear at present, a possible reac-
tion mechanism was shown in Scheme 3. Firstly, a cy-
clopalladated dimer intermediate I by a chelate-di-
À
rected C
ACHTUNGTRENUN(NG benzene) H activation of 2-phenylpyridine
with PdACTHGUNTRNE(NUG OAc)2 was formed. The obtained I then re-
acted with ethoxycarbonyl radical, which was generat-
ed in situ by the reaction of ethyl benzoylformate
with TBHP,[12,17] providing a reactive Pd(IV) inter-
mediate II.[14,18] Finally, carbon-carbon bond forma-
tion through a reductive elimination of II generated
the corresponding product and regeneration of Pd(II)
species for the next run. It is important to note that
there is no carbon-acylation product, (2’-benzoyl)-2-
[a]
[b]
Reaction conditions: 2-arylpyrimidine (3, 0.50 mmol), a-
keto ester (2, 0.75 mmol), Pd(OAc)2 (0.025 mmol), anhy-
drous TBHP (0.75 mmol), anhydrous THF (2.0 mL),
sealed tube, 1108C, 12 h.
Isolated yields.
AHCTUNGTRENNUNG
line is higher than that of 2-phenylpyridine when they phenylpyridine was formed in the reaction of 2-phe-
reacted with a-keto esters (3a vs. 3r, 3o vs. 3s, 3p vs. nylpyridine and ethyl benzoylformate. This is proba-
3t, 3q vs. 3u). The higher reactivity of benzo[h]quino- bly the superior reactivity of ethoxycarbonyl radical
line may result from its planar structure.[14,15]
to benzoyl radical in the reaction.[12,17]
Furthermore, pyrimidine, which is similar to pyri-
dine in molecular structure, was also explored as the
À
directing group for the direct C H bond alkoxycarbo- Conclusions
nylation. As can be seen from Table 3, pyrimidine is
an efficient directing group and the alkoxycarbonyla- In conclusion, a novel and efficient Pd-catalyzed
À
tion generated the corresponding products (Table 3, direct alkoxycarbonylation of aromatic C H bonds
4a–j) in moderate to good yields under the standard via selective C C cleavage of a-keto esters to aromat-
conditions.
À
ic esters has been developed. In the presence of
A series of a-keto esters, such as methyl benzoyl- TBHP and Pd
N
formate, ethyl benzoylformate, isopropyl benzoylfor- 2-arylquinolines, benzo[h]quinolines, 2-phenylpyrimi-
mate and propyl benzoylformate reacted with 2-phe- dines, N-pyrimidinylpyrroles and N-pyrimidinylin-
nylpyrimidine smoothly and the desired products 4a– doles with diverse benzoylformates proceeded
d were obtained in 57–78% yields. Moreover, 2-phe- smoothly to generate the desired alkoxycarbonylation
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Palladium-Catalyzed Direct Alkoxycarbonylation of Aromatic C H Bonds
Scheme 3. Proposed reaction mechanism.
by a Teflon-coated screw cap, and the reaction vessel placed
products in good yields. The method has the advan-
tages of wide functional group tolerance, high selec-
tivity, broad range of substrates and excellent selectiv-
ity. The detailed mechanistic study and its further ap-
plication are currently underway.
in an oil bath at 1108C for 12 h. After the reaction was com-
pleted, it was cooled to room temperature and quenched
with water and extracted with ethyl acetate. The resulting
solution was directly filtered through a pad of silica gel
using a sintered glass funnel, and concentrated under re-
duced pressure. The residue was purified by flash chroma-
tography on silica gel (eluant: petroleum ether/ethyl ace-
tate) to give the desired product ethyl 2-(pyridin-2-yl)ben-
zoate (3a).
Experimental Section
General Considerations
Characterization Data for all Products
Ethyl 2-(pyridin-2-yl)benzoate (3a):[8] 1H NMR (400 MHz,
CDCl3): d=8.64 (d, J=4.8 Hz, 1H), 7.84 (d, J=7.6 Hz, 1H),
All the reactions of 2-arylpyridines and a-keto esters were
carried out under an air atmosphere. THF was dried over
1
sodium and freshly distilled. H NMR and 13C NMR spectra
were measured on a Bruker Avance NMR spectrometer
(400 MHz or 100 MHz, respectively) with CDCl3 as solvent
and recorded in ppm relative to internal tetramethylsilane
standard. The peak patterns are indicated as follows: s, sin-
glet; d, doublet; t, triplet; m, multiplet; q, quartet. The cou-
pling constants, J, are reported in Hertz (Hz). High resolu-
tion mass spectroscopy data were collected on an Agilent
Technologies 6540 UHD Accurate-Mass Q-TOF LC/MS in-
strument using ESI. 2-Arylpyridines were prepared by
Suzuki coupling[19] from boronic acids with 2-bromopyridine.
6-Methyl-4-phenyl-2-(p-tolyl)quinoline[20] was prepared by
tandem reaction of the corresponding aldehyde, alkyne, and
amine. General chemicals and solvents were purchased from
commercial suppliers and used without further purification.
7.76–7.72 (m, 1H), 7.57–7.54 (m, 2H), 7.48–7.44 (m, 2H),
7.27–7.24 (m, 1H), 4.14 (q, J=7.2 Hz, 2H), 1.05 (t, J=
7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=168.65,
158.80, 148.88, 140.91, 136.07, 131.73, 130.96, 129.68, 128.18,
122.77, 121.90, 60.82, 13.71.
Ethyl 3-methoxy-2-(pyridin-2-yl)benzoate (3b): 1H NMR
(400 MHz, CDCl3): d=8.64 (d, J=4.8 Hz, 1H), 7.74–7.69
Typical Procedure for the Alkoxycarbonylation of 2-
Arylpyridine
Under an air atmosphere, a sealable reaction tube with
a Teflon-coated screw cap equipped with a magnetic stir bar
was charged with 2-phenylpyridine (1a, 0.50 mmol), ethyl
benzoylformate (2a, 0.75 mmol), PdACTHNUTRGENUN(G OAc)2 (0.025 mmol),
anhydrous t-BuOOH (TBHP, 0.75 mmol), and freshly dis-
(m, 1H), 7.51 (d, J=7.6 Hz, 1H), 7.45–7.40 (m, 2H), 7.25–
7.22 (m, 1H), 7.13 (d, J=8.4 Hz, 1H), 4.03 (q, J=7.2 Hz,
2H), 3.76 (s, 3H), 0.98 (t, J=7.2 Hz, 3H); 13C NMR
(100 MHz, CDCl3): d=167.76, 156.99, 156.02, 148.76, 135.25,
tilled THF (2.0 mL). The rubber septum was then replaced
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133.20, 130.28, 129.17, 125.12, 121.97, 121.65, 114.26, 60.66,
56.03, 13.66; HR-MS (ESI): m/z=258.1133 ([MH]+), calcd.
for C15H16NO3: 258.1130.
Ethyl 4-(pyridin-2-yl)-[1,1’-biphenyl]-3-carboxylate (3g):
1H NMR (400 MHz, CDCl3): d=8.69 (d, J=4.4, 1H), 8.09
Ethyl
4-methoxy-2-(pyridin-2-yl)benzoate
(3c):[8]
1H NMR (400 MHz, CDCl3): d=8.65 (d, J=4.4 Hz, 1H),
(s, 1H), 7.81–7.75 (m, 2H), 7.69–7.64 (m, 3H), 7.54–7.47 (m,
3H), 7.42–7.38 (m, 1H), 7.30–7.27 (m, 1H), 4.19 (q, J=
6.8 Hz, 2H), 1.09 (t, J=7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): d=168.74, 158.40, 148.94, 141.26, 139.63, 139.52,
136.15, 132.31, 130.21, 129.41, 128.86, 128.37, 127.83, 127.10,
122.77, 121.96, 60.97, 13.76; HR-MS (ESI): m/z=304.1343
([MH]+), calcd. for C20H18NO2: 304.1338.
7.90 (d, J=8.4 Hz, 1H), 7.74–7.70 (m, 1H), 7.39 (d, J=
8.0 Hz, 1H), 7.29–7.25 (m, 1H), 7.00–6.95 (m, 2H), 4.09 (q,
J=7.2 Hz, 2H), 3.87 (s, 3H), 1.03 (t, J=7.2 Hz, 3H);
13C NMR (100 MHz, CDCl3): d=167.58, 161.76, 159.33,
148.79, 143.78, 135.83, 132.23, 123.24, 123.16, 121.96, 115.41,
113.61, 60.48, 55.48, 13.76.
Ethyl 5-chloro-2-(pyridin-2-yl)benzoate (3h):[11] 1H NMR
(400 MHz, CDCl3): d=8.64 (d, J=4.4 Hz, 1H), 7.81 (d, J=
Ethyl
5-methoxy-2-(pyridin-2-yl)benzoate
(3d):[10]
1H NMR (400 MHz, CDCl3): d=8.61 (d, J=4.8 Hz, 1H),
1.6 Hz, 1H), 7.77–7.73 (m, 1H), 7.54–7.48 (m, 2H), 7.44 (d,
J=7.6 Hz, 1H), 7.29–7.26 (m, 1H), 4.15 (q, J=7.2 Hz, 2H),
1.08 (t, J=6.8 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=
167.39, 157.60, 149.03, 139.25, 136.25, 134.38, 133.27, 131.04,
130.93, 129.71, 122.73, 122.22, 61.25, 13.72.
7.73–7.69 (m, 1H), 7.49 (d, J=8.4 Hz, 1H), 7.43 (d, J=
8.0 Hz, 1H), 7.34 (d, J=2.8 Hz, 1H), 7.23–7.20 (m, 1H),
7.09–7.06 (m, 1H), 4.14 (q, J=7.2 Hz, 2H), 3.88 (s, 3H),
1.05 (t, J=6.8 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=
168.70, 159.49, 158.48, 148.85, 136.02, 133.36, 133.08, 130.98,
122.60, 121.51, 116.87, 114.61, 60.97, 55.54, 13.72.
Ethyl 5-fluoro-2-(pyridin-2-yl)benzoate (3i):
(400 MHz, CDCl3): d=8.64 (d, J=4.4 Hz, 1H), 7.76–7.72
1H NMR
Ethyl 4-methyl-2-(pyridin-2-yl)benzoate (3e):[8] 1H NMR
(400 MHz, CDCl3): d=8.64 (d, J=4.4 Hz, 1H), 7.78 (d, J=
(m, 1H), 7.56–7.51 (m, 2H), 7.43 (d, J=8.0 Hz, 1H), 7.28–
7.22 (m, 2H), 4.15 (q, J=7.2 Hz, 2H), 1.07 (t, J=7.2 Hz,
3H); 13C NMR (100 MHz, CDCl3): d=167.27 (d, J=
2.5 Hz), 162.23 (d, J=247.7 Hz), 157.80, 148.87, 137.41 (d,
J=3.5 Hz), 136.22, 133.59 (d, J=17.4 Hz), 131.64 (d, J=
7.9 Hz), 122.82, 122.05, 117.89 (d, J=21.7 Hz), 116.76 (d, J=
23.5 Hz), 61.19, 13.66; HR-MS (ESI): m/z=246.0933
([MH]+), calcd. for C14H13FNO2: 246.0930.
8.0 Hz, 1H), 7.74–7.69 (m, 1H), 7.41 (d, J=8.0 Hz, 1H),
7.34 (s, 1H), 7.27–7.23 (m, 2H), 4.11 (q, J=7.2 Hz, 2H),
2.43 (s, 3H), 1.04 (t, J=7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): d=168.36, 159.25, 148.87, 141.58, 141.31, 135.83,
130.61, 130.01, 128.80, 128.54, 122.98, 121.78, 60.63, 21.34,
13.73.
Ethyl 2-(3-methylpyridin-2-yl)benzoate (3j):[11] 1H NMR
(400 MHz, CDCl3): d=8.47 (d, J=4.8 Hz, 1H), 8.06 (d, J=
Ethyl 5-methyl-2-(pyridin-2-yl)benzoate (3f:)[8] 1H NMR
(400 MHz, CDCl3): d=8.64 (d, J=4.8 Hz, 1H), 7.73–7.69
8.0 Hz, 1H), 7.61–7.54 (m, 2H), 7.50–7.46 (m, 1H), 7.32 (d,
J=7.6 Hz, 1H), 7.22–7.19 (m, 1H), 4.07 (q, J=7.2 Hz, 2H),
2.12 (s, 3H), 1.01 (t, J=7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): d=168.89, 159.59, 146.08, 141.80, 137.15, 131.89,
131.13, 130.42, 129.99, 129.87, 127.91, 122.12, 60.66, 19.13,
13.69.
(m, 1H), 7.65 (s, 1H), 7.44–7.41 (m, 2H), 7.35–7.33 (m, 1H),
7.24–7.21 (m, 1H), 4.12 (q, J=7.2 Hz, 2H), 2.42 (s, 3H),
1.04 (t, J=7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=
168.75, 158.67, 148.66, 138.20, 137.93, 136.04, 131.57, 131.50,
130.16, 129.60, 122.73, 121.68, 60.71, 20.88, 13.66.
Ethyl 2-(4-methylpyridin-2-yl)benzoate (3k):[21] 1H NMR
(400 MHz, CDCl3): d=8.48 (d, J=4.8 Hz, 1H), 7.82 (d, J=
6
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Palladium-Catalyzed Direct Alkoxycarbonylation of Aromatic C H Bonds
(100 MHz, CDCl3): d=169.16, 158.51, 148.98, 140.86, 136.14,
131.45, 131.05, 129.69, 129.64, 128.22, 122.64, 121.98, 51.90.
Propyl 2-(pyridin-2-yl)benzoate (3p):
1H NMR
7.6 Hz, 1H), 7.54–7.53 (m, 2H), 7.46–7.42 (m, 1H), 7.29 (s,
1H), 7.08 (d, J=4.8 Hz, 1H), 4.14 (q, J=7.2 Hz, 2H), 2.40
(s, 3H), 1.07 (t, J=7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): d=168.76, 158.60, 148.68, 147.11, 141.00, 131.85,
130.85, 129.60, 129.56, 128.04, 123.59, 122.90, 60.78, 20.99,
13.73.
(400 MHz, CDCl3): d=8.63 (d, J=4.4 Hz, 1H), 7.83 (d, J=
Ethyl 2-(5-methylpyridin-2-yl)benzoate (3l):
1H NMR
(400 MHz, CDCl3): d=8.47 (s, 1H), 7.81 (d, J=8.0 Hz, 1H),
7.6 Hz, 1H), 7.74–7.69 (m, 1H), 7.53 (d, J=4.0 Hz, 2H),
7.46–7.43 (m, 2H), 7.24–7.21 (m, 1H), 4.03 (t, J=6.4 Hz,
2H), 1.48–1.39 (m, 2H), 0.73 (t, J=7.6 Hz, 3H); 13C NMR
(100 MHz, CDCl3): d=168.74, 158.72, 148.88, 140.81, 136.03,
131.75, 130.86, 129.67, 129.62, 128.11, 122.66, 121.86, 66.50,
21.51, 10.13; HR-MS (ESI): m/z=242.1185 ([MH]+), calcd.
for C15H16NO2: 242.1181.
7.56–7.53 (m, 3H), 7.46–7.42 (m, 1H), 7.36 (d, J=8.0 Hz,
1H), 4.16 (q, J=7.2 Hz, 2H), 2.38 (s, 3H), 1.10 (t, J=
6.8 Hz, 3H); 13C NMR (100 MHz, CDCl3): d 168.77, 155.94,
149.33, 140.90, 136.65, 131.73, 131.43, 130.90, 129.68, 129.59,
127.94, 122.22, 60.83, 18.14, 13.80; HR-MS (ESI): m/z=
242.1185 ([MH]+), calcd. for C15H15NO2: 242.1181.
Isopropyl 2-(pyridin-2-yl)benzoate (3q):[9]
1H NMR
(400 MHz, CDCl3): d=8.63 (d, J=4.4 Hz, 1H), 7.83 (d, J=
Ethyl
5-methyl-2-(6-methyl-4-phenylquinolin-2-yl)ben-
zoate (3m): 1H NMR (400 MHz, CDCl3): d=8.08 (d, J=
7.6 Hz, 1H), 7.75–7.71 (m, 1H), 7.56–7.51 (m, 2H), 7.47–
7.43 (m, 2H), 7.27–7.23 (m, 1H), 5.08–4.99 (m, 1H), 1.08 (d,
J=6.0 Hz, 6H); 13C NMR (100 MHz, CDCl3): d=168.14,
158.95, 148.92, 140.83, 136.02, 132.20, 130.78, 129.68, 129.61,
128.12, 122.83, 121.84, 68.37, 21.40.
8.4 Hz, 1H), 7.69 (d, J=5.6 Hz, 2H), 7.62 (d, J=7.6 Hz,
1H), 7.57–7.50 (m, 7H), 7.40 (d, J=8.0 Hz, 1H), 4.13 (q, J=
6.8 Hz, 2H), 2.49 (s, 3H), 2.46 (s, 3H), 0.94 (t, J=7.2 Hz,
3H); 13C NMR (100 MHz, CDCl3): d=169.06, 157.29,
147.56, 146.81, 138.43, 138.34, 138.33, 136.22, 131.87, 131.70,
131.58, 130.29, 129.83, 129.56, 129.47, 128.49, 128.20, 125.27,
124.27, 121.41, 60.85, 21.76, 21.03, 13.77; HR-MS (ESI):
m/z=382.1812 ([MH]+), calcd. for C26H24NO2: 382.1807.
Ethyl benzo[h]quinoline-10-carboxylate (3r):[8] 1H NMR
(400 MHz, CDCl3): d=8.90 (d, J=4.0 Hz, 1H), 8.14 (d, J=
Ethyl 3-(pyridin-2-yl)-2-naphthoate (3n):[10]
1H NMR
8.0 Hz, 1H), 7.97–7.94 (m, 1H), 7.80 (d, J=8.8 Hz, 1H),
7.71–7.70 (m, 3H), 7.51–7.48 (m, 1H), 4.63 (q, J=7.2 Hz,
2H), 1.45 (t, J=7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3):
d=172.22, 147.58, 144.99, 135.42, 133.89, 132.47, 129.88,
129.20, 127.60, 127.31, 126.84, 126.05, 125.98, 121.85, 61.36,
14.18.
(400 MHz, CDCl3): d=8.67 (d, J=4.4 Hz, 1H), 8.39 (s, 1H),
Methyl benzo[h]quinoline-10-carboxylate (3s): 1H NMR
(400 MHz, CDCl3): d=8.92 (d, J=4.0 Hz, 1H), 8.17–8.15
8.00 (s, 1H), 7.95 (d, J=7.6 Hz, 1H), 7.89 (d, J=7.6 Hz,
1H), 7.79–7.75 (m, 1H), 7.60–7.54 (m, 3H), 7.28–7.25 (m,
1H), 4.20 (q, J=7.2 Hz, 2H), 1.10 (t, J=7.2 Hz, 3H);
13C NMR (100 MHz, CDCl3): d=168.66, 158.90, 148.85,
137.43, 136.15, 133.98, 132.08, 130.74, 129.56, 129.31, 128.49,
128.03, 127.97, 127.05, 122.78, 121.73, 60.93, 13.77.
Methyl 2-(pyridin-2-yl)benzoate (3o):[11]
1H NMR
(400 MHz, CDCl3): d=8.65 (d, J=4.8 Hz, 1H), 7.82 (d, J=
7.6 Hz, 1H), 7.77–7.73 (m, 1H), 7.57–7.54 (m, 2H), 7.48–
7.44 (m, 2H), 7.27–7.24 (m, 1H), 3.68 (s, 3H); 13C NMR
(m, 1H), 7.98–7.96 (m, 1H), 7.82 (d, J=8.8 Hz, 1H), 7.73–
7.70 (m, 3H), 7.52–7.49 (m, 1H), 4.09 (s, 3H); 13C NMR
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(100 MHz, CDCl3): d=172.74, 147.92, 144.95, 135.52, 133.91,
132.09, 129.37, 127.74, 127.64, 127.34, 126.91, 126.06, 126.02,
121.92, 52.40; HR-MS (ESI): m/z=238.0872 ([MH]+), calcd.
for C15H12NO2: 238.0868.
d=169.09, 165.85, 156.72, 138.14, 132.90, 130.66, 129.83,
129.46, 129.01, 118.96, 60.97, 13.86.
Isopropyl 2-(pyrimidin-2-yl)benzoate (4c):
1H NMR
(400 MHz, CDCl3): d=8.77 (d, J=4.8 Hz, 2H), 7.95 (d, J=
Propyl benzo[h]quinoline-10-carboxylate (3t): 1H NMR
(400 MHz, CDCl3): d=8.83 (dd, J=4.0, 1.2 Hz, 1H), 8.10–
7.6 Hz, 1H), 7.72 (d, J=7.6 Hz, 1H), 7.57–7.53 (m, 1H),
7.51–7.47 (m, 1H), 7.22–7.20 (m, 1H), 5.16–5.07 (m, 1H),
1.16 (d, J=6.0 Hz, 6H); 13C NMR (100 MHz, CDCl3): d=
168.50, 165.89, 156.71, 138.00, 133.27, 130.47, 129.77, 129.36,
128.94, 118.92, 68.47, 21.48; HR-MS (ESI): m/z=243.1132
([MH]+), calcd. for C14H15N2O2: 243.1134.
8.08 (m, 1H), 7.90–7.88 (m, 1H), 7.74 (d, J=8.8 Hz, 1H),
7.65–7.62 (m, 3H), 7.45–7.42 (m, 1H), 4.44 (t, J=6.8 Hz,
2H), 1.82–1.73 (m, 2H), 0.92 (t, J=7.6 Hz, 3H); 13C NMR
(100 MHz, CDCl3): d=172.23, 147.53, 144.86, 135.31, 133.77,
132.44, 129.06, 127.50, 127.48, 127.18, 126.71, 125.89, 121.74,
66.95, 21.71, 10.43; HR-MS (ESI): m/z=266.1184 ([MH]+),
calcd. for C17H16NO2: 266.1181.
Propyl 2-(pyrimidin-2-yl)benzoate (4d):
(400 MHz, CDCl3): d=8.79 (d, J=4.8 Hz, 2H), 7.98 (d, J=
1H NMR
Isopropyl
benzo[h]quinoline-10-carboxylate
(3u):[8]
1H NMR (400 MHz, CDCl3): d=8.89 (dd, J=4.4, 1.6 Hz,
7.6 Hz, 1H), 7.75 (d, J=7.6 Hz, 1H), 7.60–7.56 (m, 1H),
7.53–7.50 (m, 1H), 7.24–7.21 (m, 1H), 4.12 (t, J=6.4 Hz,
2H), 1.58–1.49 (m, 2H), 0.80 (t, J=7.2 Hz, 3H); 13C NMR
(100 MHz, CDCl3): d=169.25, 165.89, 156.76, 138.16, 132.98,
130.66, 129.88, 129.48, 129.03, 118.97, 66.71, 21.64, 10.29;
HR-MS (ESI): m/z=243.1131 ([MH]+), calcd. for
C14H15N2O2: 243.1134.
1H), 8.14 (d, J=8.0 Hz, 1H), 7.95–7.93 (m, 1H), 7.79 (d, J=
8.8 Hz, 1H), 7.72–7.68 (m, 3H), 7.51–7.48 (m, 1H), 5.63–
5.53 (m, 1H), 1.49 (d, J=6.4 Hz, 6H); 13C NMR (100 MHz,
CDCl3): d=171.62, 147.35, 145.08, 135.38, 133.93, 132.93,
129.06, 127.63, 127.47, 127.32, 126.83, 126.12, 125.93, 121.83,
68.78, 21.86.
Ethyl 5-chloro-2-(pyrimidin-2-yl)benzoate (4e): 1H NMR
(400 MHz, CDCl3): d=8.77 (d, J=4.8 Hz, 2H), 7.98 (d, J=
Methyl 2-(pyrimidin-2-yl)benzoate (4a):
1H NMR
(400 MHz, CDCl3): d=8.78 (d, J=4.8 Hz, 2H), 8.01 (d, J=
8.4 Hz, 1H), 7.67 (d, J=0.80 Hz, 1H), 7.53 (d, J=8.4 Hz,
1H), 7.23–7.21 (m, 1H), 4.23 (q, J=6.8 Hz, 2H), 1.16 (t, J=
7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=167.97,
164.55, 156.76, 136.11, 135.75, 134.64, 131.27, 130.51, 128.90,
119.15, 61.35, 13.81; HR-MS (ESI): m/z=263.0589 ([MH]+),
calcd. for C13H12ClN2O2: 263.0587.
8.0 Hz, 1H), 7.71 (d, J=7.6 Hz, 1H), 7.59–7.55 (m, 1H),
7.52–7.48 (m, 1H), 7.22–7.19 (m, 1H), 3.73 (s, 3H);
13C NMR (100 MHz, CDCl3): d=169.66, 165.49, 156.73,
137.94, 132.65, 130.68, 129.84, 129.50, 128.86, 118.99, 52.00;
HR-MS (ESI): m/z=215.0824 ([MH]+), calcd. for
C12H11N2O2: 215.0821.
Ethyl 5-methyl-2-(pyrimidin-2-yl)benzoate (4f): 1H NMR
(400 MHz, CDCl3): d=8.76 (d, J=4.8 Hz, 2H), 7.92 (d, J=
Ethyl 2-(pyrimidin-2-yl)benzoate (4b):[11]
1H NMR
(400 MHz, CDCl3): d=8.79 (d, J=4.8 Hz, 2H), 7.98 (d, J=
7.6 Hz, 1H), 7.52 (s, 1H), 7.37 (d, J=8.0 Hz, 1H), 7.20–7.17
(m, 1H), 4.22 (q, J=7.2 Hz, 2H), 2.43 (s, 3H), 1.15 (t, J=
7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=169.51,
165.64, 156.65, 139.86, 135.11, 133.05, 131.20, 129.82, 129.45,
118.72, 60.93, 21.09, 13.87; HR-MS (ESI): m/z=243.1131
([MH]+), calcd. for C14H15N2O2: 243.1134.
7.6 Hz, 1H), 7.75 (d, J=7.2 Hz, 1H), 7.60–7.56 (m, 1H),
7.53–7.49 (m, 1H), 7.24–7.21 (m, 1H), 4.21 (q, J=7.2 Hz,
2H), 1.14 (t, J=7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3):
Methyl 1-(pyrimidin-2-yl)-1H-indole-2-carboxylate (4g):
1H NMR (400 MHz, CDCl3): d=8.79 (d, J=4.8 Hz, 2H),
8
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Palladium-Catalyzed Direct Alkoxycarbonylation of Aromatic C H Bonds
Benzoic acid: 1H NMR (400 MHz, CDCl3): d=11.65 (s,
1H), 8.16 (d, J=7.6 Hz, 2H), 7.66–7.62 (m, 1H), 7.52–7.48
(m, 2H); 13C NMR (100 MHz, CDCl3): d=172.44, 133.79,
130.21, 129.37, 128.47.
8.18 (d, J=8.4 Hz, 1H), 7.71 (d, J=7.6 Hz, 1H), 7.43–7.39
(m, 1H), 7.36 (s, 1H), 7.29–7.26 (m, 1H), 7.21–7.19 (m, 1H),
3.86 (s, 3H); 13C NMR (100 MHz, CDCl3): d=162.50,
158.05, 157.48, 138.55, 129.98, 127.57, 126.26, 122.56, 122.34,
117.93, 114.12, 113.48, 51.97; HR-MS (ESI): m/z=254.0928
([MH]+), calcd. for C14H12N3O2: 254.0930.
Ethyl 1-(pyrimidin-2-yl)-1H-indole-2-carboxylate (4h):
1H NMR (400 MHz, CDCl3): d=8.78 (d, J=4.8 Hz, 2H),
Acknowledgements
This work was financially supported by the National Science
Foundation of China (No. 21172092).
References
8.16 (d, J=8.4 Hz, 1H), 7.70 (d, J=8.0 Hz, 1H), 7.42–7.36
(m, 2H), 7.29–7.25 (m, 1H), 7.21–7.18 (m, 1H), 4.32 (q, J=
6.8 Hz, 2H), 1.28 (t, J=7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): d=162.04, 158.03, 157.54, 138.49, 130.40, 127.57,
126.15, 122.50, 122.28, 117.89, 113.93, 113.39, 60.93, 14.03;
HR-MS (ESI): m/z=268.1088 ([MH]+), calcd. for
C15H14N3O2: 268.1086.
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(br, 1H), 4.26 (q, J=7.2 Hz, 2H), 1.27 (t, J=7.2 Hz, 3H);
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Palladium-Catalyzed Direct Alkoxycarbonylation of
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Aromatic C H Bonds via Selective C C Cleavage of a-
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Wei Zhou, Pinhua Li, Yicheng Zhang, Lei Wang*
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