Palladium-catalyzed regioselective aerobic oxidative C-H/N-H carbonylation of heteroarenes under base-free conditions

Article abstract of DOI:10.1002/chem.201101300

Clearing the air! By using a balloon pressure of CO, the direct oxidative carbonylation of various heteroarenes with different alcohols was achieved in good to high yields with air as the oxidant in the presence of PdCl ₂(PPh₃)₂ (see scheme). Notably, this transformation was carried out under base-free conditions. The reaction showed remarkably high regioselectivity and presents an environmentally benign protocol for the synthesis of carboxylic acid derivatives.

Full text of DOI:10.1002/chem.201101300

COMMUNICATION
DOI: 10.1002/chem.201101300
À
À
Palladium-Catalyzed Regioselective Aerobic Oxidative C H/N H
Carbonylation of Heteroarenes under Base-Free Conditions
Hua Zhang,[a] Dong Liu,[a] Caiyou Chen,[a] Chao Liu,[a] and Aiwen Lei*[a, b]
Transition-metal-catalyzed alkoxycarbonylation reactions
usually involve aryl halide ArX as the electrophile and CO/
ROH as the nucleophile (Scheme 1, Path 1). As an alterna-
Recently, the oxidative carbonylation of an aryl metal re-
agent ArM (M=In, B) has emerged as a new alternative to-
wards “classic carbonylation”.[3] However, the preparation
of ArM also involves the prefunctionalization of ArH and a
stoichiometric amount of metal wastes is produced. Evident-
ly, the direct utilization of ArH in carbonylation reaction
would be attractive for preparation of carbonyl compounds,
as it shortens synthetic routes and presents an environmen-
tally friendly protocol.
À
During the past decade, Pd-catalyzed aromatic C H func-
À
À
tionalization to form C C and C X bonds has been inten-
sively investigated.[4] However, C H activation/carbonyla-
À
tion catalyzed by PdII remains an outstanding challenge
since the depalladation process is often complicated by the
reduction of PdII to Pd0 under a CO atmosphere.[5] Benzene
was firstly carbonylated to benzoic acid by using Pd cataly-
sis, in which the substrate was used as the solvent and
K2S2O8 as the oxidant.[6] Recently, after the Pd-catalyzed
carboxylation of benzoic and phenylacetic acid,[7] the direct
Scheme 1. Transition-metal-catalyzed alkoxycarbonylation with CO.
tive avenue, the oxidative carbonylation between an aryl
metal ArM and CO/ROH by employing stoichiometric
amount of oxidants has recently attracted increasing atten-
tion (Scheme 1, Path 3). Apparently, if simple arenes ArH
were directly employed as the nucleophile and air or O2 as
the terminal oxidant in oxidative carbonylation, this chal-
lenging transformation will present an attractive and sustain-
able approach towards the synthesis of carbonyl compounds
(Scheme 1, Path 2).
Carboxylic acids and derivatives (e.g., esters) are valuable
commodity chemicals and useful synthetic building blocks
for agrochemicals, active pharmaceutical ingredients and
process chemicals. Since the pioneering work of Heck and
co-workers in 1974,[1] transition-metal-catalyzed carbonyla-
tion reactions of aromatic halides ArX in the presence of
CO and ROH affording ArCO2R have undergone rapid de-
velopment and been widely applied in industry in the last
several decades,[2] whereas ArX is usually prepared from the
corresponding ArH and a stoichiometric amount of bases is
required to facilitate the reaction.
À
ortho-selective carbonylation of aromatic C H bonds in the
presence of inorganic salts or benzoquinone as the oxidants
attracted widespread attention.[8] However, extending the
scope of ArH and employing an environmentally benign ter-
minal oxidant, such as air or O2, are still emerging challeng-
es in this area.[9]
Heterocyclic carboxylic acids and derivatives are impor-
tant structural motifs that are widely found in pharmaceuti-
cally important molecules and synthetically useful fine
chemicals.[10] To the best of our knowledge, direct C H car-
À
bonylation of heteroarenes to construct an ester functional
group has remained almost unexplored.[11] Herein, we report
a novel and efficient protocol for the Pd-catalyzed aerobic
C H carbonylation of heteroarenes to form esters under
base-free conditions. In addition, the reaction conditions are
À
À
also amendable to N H carbonylation to afford indole car-
bamates.
Our experiment was initiated by treating N-methyl indole
(1a) with n-butanol (2a) in the presence of a balloon pres-
sure of CO (Table 1). By optimizing the various reaction pa-
rameters, the best results were obtained with a catalytic
amount of PdCl2ACHTNUTRGENN(UG PPh3)2, PPh3, and CuACHTUGNTERN(NUGN OAc)2 in a mixed
solvent of toluene and DMSO using air as the terminal oxi-
dant (Table 1, entry 1).
With these conditions, a 71% yield of butyl 1-methyl-1H-
indole-3-carboxylate (3a) was obtained within 36 h at 1008C
using 2.5 mol% of PdCl2ACHTUNRGTNEUNG(PPh3)2. The functionalization selec-
[a] H. Zhang, D. Liu, C. Chen, C. Liu, Prof. A. Lei
The College of Chemistry and Molecular Sciences
Wuhan University, Wuhan, Hubei (P.R. China)
Fax : (+86)27-68754067
E-mail: aiwenlei@whu.edu.cn
[b] Prof. A. Lei
State Key Laboratory for Oxo Synthesis and Selective Oxidation
Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences
730000, Lanzhou (P.R. China)
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201101300.
Chem. Eur. J. 2011, 17, 9581 – 9585
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9581

[a]
[a]
À
À
Table 1. Optimization of the direct C H carbonylation of 1a.
Table 2. Pd-Catalyzed direct C H carbonylation of indoles.
Entry
Variation from the “standard conditions”
None
Yield [%][b]
71 (65)[c]
Entry
1
3
Product
Yield
[%][b]
1
2
3
4
5
6
7
8
No PdCl
No PPh3
N
0
62
61
42
0
29
<5
3a
65
66
62
66
Pd
PdCl
No Cu
CuCl2, instead of Cu
N
2ACHTUNGTERN(NUNG PPh3)2
CHTUNGTRENNUNG
ACHTUNGTRENNUNG
(OAc)2
2
3
4
3b
3c
3d
N-Ac indole, instead of N-Me indole
Toluene, instead of toluene/DMSO
808C, instead of 1008C
9
10
14
0
[a] Standard reaction conditions: 1a (0.2 mmol), PdCl
(2.5 mol%), PPh3 (5 mol%), Cu(OAc)2 (10 mol%), 1 atm CO/Air (7:1),
2a (0.2 mL), toluene/DMSO (1.5 mL/0.1 mL), 1008C, 36 h. [b] The yield
was determined by HPLC, calibrated using dibenzofuran as the internal
standard. [c] Yield of the isolated product.
2ACHTUNGTERN(NUNG PPh3)2
AHCTUNGTRENNUNG
tively occurred at the C3 position of the indole. In the ab-
sence of PdCl2ACHTUNGTRENNUNG(PPh3)2, essentially no oxidative carbonylation
5
3e
3 f
3g
3h
3i
74
72
50
75
46
67
reactions occurred (Table 1, entry 2). Removing the PPh3
ligand or varying the palladium catalyst both led to de-
creased yields (Table 1, entries 3 and 4). Surprisingly, in-
creasing the catalyst loading showed less efficiency in terms
of chemical yields (Table 1, entry 5). The use of a copper
6
salt is essential for the reaction to proceed and CuACTHNUTRGNEUNG(OAc)2
7
shows higher activity than CuCl2 (Table 1, entries 6 and 7).
Only a trace amount of carbonylation product was observed
when the methyl substituent was replaced with an acetyl
group (Table 1, entry 8). Without DMSO, the reaction yield
decreased dramatically (Table 1, entry 9). Lowering the re-
action temperature to 808C shut down the reaction com-
pletely (Table 1, entry 10).
With the above-optimized conditions, the oxidative car-
bonylation of a range of indoles with n-butanol was tested
and the results are complied in Table 2. As shown in
Table 2, C5, C6, or C7 substituted indoles worked well in
the optimized system, and the corresponding reactions af-
forded good yields of indole-3-carboxylates (Table 2, en-
tries 2–4). It is noteworthy that C3 functionalization of 2-
substituted indoles gave 2,3-disubstituted products in good
yield (Table 2, entry 5). Both electron-donating and elec-
tron-withdrawing substituents on indole ring were well-toler-
ated in this oxidative carbonylation conditions (Table 2, en-
tries 6–8). The carbonylation product was achieved in 46%
yield when electron-deficient 7-azaindole was carbonylated
(Table 2, entry 9). In addition, N-benzyl indole could also be
carbonylated in 67% yield with a longer reaction time
(Table 2, entry 10).
8
9
10[c]
3j
[a] Reaction conditions: 1 (0.2 mmol), PdCl
(5 mol%), Cu(OAc)2 (10 mol%), 1 atm CO/Air (7:1), 2a (0.2 mL), Tolu-
ene/DMSO (1.5 mL/0.1 mL), 1008C, 36 h. [b] Yield of the isolated prod-
uct. [c] 50 h.
2ACHTUNGTRENUN(GN PPh3)2 (2.5 mol%), PPh3
AHCTUNGTRENNUNG
3). Secondary aliphatic alcohols were also examined, and
the reactions provided corresponding oxidative carbonyla-
tion products in moderate to good yields (Table 3, entries 4–
6). The carbonylation of different indoles with benzyl alco-
hol gave the corresponding products in good to high yields
(Table 3, entries 7–9). An ester group could also be tolerat-
ed and 3t was obtained in 80% yield (Table 3, entry 10).
Thiophene and benzo[b]thiophene were also investigated
Furthermore, we investigated the scope of ROH and the
results are listed in Table 3. Aliphatic alcohols, such as n-
pentanol, n-dodecanol and others, were all suitable nucleo-
philes under the optimized conditions and these reactions
gave the desired products in good yields (Table 3, entries 1–
À
in this oxidative carbonylation reaction and C H activation
predominantly occurs at C2 position. 2-Methyl thiophene
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Chem. Eur. J. 2011, 17, 9581 – 9585

À
À
Palladium-Catalyzed Oxidative C H/N H Carbonylation
COMMUNICATION
À
À
Table 3. Pd-Catalyzed direct C H carbonylation of different indoles and
Table 4. Direct C H carbonylation of thiophenes and benzo[b]thiophene
alcohols.[a]
with different alcohols.[a]
Entry
1
3
Product
Yield [%][b]
79
Entry
1
3
Product
Yield
[%][b]
3u
3k
76
72
72
64
68
59
86
78
75
2
3v
81
ACHTUNGTRENNUNG
(65:35)[c]
3w
2
3
4
5
6
7
8
9
3l
3[d]
4[d]
3x
3y
70
79
3m
3n
3o
3p
3q
3r
[a] Reaction conditions: 1 (0.2 mmol), PdCl
2ACHTUNGTRENUN(GN PPh3)2 (2.5 mol%), PPh3
(5 mol%), Cu(OAc)2 (10 mol%), 1 atm CO/air (7:1), 2 (0.2 mL), tolu-
AHCTUNGTRENNUNG
ene/DMSO (1.5 mL/0.1 mL), 908C, 36 h. [b] Yield of the isolated prod-
uct. [c] The ratio was determined by 1H NMR spectroscopy. [d] PdCl2-
A
ACHTUNGRTEN(NUNG OAc)2 (2 equiv), 1 atm CO,
À
switched in favor of reaction at N H site. The reactions
with primary and secondary alcohols both underwent N H
À
carbonylation to afford the corresponding carbamates
(Table 5, entries 1 and 2). Various indoles with both elec-
tron-donating and -withdrawing groups were tested and the
N-carbonylation products were formed in high to excellent
yields (Table 5, entries 3–5). Halo substituents were also
well tolerated in this carbonylation reaction (Table 5, en-
tries 6–8). This transformation provides a novel and efficient
strategy for the preparation of indole carbamates, which
serve as fragrance ingredients and leukotriene antago-
nists.[12]
It is well known that the C3 position of indole and C2 po-
sition of thiophene and benzothiophene are the most elec-
tron-efficient sites on each aromatic ring. The regioselectivi-
ty of this oxidative carbonylation revealed that the reaction
was probably initiated through an electrophilic palladation
process. On the basis of above results and previous stud-
ies,[13] we proposed a mechanism for this Pd-catalyzed oxida-
3s
10
3t
80
[a] Reaction conditions: 1 (0.2 mmol), PdCl
2ACHTUNGTRENUN(GN PPh3)2 (2.5 mol%), PPh3
(5 mol%), Cu(OAc)2 (10 mol%), 1 atm CO/Air (7:1), 2 (0.2 mL), tolu-
ACHTUNGTRENNUNG
ene/DMSO (1.5 mL/0.1 mL), 1008C, 36 h. [b] Yield of the isolated prod-
uct.
À
tive C H carbonylation reaction (Scheme 2). Taking indole
as example, the electrophilic palladation of indole (1a) at
the C3 position with the PdII species I afforded the inter-
mediate II, which further reacted with CO and ROH (2) to
produce the final oxidative carbonylation product and gen-
erate the Pd0 species.[14] The PdII species I could be regener-
ated by O2 (air) in the presence of a CuII species.
was coupled with n-butanol and CO affording the corre-
sponding ester in 79% yield (Table 4, entry 1). When 3-sub-
stitueted thiophene was employed as a substrate, two iso-
mers were formed (Table 4, entry 2). By employing two
equivalents of copper salts, benzo[b]thiophene underwent
smooth reactions with n-butanol and 2-octanol to give the
desired products in 70 and 79% yield, respectively (Table 4,
entries 3 and 4).
In conclusion, we have developed an efficient protocol for
aerobic oxidative C H carbonylation of heteroarenes to
form a variety of heterocyclic esters using a balloon pressure
of CO. High regioselectivity was obtained and an electro-
philic palladation mechanism was proposed. Compared with
the classical carbonylation, the oxidative carbonylation in-
À
À
When N H indoles were employed in this oxidative car-
bonylation, the regioselectivity of the oxidative process was
Chem. Eur. J. 2011, 17, 9581 – 9585
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
9583

A. Lei et al.
[a]
À
Table 5. Oxidative carbonylation of N H indole with different alcohols.
synthesis of carboxylic compounds. In addition, this oxida-
tive carbonylation catalytic system was also applied in the
À
aerobic N H carbonylation of N-free indoles to afford vari-
ous indole carbamates. Further studies, with regards to sub-
strate scope and mechanism, are currently underway and
will be reported in due course.
Entry
5
Product
Yield
[%][b]
Experimental Section
1
2
3
5a
5b
5c
68
97
68
General procedure: In an oven-dried Schlenk tube equipped with a stir-
bar, PdCl
(PPh3)2 (2.5 mol%), PPh3 (5 mol%), and heteroarene
(OAc)2 (10 mol%) was
(0.2 mmol) were combined. In a glove box, CuACHTUNGTRENNNUG
added in the tube. A balloon filled with CO and air (the ratio is 7:1) was
connected to the Schlenk tube by the side tube and purged three times.
Then, alcohol (0.2 mL), DMSO (0.1 mL) and toluene (1.5 mL) were
added to the tube through a syringe. The Schlenk tube was heated at
1008C for 36 h and then cooled to room temperature. After the balloon
gas was released carefully, the reaction was quenched by water and ex-
tracted with CH2Cl2 three times. The combined organic layers were dried
over anhydrous Na2SO4 and evaporated in vacuum. The desired products
were obtained in the corresponding yields after purification by flash
chromatography on silica gel with hexane, ethyl acetate, and triethyl-
4
5d
88
AHCTUNGTRENGNaUN mine.
5
6
7
8
5e
5 f
5g
5h
98
92
95
83
Acknowledgements
This work was supported by the National Natural Science Foundation of
China (21025206, 20832003, and 20972118) and the “973” Project from
the MOST of China (2011CB808600). In addition, the authors also thank
the support from “the Fundamental Research Funds for the Central Uni-
versities”, and Program for New Century Excellent Talents in University
(NCET).
[a] Reaction conditions: 4 (0.2 mmol), PdCl
2ACHTUNGTRENUN(GN PPh3)2 (2.5 mol%), PPh3
À
Keywords: alcohols
oxidative carbonylation · palladium
·
C H activation
·
heteroarenes
·
(5 mol%), Cu(OAc)2 (10 mol%), 1 atm CO/Air (7:1), 2 (0.2 mL), tolu-
ACHTUNGTRENNUNG
ene/DMSO (1.5 mL/0.1 mL), 1008C, 36 h. [b] Yield of the isolated prod-
uct.
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Palladium-Catalyzed Oxidative C H/N H Carbonylation
COMMUNICATION
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Received: April 28, 2011
Revised: June 16, 2011
Published online: July 26, 2011
Chem. Eur. J. 2011, 17, 9581 – 9585
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9585