Phosphane-free copper-catalyzed decarboxylative coupling of alkynyl carboxylic acids with aryl halides under aerobic conditions

Article abstract of DOI:10.1002/ejoc.201100659

A phosphane-free copper-catalyzed decarboxylative cross-coupling reaction of alkynyl carboxylic acids with aryl halides was developed. CuBr (1-5 mol-%) was used as a catalyst in the presence of a β-diketone ligand in air. The reactions of aryl iodides wer

Full text of DOI:10.1002/ejoc.201100659

SHORT COMMUNICATION
DOI: 10.1002/ejoc.201100659
Phosphane-Free Copper-Catalyzed Decarboxylative Coupling of Alkynyl
Carboxylic Acids with Aryl Halides under Aerobic Conditions
Delin Pan,[a] Chun Zhang,[a] Shengtao Ding,[a] and Ning Jiao*[a,b]
Keywords: Cross-coupling / Copper / Decarboxylation / Carboxylic acids / O ligands
A phosphane-free copper-catalyzed decarboxylative cross-
coupling reaction of alkynyl carboxylic acids with aryl ha-
lides was developed. CuBr (1–5 mol-%) was used as a cata-
catalyst. The ligand plays a key role in this kind of copper
catalysis. NaNO2 was disclosed to efficiently improve this
kind of decarboxylative cross-coupling when a nitro group
lyst in the presence of a β-diketone ligand in air. The reac- was not present in the substrates.
tions of aryl iodides were conducted in the absence of a Pd
Introduction
Transition-metal-catalyzed cross-coupling reactions can
nowadays be considered a cornerstone in organic synthe-
sis.[1] Among them, Sonogashira-type reactions,[2] which in-
volve the coupling of aryl or alkenyl halides or triflates with
terminal alkynes (Scheme 1, type a), have been studied in
detail as a powerful tool for preparing acetylene derivatives,
which have been used as precursors for natural products,
pharmaceuticals, and molecular organic materials.[3] Since
its introduction in 1975,[4] efforts have been made to push
the limits of this methodology through the discovery and
Scheme 1. Sonogashira-type cross-coupling reactions.
development of more facile procedures, such as the use of
improved metal acetylides as the coupling partners
(Scheme 1, type b),[5,6] the employment of 2-methyl-3-but-
yn-2-ol as the acetylene source (Scheme 1, type c),[7] as well
as the discover of more active catalysts for cross-coupling
with unactivated arene chlorides[8] or arenes.[9] Generally,
Sonogashira reactions are performed using a palladium cat-
alyst in the presence or absence of a copper(I) co-catalyst.
To satisfy economic concerns, the use of inexpensive
metals[10–12] as catalysts has been studied. Despite great ad-
vances, most methods require the use of oxygen-free reac-
tion conditions to inhibit the Glaser reaction (oxidative
homocoupling of terminal alkynes).[13] Hence, the develop-
ment of environmentally benign and efficient methods is
still important for continued advancements in this area.
The importance of transition-metal-catalyzed decarbox-
ylative cross-coupling chemistry has grown rapidly in recent
years.[14,15] Carboxylic acids are among the most common
functionalities in organic molecules. They are largely avail-
able, stable, and easy to handle and store. Recently, the de-
carboxylative sp–sp2 cross-coupling reaction of alkynyl carb-
oxylic acids with aryl halides has been developed.[16] All
these reactions were performed by using a Pd catalyst in the
presence of a phosphane ligand, which is sensitive to air. In
addition, the use of an excess amount of tetra-n-butylam-
monium fluoride (TBAF, 2–6 equiv.)[16f,16h] or Ag2O (1–
2 equiv.)[16g] in some cases also limits their application.
Herein, we introduce a copper-catalyzed decarboxylative
cross-coupling of propiolic acids with aryl halides in air
(Scheme 1, type d).
[a] State Key Laboratory of Natural and Biomimetic Drugs,
School of Pharmaceutical Sciences, Peking University,
Xue Yuan Road 38, Beijing 100191, China
Fax: +86-10-8280-5297
Results and Discussion
E-mail: jiaoning@bimu.edu.cn
Recently, Kolarovicˇ and co-workers reported a CuCl-cat-
alyzed decarboxylation of propiolic acids.[17] We have devel-
oped a Cu-catalyzed decarboxylative cross-coupling of pro-
piolic acids with amides[18a] or terminal alkynes[18b] in air.
We hypothesized that the decarboxylative cross-coupling of
[b] Shanghai Key Laboratory of Green Chemistry and Chemical
Processes, Department of Chemistry, East China Normal
University,
Shanghai 200062, China
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201100659.
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© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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D. Pan, C. Zhang, S. Ding, N. Jiao
SHORT COMMUNICATION
alkynyl carboxylic acids with aryl halides could be achieved ciency was obtained by employing K3PO4 as the base
by using a copper catalyst under proper conditions. We ini- (Table 1, Entry 13). However, reactions performed in
tially chose the coupling of 4-nitro-1-iodobenzene (1a) with dichloroethane (DCE) or CH3CN (Table 1, Entries 11 &
phenylpropiolic acid (2a) as a model reaction (Table 1). 12) in the absence of a base or in the presence of the organic
However, no product was observed when the reaction was base Et3N (Table 1, Entries 14 & 15) did not proceed.
catalyzed by CuBr (5 mol-%) in DMF at 120 °C (Table 1, Furthermore, a low yield was obtained when the reaction
Entry 1). Gratifyingly, the expected product, 1-nitro-4- was carried out under an atmosphere of N2 (Table 1, En-
(phenylethynyl)benzene (3a), was obtained in 65% yield try 16).
when 1,3-diphenylpropane-1,3-dione (L1, 5 mol-%) was
To exclude the effect of palladium, the CuBr used in
added as a ligand in the above catalytic system (Table 1, these reactions was analyzed by plasma mass spectrometry
Entry 2). It is noteworthy that the presence of H2O (ICP-MS). However, no palladium content was detected in
(5 equiv.) led to a dramatic improvement, giving 3a in 95% the CuBr catalyst (see the Supporting Information).
yield (Table 1, Entry 3). However only a trace amount of 3a Furthermore, the reaction of 1a with 2a catalyzed by PdCl2
was produced when water was used as the solvent (Table 1, (0.1 mol-%) instead of CuBr in air only produced 3a in 60%
Entry 4). It is obvious that the ligand plays a key role in yield [Equation (1)].
this kind of copper catalysis. Low efficiency was observed
when L1 was replaced by β-diketone ligand L2 (Table 1,
Entry 5). The reactions did not work when nitrogen-donor
ligand L3 or L4 was used (Table 1, Entries 6 & 7). Further
investigations indicated that the reaction proceeded
smoothly to give an excellent yield even when the loading
of CuBr/L1 was reduced to 1 mol-% (Table 1, Entry 8). The
Under the optimized conditions, the scope of this decarb-
use of other catalysts such as Cu(OAc)2 or Cu(acac)2 gave oxylative cross-coupling reaction was expanded to a vari-
a lower yield (Table 1, Entries 9 & 10). Similar high effi- ety of aryl iodides (Table 2). Employing only 1 mol-% of
CuBr and L1, iodobenzenes containing a nitro group at the
ortho, meta, or para position reacted smoothly with phenyl-
Table 1. Copper-catalyzed decarboxylative cross-coupling of phen-
ylpropiolic acid (2a) with 4-nitro-1-iodobenzene (1a).[a]
propiolic acid (2a) to give the corresponding products in
good to excellent yields (Table 2, Entries 1–4). However, a
low yield was obtained when 4-methoxy-1-iodobenzene (1e)
was employed as the substrate under the optimized condi-
tions (Table 2, Entry 5). To improve the efficiency of the
reaction with 4-methoxy-1-iodobenzene (1e), screening of
different parameters including base, ligand, and catalyst
was undertaken (see the Supporting Information). Con-
sidering that the iron/copper co-catalytic system[19] may af-
fect this transformation, reactions catalyzed by CuBr in the
presence of different iron catalysts were investigated (Sup-
porting Information; Table S1, Entries 21–27). However, a
low yield was obtained in each case.
Entry
[Cu]
[mol-%]
Ligand
[mol-%]
Base
Solvent
Yield
[%][b]
On the basis of the above results and the reported ef-
ficient decarboxylative cross-coupling reactions with sub-
strates containing a nitro group,[15,20] we envisioned that the
1[c]
2[c]
3
CuBr (5)
CuBr (5)
CuBr (5)
CuBr (5)
CuBr (5)
CuBr (5)
CuBr (5)
CuBr (5)
Cu(OAc)2 (1)
Cu(acac)2 (1)
CuBr (1)
CuBr (1)
CuBr (1)
CuBr (1)
CuBr (1)
CuBr (1)
–
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K3PO4
Et3N
DMF
DMF
DMF
H2O
DMF
DMF
DMF
DMF
DMF
DMF
DCE
CH3CN
DMF
DMF
DMF
DMF
NR
65
95
trace
16
NR
NR
96
L1 (5)
L1 (5)
L1 (5)
L2 (5)
L3 (5)
L4 (5)
L1 (1)
L1 (1)
L1 (1)
L1 (1)
L1 (1)
L1 (1)
L1 (1)
L1 (1)
L1 (1)
4[d]
5
–
presence of NO2 in the catalytic system may improve the
decarboxylative transformation. After screening different
reaction parameters (see the Supporting Information), we
finally found that the expected product 1-methoxy-4-(phen-
ylethynyl)benzene (3e) was formed in the highest yield
(63%) when NaNO2 (1.0 equiv.) was employed with CuBr
(5 mol-%) and L1 (Table 2, Entry 6). Moreover, it is surpris-
ing that a lower yield was obtained when NaNO2 was used
in the presence of H2O (see the Supporting Information).
Assisted by NaNO2, iodobenzenes bearing electron-with-
drawing and electron-donating groups were tolerated in this
reaction (Table 2, Entries 6–10). The reaction of 4-bromo-1-
iodobenzene (1h) with 2b proceeded under these conditions,
producing 3h in 30% yield (Table 2, Entry 11). In addition,
the addition of a palladium catalyst did not dramatically
improve the yield of this coupling reaction [Table 2, En-
6
7
8
9
10
11[e]
12[e]
13
14
15
16[f]
92
84
NR
NR
93
NR
NR
Ͻ5
–
K2CO3
[a] Reaction conditions: 1a (0.5 mmol, 1.0 equiv.), 2a (0.6 mmol),
base (1.0 mmol), H2O (5.0 equiv.), copper catalyst, ligand, and sol-
vent (3 mL), 120 °C, 20 h, in air. [b] Isolated yield; NR = no reac-
tion. [c] H2O was not added. [d] The reaction was conducted at
100 °C. [e] The reaction was conducted at 80 °C. [f] The reaction
was conducted under N2.
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Phosphane-Free Copper-Catalyzed Decarboxylative Coupling
Table 2. The reactions of phenylpropiolic acid (2a) or 4Ј-methoxy- piolic acid 2f proceeded efficiently to give expected product
phenylpropiolic acid (2b) with aryl iodides 1.[a]
3m in 82% yield (Table 3, Entry 5). Moreover, 3-styryl-
propiolic acid (2g) reacted successfully with 1a to give the
corresponding arylvinylacetylene 3n in 85% yield (Table 3,
Entry 6).
Table 3. The reactions of 4-nitro-1-iodobenzene (1a) with aryl or
vinylpropiolic acids 2.[a]
[a] Reaction conditions: 1a (0.5 mmol), 2 (0.6 mmol), K2CO3
(1.0 mmol), CuBr (0.005 mmol), L1 (0.005 mmol), H2O
(2.5 mmol), and DMF (3 mL), 120 °C, 20 h, in air. [b] Isolated
yield. [c] 1a (0.25 mmol), 2 (0.3 mmol), K2CO3 (0.5 mmol), CuBr
(0.0125 mmol), L1 (0.0125 mmol), H2O (1.25 mmol), and DMF
(1.5 mL) was used.
Although, the decarboxylative cross-coupling reactions
of phenylpropiolic acid (2a) with 4-nitro-1-bromobenzene
(4) produced expected product 3a in low yield (Table 4, En-
try 1). The reaction in the presence of a trace amount of
PdCl2 (0.5 mol-%) notably increased the yield to 92%
(Table 4, Entry 2). Under these conditions, 4 reacted
smoothly with propiolic acids containing various aryl or
vinyl groups, generating the corresponding products in
moderate to good yields (Table 4, Entries 3–7). Notably, 1-
nitro-4-(β-styrylethynyl)benzene (3p) was highly stereoselec-
tively generated (E/Z Ͼ99:1; Table 4, Entry 7 vs. Table 3,
Entry 6).
[a] Reaction conditions:
1 (0.5 mmol), 2 (0.6 mmol), K2CO3
(1.0 mmol), CuBr (0.005 mmol), L1 (0.005 mmol), H2O
(2.5 mmol), and DMF (3 mL), 120 °C, 20 h, in air. [b] Isolated
yield. [c] 1 (0.25 mmol), 2 (0.3 mmol), K2CO3 (0.25 mmol), CuBr
(0.0125 mmol), L1 (0.0125 mmol), NaNO2 (0.25 mmol), and DMF
(1.5 mL) were used. [d] PdCl2 (0.00125 mmol) was added.
try 12; also see Equations (1) and (2) in the Supporting In-
formation].
Conclusions
The reactions of 1a with variously substituted alkynyl
In conclusion, we have developed an efficient copper-cat-
carboxylic acids were then investigated (Table 3). The corre- alyzed decarboxylative cross-coupling of aryl halides with
sponding diarylacetylenes were produced in good to excel- alkynyl carboxylic acids. The use of alkynyl carboxylic acid
lent yields under the optimized conditions (Table 3). No- derivatives, which are readily available, easy to store, and
tably, the decarboxylative cross-coupling of heteroarylpro- simple to handle, as the coupling partner efficiently inhibits
Eur. J. Org. Chem. 2011, 4751–4755
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D. Pan, C. Zhang, S. Ding, N. Jiao
SHORT COMMUNICATION
Table 4. The reactions of 4-nitro-1-bromobenzene (4) with aryl or
vinylpropiolic acids 2.[a]
Acknowledgments
Financial support from the National Natural Science Foundation
of China (20872003), National Basic Research Program of China
(973 Program) (Grant No. 2009CB825300), and the Program for
New Century Excellent Talents in University (NCET) are greatly
appreciated. We thank Chong Qin in this group for reproducing
the results of 3e in Table 2.
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4 (0.5 mmol), 2 (0.6 mmol), K2CO3
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Experimental Section
Typical Procedure: To a mixture of CuBr (0.005 mmol), 1,3-di-
phenylpropane-1,3-dione (0.005 mmol), aryl halide (0.5 mmol),
alkynyl carboxylic acid (0.6 mmol), and K2CO3 (1.0 mmol) was
added DMF (3 mL) and the additive(s). The resulting mixture was
heated at 120 °C in air for 20 h as monitored by TLC. The reaction
mixture was diluted with ethyl acetate (10 mL) and washed with
saturated NH4Cl (10 mL). The layers were separated, and the aque-
ous layer was extracted with ethyl acetate (10 mL). The combined
organic layers were then concentrated by evaporation, and the resi-
due was purified by flash chromatography on silica gel (petroleum
ether/ethyl acetate) to afford the desired product.
Supporting Information (see footnote on the first page of this arti-
cle): Experimental details, characterization data, and 1H and 13C
NMR spectra for the products included in this paper.
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Received: May 11, 2011
Published Online: July 18, 2011
Eur. J. Org. Chem. 2011, 4751–4755
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
4755