Ruthenium-catalyzed carbonylative C-C coupling in water by directed C-H bond activation

Article abstract of DOI:10.1002/anie.201301663

First things first: The title reaction of arenes bearing ortho-directing groups (DG) in the presence of a ruthenium catalyst and aryl iodide is presented. The reaction is general for variously substituted aryl iodides to give ketones in moderate to good yields, and water serves as the solvent. The system is highly selective towards the mono-carbonylative arylation by ortho C-H functionalization. cod=cyclo-1,5-octadiene. Copyright

Full text of DOI:10.1002/anie.201301663

Angewandte
Chemie
DOI: 10.1002/anie.201301663
Synthetic Methods
À
Ruthenium-Catalyzed Carbonylative C C Coupling in Water by
Directed C H Bond Activation**
À
Anis Tlili, Johannes Schranck, Jola Pospech, Helfried Neumann, and Matthias Beller*
Benzophenones constitute attractive targets for the fine-
chemical industry, life sciences, and organic synthesis. Espe-
cially, those with heterocyclic substituents exhibit a plethora
of biological activities including cholesterol regulation
(Tricor), anti-inflammatory effects (Sector), and selective
estrogen receptor modulation (Evista). Hence, it is not
surprising that several benzophenone derivatives were clas-
sified worldwide to be among the top 200 most-sold pharma-
ceutical compounds in 2009.[1]
prepare these in a separate manner lowers their synthetic
value.
[4]
À
In general, direct transition metal catalyzed C H bond
functionalization reactions of arenes and heteroarenes offer
an attractive benign alternative to the aforementioned
processes. In fact, transition-metal catalysts are often used
À
for selective C H functionalizations in the preparation of
various chemical building blocks.[5,6] With respect to catalysts,
in addition to rhodium and palladium salts, ruthenium
À
Regarding their synthesis, carbon monoxide represents an
inexpensive and atom efficient C1 building block, which
allows the introduction of a carbonyl group into the desired
target molecule by various carbonylation reactions. These
transformations are typically catalyzed by palladium com-
plexes. Representative examples include the carbonylative
Suzuki, Negishi, Stille, and Hiyama reactions (Scheme 1).[2,3]
It is worth noting that a few reports also make use of
organoaluminum and organoindium compounds.[2b] Although
these transformations have become powerful tools in organic
chemistry, the necessity to use (over)stoichiometric amounts
of organometallic coupling reagents as well as the need to
complexes have evolved as effective systems for C H bond
activation in recent years.[7] More specifically, important
2
2
À
progress in the direct C(sp ) C(sp ) bond formation between
arenes bearing a directing group and aryl halides has been
reported by the groups of Inoue,[8] Ackermann,[9] and
Dixneuf.[10]
In contrast to the commonly developed arylations and
À
vinylations, carbonylative C H bond functionalizations have
been investigated to a lesser extent.[11] To the best of our
knowledge, there exists no examples of carbonylative cou-
À
pling reactions of aryl halides by directed C H bond
activation.[12]
Based on our continuous interest to discover novel and
improve existing carbonylative processes,[13] we report herein
a general and selective ruthenium-catalyzed aroylation with
carbon monoxide of (hetero)arenes bearing ortho-directing
groups (Scheme 1).
Initial experiments were carried out using 2-phenylpyr-
idine as a model substrate, phenyl iodide, and 5 mol% of
a [Ru(cod)Cl2] polymer at medium pressure (30 bar of carbon
monoxide). Different bases, solvents, and several additives
were tested under these reaction conditions. When DMSO
was employed as a solvent in the presence of potassium
carbonate (2 equiv) and potassium acetate (0.2 equiv) as
additives, no conversion of the starting materials was
observed (Table 1, entry 1). In the presence of other organic
solvents the desired carbonylative product was observed in
disappointing yields (Table 1, entries 1–6). However, similar
to the recent work of Dixneuf and co-workers, changing the
organic solvent to water increased the reactivity of the
carbonylative reaction dramatically and 56% of the desired
product was obtained. This improvement is also in agreement
with the positive effect of water in several classical organic
reactions.[14]
À
Scheme 1. Carbonylative three component C C coupling reactions.
TM=transition metal.
[*] Dr. A. Tlili, J. Schranck, J. Pospech, Dr. H. Neumann,
Prof. Dr. M. Beller
Leibniz-Institut fꢀr Katalyse an der Universitꢁt Rostock
Albert-Einstein-Straße 29a, 18059 Rostock (Germany)
E-mail: Matthias.Beller@catalysis.de
Notably, the reaction is highly selective towards the
monoaroylation of 2-phenyl pyridine as no traces of the direct
[**] We thank the state of Mecklenburg-Vorpommern and the Bundes-
ministerium fꢀr Bildung und Forschung (BMBF) for financial
support. We also thank Dr. W. Baumann, Dr. C. Fischer, and S.
Buchholz (LIKAT) for analytical support.
À
mono or the double C C bond formation have been detected
under these reaction conditions. With respect to the con-
version of phenyl iodide, traces of benzaldehyde, benzyl
alcohol, and the reduction of iodobenzene to benzene caused
by a ruthenium-catalyzed water gas shift reaction were
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.201301663.
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Table 1: Ruthenium-catalyzed carbonylative C H activation of 2-phenyl-
Table 2: Ruthenium-catalyzed carbonylative C H activation of 2-
pyridine: Variation of reaction conditions.[a]
phenylpyridine: Variation of ruthenium complexes.[a]
Entry
[Ru]
Yield [%][b]
Entry
Solvent
(1 mL)
Base
(2 equiv)
Additive
(0.2 equiv)
Yield[b] [%]
1
2
3
4
5
6
7
8
9
[{RuCl2(cod)}n]
65
<1
<1
24
16
0
<1
<1
<1
[{RuCl2(cod)}n] + 0.1 equiv Ag(OAc)2
[{RuCl2(cod)}n] + 0.1 equiv AgSbF6
[Ru(OAc)2(cod)]
[{RuCl2(p-cymene)}2]
[CpRuCl(PPh3)2]
[Ru(CO)3Cl2]
[Ru(acac)3]
[Ru3(CO)12]
1
2
3
4
5
6
7
8
DMSO
DMF
NMP
PhMe
MeCN
tAmOH
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
Cs2CO3
K3PO4
KOH
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
KOAc
NaOAc
CsOPiv
MesCOOH
Cl3COOH
KOAc
KOAc
KOAc
KOAc
–
0
4
13
5
12
8
56, 44,[c] 54[d]
54
36
28
54
54
44
44
<1
<1
65
9
[a] Reactions were performed with 1 mmol of iodobenzene, 0.5 mmol of
2-phenylpyridine, 0.05 equiv of ruthenium complex, 0.2 equiv of KOAc
and 1 mmol of base under 30 bar of carbon monoxide at 1208C for 20 h.
[b] GC yields with hexadecane as an internal standard; average of two
runs. acac=acetylacetonate.
10
11
12
13
14
15
16
17
NaOtBu
KOAc
NaHCO3
catalyst system completely (Table 2, entries 2 and 3). Fur-
thermore, lower conversion and yield was observed when
starting from the presumed active species and only 24 mol%
of the product was formed (Table 2, entry 4). A low product
yield was also observed when the ruthenium dimer dichloro-
(p-cymene)ruthenium(II) was used (Table 2, entry 5).
Employing other ruthenium catalysts with different oxidation
states (0, II, and III) gave marginal product formation
(Table 2, entries 7–9).
KOAc
[a] Reactions were performed with 1 mmol of iodobenzene, 0.5 mmol of
2-phenylpyridine, 0.05 equiv of ruthenium complex, 0.2 equiv of additive,
and 1 mmol of base under 30 bar of carbon monoxide, at 1208C for 20 h
unless otherwise noted. [b] GC yields with hexadecane as an internal
standard; average of two runs. [c] Reaction was performed under 20 bar
of CO. [d] Reaction was performed under 40 bar of CO. cod=cyclo-1,5-
octadiene, DMF=N,N-dimethylformamide, DMSO=dimethylsulfoxide,
NMP=N-methylpyrrolidone.
With the best reaction conditions in hand ([{RuCl2-
(cod)}n]/NaHCO3/KOAc), we turned our attention to the
evaluation of the substrate scope of ruthenium-catalyzed
observed in minor amounts.[15] A change of the carbon
monoxide pressure to 20 bar decreased the yield slightly to
44% (Table 1, entry 7). However, at higher CO pressure
(40 bar) a similar yield was obtained.
À
À
carbonylative C C bond formation by direct C H activation.
Using aryl iodides with either electron-donating (Table 3,
entries 1–6) or electron-withdrawing groups (Table 3,
entries 9–11) led to the formation of the corresponding
benzophenone derivatives in moderate to good yields in all
the cases. Aryl iodides substituted with alkyl groups in para-,
meta-, or ortho-positions were all effective under our reaction
conditions (Table 3, entries 2–5). It is important to note that
in the case of 4-iodotoluene the optimum yield was obtained
with potassium carbonate as a base. The use of 2-iodotoluene
as a coupling partner generated the corresponding ketone
with the best yield of the isolated product being 74%
(Table 3, entry 5). Aryl halides bearing a methoxy group
showed slightly slower reactivity (Table3, entry6). In general,
aryl iodides with an electron-withdrawing group were less
reactive than the ones with donating groups. Nevertheless, no
position effect between meta or para substitution was
observed for the synthetically interesting fluorinated aryl
halides employed in the reaction (Table 3, entries 9–11).
After having observed the general activity with several
aryl iodides, we turned our attention to study the reactivity
with different directing groups (Table 4). To our delight,
phenyl derivatives bearing pyrazole as a directing group were
also effective. Hence, 3,5-dimethyl-1-phenyl-1H-pyrazole was
Next, we examined the influence of different additives on
the reaction (Table 1, entries 8–11). Here, several acids and
bases were tested, but none of them improved the product
yield. Finally, the base effect was studied in more detail.
Cesium carbonate and potassium phosphate were effective
and the product was formed in 54 and 44% yield, respectively
(Table 1, entries 12 and 13). Strong bases like potassium
hydroxide or sodium tert-butoxide were ineffective under our
reaction conditions (Table 1, entries 14 and 15). Interestingly,
the best yield (65% of the product) was achieved in the
presence of inexpensive sodium bicarbonate (Table 1,
entry 17). It is worth noting that running the reaction
exclusively with potassium acetate (2 equiv) gives less than
1% of the product (Table 1, entry 16).
For further optimization we decided to investigate the
effect of different ruthenium complexes on the carbonylative
À
C H functionalization. In the related direct coupling reac-
tion, it is well known that the addition of silver salts had
a positive effect on the generation of the active species.[16a]
However, in the present model reaction adding silver acetate
or silver hexafluoroantimonate inhibited the reactivity of our
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Table 3: Ruthenium-catalyzed carbonylative C H activation: Substrate
Table 4: Ruthenium-catalyzed carbonylative C H activation: Substrate
scope with different aryl iodides.[a]
scope with different directing groups.[a]
Entries
Aryl iodide
Product
Yield
[%][b]
1
2
3
1a
1b
1c
61
54[c]
52
[a] Reactions were performed with 1 mmol of aryliodide, 0.5 mmol of aryl
bearing a directing group, 0.05 equiv of ruthenium complex, 0.2 equiv of
KOAc, and 1 mmol of base under 30 bar at 1208C for 20 h unless
otherwise noted. [b] Yields of isolated products.
4
1d
55
5
6
7
8
1e
1 f
74
41
62
56
ylation occurred exclusively on the C2 position of the
heterocyclic moiety.
Based on previous investigations by the groups of
Ackermann, Jutand, and Dixneuf, we propose the following
mechanism for this carbonylative coupling process. After
initial formation of the cyclometalated ruthenium complex,
subsequent carbonylation and oxidative addition of the aryl
halide takes place. Finally, reductive elimination gives the
product and regenerates the active catalyst.
1g
1h
To understand the selectivity of the process, experiments
with labeled starting materials or in deuterated water were
undertaken [Eqs. (1), (2), and (3); Scheme 2]. It is worth
noting that Ackermann et al. described a D/H exchange for
the direct arylation of phenyl pyridine when their reaction
9
1i
1j
1k
40
46
54
10
11
[a] Reactions were performed with 1 mmol of aryl iodide, 0.5 mmol of 2-
phenylpyridine, 0.05 equiv of ruthenium complex, 0.2 equiv of KOAc, and
1 mmol of NaHCO3 under 30 bar of carbon monoxide at 1208C for 20 h
unless otherwise noted. [b] Yields of isolated products. [c] Reaction
performed with K2CO3 as base.
successfully converted with 4-ethyliodobenzene as well as
with 2-iodotoluene.
When 2-iodotoluene was reacted with the monomethyl-
substituted pyrazole under carbon monoxide pressure the
corresponding ketone was observed. Furthermore, other
heterocycles bearing a directing group have been tested.
Reaction of 3-phenylfuran gave 4a in 50% yield upon
isolation. Moreover, thiophene derivatives bearing pyridine
or pyrimidine directing groups gave good yields of 5a (75%)
À
and 6a (68%), respectively. Interestingly, the C H carbon-
Scheme 2. Deuteration experiments.
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was carried out for 18 hours at 1208C.[16b] More recently, in
similar investigations by Jutand, Dixneuf, and co-workers[16a]
no H/D exchange was observed when the reaction was carried
out at room temperature. Under the carbonylative reaction
conditions using deuterated 2-phenylpyridine or deuterated
water an H/D exchange was observed after 20 hours [Eqs. (1)
and (2)]. More interestingly, when the reaction of 2-phenyl-
pyridine was stopped after five hours less than 5% of H/D
exchange was detected [Eq. (3)]. This result can be explained
by the reversibility of the second metalation after the product
has been formed.[17] Further experiments are under way in our
laboratory to elucidate the mechanism of the transformation
in more details.
d) X.-F. Wu, H. Neumann, M. Beller, Tetrahedron Lett. 2010, 51,
6146; e) X.-F. Wu, J. Schranck, H. Neumann, M. Beller, Chem.
Asian J. 2012, 7, 40; f) X.-F. Wu, H. Neumann, M. Beller, Adv.
Synth. Catal. 2011, 353, 788.
À
[4] For selected recent general reviews and highlights on C H
activation, see: a) N. Kuhl, M. N. Hopkinson, J. Wencel-Delord,
F. Glorius, Angew. Chem. 2012, 124, 10382; Angew. Chem. Int.
Ed. 2012, 51, 10236; b) J. Wencel-Delord, T. Drçge, F. Liu, F.
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Bergman, J. A. Ellman, Chem. Rev. 2010, 110, 624; d) T. W.
Lyons, M. S. Sanford, Chem. Rev. 2010, 110, 1147; e) L.
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Chem. 2011, 123, 7618; Angew. Chem. Int. Ed. 2011, 50, 7479.
[5] S. Rousseaux, B. Liꢃgault, K. Fagnou in Modern Tools for the
Synthesis of Complex Bioactive Molecules (Eds.: J. Cossy, S.
Arseniyadis), Wiley-VCH, Weinheim, 2012, p. 1.
In conclusion, we have developed the first ruthenium-
À
À
catalyzed carbonylative C C bond formation by directed C
H functionalization. The aroylation of 2-arylpyridines and
related derivatives proceeds highly selective with water as the
solvent. Compared to known carbonylative coupling process-
es stoichiometric amounts of organometallic reagents are
avoided. Currently, the effects of different directing groups as
well as further mechanistic investigations are under way in
our laboratory.
[6] For recent reviews, see: a) J. Yamaguchi, A. D. Yamaguchi, K.
Itami, Angew. Chem. 2012, 124, 9092; Angew. Chem. Int. Ed.
2012, 51, 8960; b) L. McMurray, F. OꢄHara, M. J. Gaunt, Chem.
Soc. Rev. 2011, 40, 1885.
À
[7] For recent reviews on ruthenium-catalyzed C H bond activa-
tion, see: a) P. B. Arockiam, C. Bruneau, P. H. Dixneuf, Chem.
Rev. 2012, 112, 5879; b) S. I. Kozhushkov, H. K. Potukuchi, L.
Ackermann, Catal. Sci. Technol. 2013, DOI: 10.1039/
C2CY20505J.
Experimental Section
[8] a) S. Oi, S. Fukita, N. Hirata, N. Watanuki, S. Miyano, Y. Inoue,
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Synthesis of phenyl(2-(pyridin-2-yl)phenyl)methanone: The reaction
was carried out in a Parr Instruments 4560 series 300 mL autoclave
containing an alloy plate with wells for six 4 mL Wheaton vials.
[{RuCl2(cod)}n] (5 mol%), KOAc (20 mol%), NaHCO3 (1 mmol),
benzoxazole, and a magnetic stir bar were placed in each of the vials,
which were then capped with a septum equipped with an inlet needle
and flushed with argon. Then, iodobenzene (1 mmol), 2-phenyl-
pyridine (0.5 mmol), and H2O (1 mL) were added to the vial with
a syringe. The vials were placed in an alloy plate, which was then
placed in the autoclave. Once sealed, the autoclave was purged
several times with CO, then pressurized to 30 bar at room temper-
ature and heated at 1208C for 20 h. It was then cooled to room
temperature and vented to discharge the excess CO. The product was
extracted with ethyl acetate (5 ꢀ 3 mL). The organic layers were
washed with brine, dried over Na2SO4, and evaporated to yield the
crude reaction mixture. Purification by flash chromatography on silica
gel (eluent: heptane/EtOAc 80:20) gave the product (62%) as a white
solid.
[10] a) P. B. Arockiam, C. Fischmeister, C. Bruneau, P. H. Dixneuf,
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Chem. Int. Ed. 2010, 49, 6629; c) I. ꢇzdemir, S. Demir, B.
Cetinkaya, C. Gourlaouen, F. Maseras, C. Bruneau, P. H.
Received: February 26, 2013
Published online: && &&, &&&&
À
Keywords: C H activation · homogenous catalysis · ruthenium ·
synthetic methods · water
.
ˇ
Dixneuf, J. Am. Chem. Soc. 2008, 130, 1156; d) F. Pozgan, P. H.
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[1] N. A. McGrath, M. Brichacek, J. T. Njardarson, J. Chem. Educ.
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Chem. 2011, 123, 10978; Angew. Chem. Int. Ed. 2011, 50, 10788;
b) X.-F. Wu, H. Neumann, ChemCatChem 2012, 4, 447.
[12] a) We developed recently a carbonylative coupling reaction
between aryl iodide and heterocycle in the presence of
palladium and copper. See: X.-F. Wu, P. Anbarasan, H.
Neumann, M. Beller, Angew. Chem. 2010, 122, 7474; Angew.
Chem. Int. Ed. 2010, 49, 7316; b) Aiwen Lei presented recently
[2] For recent reviews see: a) X.-F. Wu, H. Neumann, M. Beller,
Chem. Soc. Rev. 2011, 40, 4986; b) A. Brennfꢁhrer, H. Neumann,
M. Beller, Angew. Chem. 2009, 121, 4176; Angew. Chem. Int. Ed.
2009, 48, 4114; c) B. Gabriele, R. Mancuso, G. Salerno, Eur. J.
Org. Chem. 2012, 6825; d) X.-F. Wu, H. Neumann, M. Beller,
Chem. Rev. 2013, 113, 1.
[3] For recent examples, see: a) H. Neumann, A. Brennfꢁhrer, M.
Beller, Chem. Eur. J. 2008, 14, 3645; b) J. Lindh, A. Fardost, M.
Almeida, P. Nilsson, Tetrahedron Lett. 2010, 51, 2470; c) J.
Sꢂvmarker, J. Lindh, P. Nilsson, Tetrahedron Lett. 2010, 51, 6886;
À
an elegant palladium catalyst for the double C H oxidative
carbonylation of diphenyl ether derivatives to obtain xanthones:
H. Zhang, R. Shi, P. Gan, C. Liu, A. Ding, Q. Wang, A. Lei,
4
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Angew. Chem. 2012, 124, 5294; Angew. Chem. Int. Ed. 2012, 51,
5204.
[14] M.-O. Simon, C.-J. Li, Chem. Soc. Rev. 2012, 41, 1415.
[15] For our recent work on using CO and water as reductant, see: A.
Tlili, J. Schranck, H. Neumann, M. Beller, Chem. Eur. J. 2012, 18,
15935.
[16] For recent selected mechanistic studies, see: a) E. Ferrer Fle-
geau, C. Bruneau, P. H. Dixneuf, A. Jutand, J. Am. Chem. Soc.
2011, 133, 10161; b) L. Ackermann, R. Vicente, H. K. Potukuchi,
V. Pirovano, Org. Lett. 2010, 12, 5032; c) see ref. [4e].
[17] The H/D exchange is better reflected by comparison of the signal
intensity of the H on 3C in the 13C DEPT NMR data. See the
Supporting Information (p. 22).
[13] For some selected examples from our group, see: a) X.-F. Wu, H.
Neumann, M. Beller, Angew. Chem. 2010, 122, 5412; Angew.
Chem. Int. Ed. 2010, 49, 5284; b) X.-F. Wu, H. Neumann, A.
Spannenberg, T. Schulz, H. Jiao, M. Beller, J. Am. Chem. Soc.
2010, 132, 14596; c) X.-F. Wu, H. Jiao, H. Neumann, M. Beller,
ChemCatChem 2011, 3, 726; d) J. Schranck, X.-F. Wu, H.
Neumann, M. Beller, Chem. Eur. J. 2012, 18, 4827; e) J. Schranck,
A. Tlili, H. Neumann, P. G. Alsabeh, M. Stradiotto, M. Beller,
Chem. Eur. J. 2012, 18, 15592; f) P. G. Alsabeh, M. Stradiotto, H.
Neumann, M. Beller, Adv. Synth. Catal. 2012, 354, 3065.
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Communications
Synthetic Methods
A. Tlili, J. Schranck, J. Pospech,
H. Neumann, M. Beller*
&&&& — &&&&
À
Ruthenium-Catalyzed Carbonylative C C
First things first: The title reaction of
arenes bearing ortho-directing groups
(DG) in the presence of a ruthenium
catalyst and aryl iodide is presented. The
reaction is general for variously substi-
tuted aryl iodides to give ketones in
moderate to good yields, and water
serves as the solvent. The system is
highly selective towards the mono-car-
À
Coupling in Water by Directed C H Bond
Activation
À
bonylative arylation by ortho C H func-
tionalization. cod=cyclo-1,5-octadiene.
6
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Angew. Chem. Int. Ed. 2013, 52, 1 – 6
These are not the final page numbers!