Extrusion of CO from aryl ketones: Rhodium(I)-catalyzed C-C bond cleavage directed by a pyridine group

Article abstract of DOI:10.1002/anie.201107136

Snipping tool: The rhodium(I)-catalyzed extrusion of carbon monoxide from biaryl ketones and alkyl/alkenyl aryl ketones was developed to produce biaryls and alkyl/alkenyl arenes, respectively, in high yields (see scheme). A wide range of functionalities are tolerated. Not only does this method provide an alternative pathway to construct useful scaffolds, but also offers a new strategy for C-C bond activation. Copyright

Full text of DOI:10.1002/anie.201107136

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DOI: 10.1002/anie.201107136
Biaryls
ꢀ
Extrusion of CO from Aryl Ketones: Rhodium(I)-Catalyzed C C Bond
Cleavage Directed by a Pyridine Group**
Zhi-Quan Lei, Hu Li, Yang Li, Xi-Sha Zhang, Kang Chen, Xin Wang, Jian Sun,* and
Zhang-Jie Shi*
Carbon–carbon bond cleavage is a significant strategy for
organic group transfer, and is conceptually different from
conventional organic synthesis because the existing molecular
skeletons can be reorganized through this method to build the
desired structural units. It is also a challenging field because of
the inherent stability of the carbon–carbon linkages (for
example, steric hindrance).[1] Recently, many efforts have
been made to approach this goal through transition-metal
catalysis.[2] For instance, the ring-opening of strained mole-
cules, such as three- and four-membered rings, has been well
metal-based catalysis has been rarely reported. To date only
one example has been reported by Daugulis and Brookhart,
who were the first to discover the rhodium-catalyzed decar-
bonylation of diaryl ketones albeit at a high catalyst loading,
relatively low conversion, and limited substrate scope.[12]
Herein we report the efficient extrusion of CO from both
biaryl ketones and alkyl/alkenyl aryl ketones to construct
biaryls and alkenyl/alkyl arenes, respectively by rhodium(I)
catalysis directed by a pyridinyl group. The reported protocol
involves a simple and easy-to-handle catalyst system and has
a broad substrate scope for accessing biaryls as well as alkenyl
and alkyl benzenes from aryl ketones, which can easily be
produced through direct acylation (Scheme 1).[13] The use of
directing groups aids the decarbonylation although it com-
plicates the overall synthesis and limits the scope of the
accessible products to those that can be made by the direct
arylation of pyridyl arenes.[14]
studied.[3] Other than these studies, the cleavage of the
[4]
ꢀ
carbon–nitrile (C CN) bond of nitriles and various unique
substrates by forming the stable organometallic intermediates
(for example, p-allyl species) and releasing the small mole-
cules have been well investigated.[5] Another significant
ꢀ
contribution to the C C bond-cleavage approach using
a group-directing strategy has been made by Suggs et al.,
Jun et al., and others.[6]
Biaryls are useful scaffolds in natural products, synthetic
drugs, and organic materials.[7] Transition-metal-catalyzed
cross-coupling reactions have been developed as one of the
most powerful tools for constructing such motifs.[8] Addition-
ally, transition-metal-catalyzed decarbonylation of aldehydes
and decarboxylation of acids and their derivatives, for
example anhydride and acyl chlorides, were carried out
under many different reaction conditions.[9] Although the
photolytic decarbonylation with the bridged ring substrates[10]
and transition-metal-catalyzed decarbonylation of strained
ring system have been well developed,[11] direct decarbon-
Scheme 1. Reaction design.
ꢀ
ylation of stable, linear ketones to construct C C bonds by
Starting from this point, we searched for efficient catalytic
systems to carry out the designed decarbonylation. We first
tested the idea using phenyl(2-(pyridin-2-yl)phenyl) metha-
none (1a) under various reaction conditions (Table 1).
Actually, this substrate is extremely stable under thermal
conditions (entry 1). To our delight, in the presence of
5.0 mol% of [(CO)2Rh(acac)], the extrusion of CO was
observed at 1508C at a high efficiency with PhCl as the
solvent. After 7 hours, the decarbonylation was complete and
2a was isolated in 91% yield (entry 2). Wilkinsonꢀs catalyst
does not show any catalytic ability regardless of the presence
AgSbF6 (entries 3 and 4). The [{(CO)2RhCl}2] dimer showed
comparable reactivity as [(CO)2Rh(acac)] while the corre-
sponding cationic complex did not enhance the yield
(entries 5 and 6).[15] [{Rh(C2H4)2Cl}2] also showed good
reactivity (entry 7). Other RhI and RhIII salts showed much
lower efficacies (entries 8–10). Metal catalysts other than
rhodium completely failed to react and the starting material
remained unreacted (entries 11–14).
[*] Z.-Q. Lei, H. Li, Dr. Y. Li, X.-S. Zhang, K. Chen, X. Wang,
Prof. Dr. Z.-J. Shi
Beijing National Laboratory of Molecular Sciences (BNLMS) and
Key Laboratory of Bioorganic Chemistry and Molecular Engineering
of the Ministry of Education College of Chemistry and
Green Chemistry Center, Peking University, Beijing 100871 (China)
E-mail: zshi@pku.edu.cn
Homepage: http://www.chem.pku.edu.cn/zshi/
Z.-Q. Lei, Prof. Dr. J. Sun
Chengdu Institute of Biology, Chinese Academy of Sciences
Chengdu, Sichuan 400062 (China)
Prof. Dr. Z.-J. Shi
State Key Laboratory of Organometallic Chemistry
Chinese Academy of Sciences, Shanghai 200032 (China)
[**] Support of this work by the “973” Project from the MOST of China
(2009CB825300) and NSFC (Nos. 20925207 and 21002001) is
gratefully acknowledged.
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.201107136.
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Table 1: Exploration of reaction conditions to carry out CO extrusion.
Entry[a]
Catalyst
Solvent
Yield [%]
1
2
3
–
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
anisole
mesitylene
PhNO2
DMSO
trans-decalin
PhCl
0
91[j]
<5
<5
95
95
91
<5
<5
<5
0
[(CO)2Rh(acac)]
[(PPh3)3RhCl]
4[b]
5[c]
6[b,c]
7[d]
8[e]
9
[(PPh3)3RhCl], AgSbF6
[{(CO)2RhCl}2]
[{(CO)2RhCl}2], AgSbF6
[{(C2H4)2RhCl}2]
[{(cod)2RhCl}2]
[Cp*Rh(CH3CN)3][SbF6]2
[{Cp*RhCl2}2], AgSbF6
Pd(OAc)2
10[b,f]
11
12
13
14
15
16
17
18
19
20[g]
21[h]
22[i]
[Ru(PPh3)2Cl2]
[NiCl2(dppe)]
[{Ir(cod)Cl}2]
0
0
0
[(CO)2Rh(acac)]
[(CO)2Rh(acac)]
[(CO)2Rh(acac)]
[(CO)2Rh(acac)]
[(CO)2Rh(acac)]
[(CO)2Rh(acac)]
[(CO)2Rh(acac)]
[(CO)2Rh(acac)]
82[j]
43[j]
82[j]
10
40[j]
83[j]
93[j]
86[j]
PhCl
PhCl
[a] The reactions were carried out in the scale of 0.2 mmol of 1a in the
presence of 5.0 mol% catalyst in 2.0 mL solvent. Yield of isolated
product. [b] 5.0 mol% of AgSbF6 was added. [c] 2.5 mol% of
[{(CO)2RhCl}2] was added. [d] 2.5 mol% of [{(C2H4)2RhCl}2] was added.
[e] 2.5 mol% of [{(cod)2RhCl}2] was added. [f] 2.5 mol% of [{Cp*RhCl2}2]
was added. [g] 1608C for 6 h. [h] 1408C for 22 h. [i] 2.5 mol% of
[(CO)2Rh(acac)] was used for 34 h. [j] ortho-substituted monoaryl/diaryl
>20:1 as determined by 1H NMR (400 MHz) analysis of the crude
reaction mixture. acac=acetylacetonate, cod=1,5-cyclooctadiene,
Cp*=C5(CH3)5, DMSO=dimethylsulfoxide, dppe=1,2-bis(diphenyl-
phosphino)ethane.
Scheme 2. Extrusion of CO by pyridine-directed rhodium(I)-catalyzed
carbon–carbon bond activation. The reactions were carried out using
0.2 mmol of 1 in the presence of 5.0 mol% catalyst in 2.0 mL of PhCl
at 1408C. For experimental details see the Supporting Information.
Reported yield is that of the of isolated product. 2-PE=2-phenylethyl.
ing AcO (2h), MeO (2c), and different halides (2e–g) were
tolerated, and thus offered the possibility for additional
functionalization.[16] Steric hindrance did not significantly
affect the efficiency of the reaction. For example, para- (2b),
meta- (2l), and ortho-methyl (2m) groups gave similar yields.
Heteroaryl groups such as thiophenyl, were tolerated. More-
over, the decarbonylation of the styryl ketone worked well
and the corresponding stilbene derivative 2p was isolated in
excellent yield.
We further examined alkyl aryl ketones (Scheme 2).
Various alkyl groups were suitable for this transformation
(2s–2x). When starting from methyl and ethyl ketones, the
corresponding arenes were obtained in excellent yields (2s
and 2t). A long-chain alkyl group is suitable for this
decarbonylation (e.g., 2u). Notably, the isomerization of
a normal alkyl group was not observed, therefore this method
might be a complementary method of the Friedel–Crafts
reaction for the alkylation of arenes. Secondary alkyl groups
were also feasible and the corresponding decarbonylated
products were isolated in good yields (2v and 2w). Starting
from a phenethyl substrate, direct decarbonylation took place
(2x), which partially ruled out cationic and radical inter-
mediates.
Additional studies indicated the great catalytic power of
[(CO)2Rh(acac)]. To avoid the confusion on the source of the
phenyl group, other solvents were also tested. Anisole and
PhNO2 provided credible yields whereas mesitylene showed
a moderate efficiency (Table 1, entries 15–17). DMSO and
trans-decalin were not ideal solvents and only a small amount
of product was obtained (entries 18 and 19). Although the
slight change of the temperature did not show significant
effect on the yields, the high yield was only obtained at 1408C
by lengthening the reaction time (entries 20 and 21). Finally,
a full conversion and high yield was also obtained at lower
catalyst loadings with a prolonged reaction time (entry 22).
By using the optimized reaction conditions, we inves-
tigated various substrates. First, we tested the substituents on
the phenyl group (Scheme 2). The results indicated that the
decarbonylation was not very sensitive to the electron density
of the phenyl group (2b–k). Both electron-donating (2b and
2c) and electron-withdrawing groups (2e–k) provided good
results. However, a strong electron-donating group (e.g., 2o)
slightly decreased the efficacy. Various functionalities, includ-
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The functionality tolerance of the pyridinyl unit was
further surveyed (Scheme 3). The decarbonylation of the
substrates having different substituents were carried out.
Both electron-donating (3e, 3 f) and electron-withdrawing
groups (3c) offered good results. Similarly, the halide
functionality (3b) is tolerated and offers the potential for
orthogonal transformations.[16] The substrates with or without
a substituent at the 4-position of the phenyl ring (3h, 3l, 3j)
gave good results, and surprisingly contained a trace amount
of the ortho-diarylated by-product and the unsubstituted 2-
arylpyridine. When other solvents were used, trace amounts
of the ortho-diarylated by-product was also observed, thus
indicating that the second aryl group derives from phenyl
scrambling rather than the solvent (PhCl).[17] To our delight,
the aryl scrambling could be inhibited by using
[{(CO)2RhCl}2} instead of [Rh(CO)2(acac)] as the catalyst.
Notably, the alcohol motif survived under the reaction
conditions (3d). 8-Bezoylbenzoquinoline was introduced to
these conditions and the decarbonylation worked well to
produce the desired product 3m in 91% yield. Other N-based
directing groups, such as quinolinyl, pyrazolyl, and oxazolyl
were effective although a prolonged reaction time was
required to achieve moderate yields (3l, 3n, and 3o). Finally,
we tested the diketone at two ortho positions. Both carbonyl
groups were extruded and 2,6-biphenylphenyl pyridine 4 was
isolated in an 89% yield, thus showing the high efficiency of
this transformation [Eq. (1)].
Given that photoirradiation can initiate decarbonylation
in a bridged ring system,[10] we investigated the potential role
of the light in this transformation. Actually, the decarbon-
ylation took place in the dark with a comparable efficiency,
whereas it was completely shut down in the absence of the
rhodium catalyst. Thus, the rhodium complex is the real
catalytic species performing this decarbonylation.
The proposed reaction pathway is shown in Scheme 4. The
decarbonylation is initiated from the oxidative cleavage of the
carbon–carbon bond in the square-planar RhI complex with
Scheme 3. Extrusion of CO by pyridine-directed rhodium(I)-catalyzed
carbon–carbon bond activation. Method A: 0.2 mmol of 1 in the
presence of 5.0 mol% [(CO)2Rh(acac)] in 2.0 mL of PhCl at 1408C.
Method B: 0.2 mmol of 1 in the presence of 2.5 mol% [{(CO)2RhCl}2]
in 2.0 mL of toluene at 1408C. For experimental details see the
Supporting Information. Reported yield is that of the isolated product;
method used is indicated in parentheses. [a] ortho-substituted mono-
aryl/diaryl ratio >20:1 as determined by crude 1H NMR analysis of the
crude reaction mixture. [b] ortho-substituted monoaryl/diaryl
ratio=16:1 as determined by 1H NMR analysis of the crude reaction
mixture. [c] ortho-substituted monoaryl/diaryl=20:1 as determined by
1H NMR analysis of the crude reaction mixture. [d] 36 h. [e] 36 h and
79% starting material was consumed. [f] 36 h and 67% starting
material was consumed. [g] Yield of the isolated product; only the
monoarylated product was obtained.
Scheme 4. Proposed mechanism.
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2 with the regeneration of the RhI catalyst which re-enters the
catalytic cycle. The acyl/RhIII species Awas trapped by phenol
to afford the phenyl benzoate A’ in addition to the desired
product [Eq. (2);reported yield is that of isolated product],[18]
thus suggesting that A could be the key intermediate of the
catalytic cycle. However, the intermediate B could not be
ruled out at this stage.
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In conclusion, we have developed a novel and efficient
rhodium(I)-catalyzed decarbonylation process through
ꢀ
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directing group. Various functionalities are compatible with
the reaction conditions. This method not only offers an
alternative way to synthesize biaryls, and alkenyl and alkyl
benzenes, but also is fundamentally important to under-
standing the reactivity of the inert carbon–carbon bonds.
Additional investigations aimed at exploring this chemistry
and understanding the real catalytic pathway are underway in
our laboratory.
Experimental Section
[(CO)2Rh(acac)] (0.01 mmol, 2.6 mg) in 2 mL of anhydrous PhCl was
added by syringe to a Schlenk flask containing ketone 1 (0.2 mmol).
After degassing three times, the reaction mixture was subsequently
heated at 1408C in Wattecs Parallel Reactor for the proper time with
stirring. After cooling down to room temperature, the solvent was
removed in vacuo and the residue was purified on silica gel
chromatography with hexanes/EtOAc (15:1!5:1) to afford the
desired product 2.
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Received: October 8, 2011
Revised: December 12, 2011
Published online: February 6, 2012
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ꢀ
Keywords: biaryls · homogeneous catalysis · C C activation ·
rhodium · synthetic methods
.
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[18] Note: 32.5% of 1m was recovered. For the related references,
see: a) M. Murakami, T. Tsuruta, Y. Ito, Angew. Chem. 2000,
112, 2600; Angew. Chem. Int. Ed. 2000, 39, 2484; b) T. Matsuda,
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c) T. Matsuda, M. Shigeno, Y. Maruyama, M. Murakami, Chem.
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