CO Gas-free Intramolecular Cyclocarbonylation Reactions of Haloarenes Having a C-Nucleophile through CO-Relay between Rhodium and Palladium

Article abstract of DOI:10.1002/asia.201901595

We describe transfer carbonylation reactions of 2-bromoarenes that contain a carbon-nucleophile using aldehydes as a substitute for CO, leading to the formation of indanone derivatives. The transformation proceeds efficiently under Rh^I/Pd⁰-hybrid catalytic conditions consisting of two discrete transition metals, rhodium and palladium, which catalyze the decarbonylation of aldehydes and the subsequent carbonylation of bromoarenes using the resulting carbonyl moiety, respectively. The majority of the abstracted CO is transferred directly to the product via a CO-relay process from rhodium to palladium.

Full text of DOI:10.1002/asia.201901595

CHEMISTRY
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Accepted Article
Title: CO Gas-free Intramolecular Cyclocarbonylation Reactions of
Haloarenes Having a C-Nucleophile through CO-Relay between
Rhodium and Palladium
Authors: Tsumoru Morimoto, Mana Yamashita, Ai Tomiie, Hiroki
Tanimoto, and Kiyomi Kakiuchi
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10.1002/asia.201901595
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CO Gas-free Intramolecular Cyclocarbonylation Reactions of
Haloarenes Having a C-Nucleophile through CO-Relay between
Rhodium and Palladium
Tsumoru Morimoto,* Mana Yamashita, Ai Tomiie, Hiroki Tanimoto, and Kiyomi Kakiuchi[a]
Abstract: We describe transfer carbonylation reactions of 2-
bromoarenes that contain a carbon-nucleophile using aldehydes as a
substitute for CO, leading to the formation of indanone derivatives.
The transformation proceeds efficiently under Rh(I)/Pd(0)-hybrid
catalytic conditions consisting of two discrete transition metals,
rhodium and palladium, which catalyze the decarbonylation of
aldehydes and the subsequent carbonylation of bromoarenes using
the resulting carbonyl moiety, respectively. The majority of the
abstracted CO is transferred directly to the product via a CO-relay
process from rhodium to palladium.
catalysts that contain both a neutral and a cationic rhodium(I)
species.[8] In this report, we describe a new strategy for a transfer
carbonylation reaction using aldehydes as a substitute for CO.
The reaction proceeds effectively in the presence of a hybrid
catalyst consisting of two discrete transition metals, namely,
rhodium and palladium.[9] Chang et al. reported on the use of a
hybrid catalyst system consisting of Ru(0) and Pd(0) that
catalyzes some CO gas-free carbonylation reactions using
formate[10a] and formamide[10b] derivatives, which includes a
pyridine core, as a carbonyl source. In these cases, Ru(0) and
Pd(0) catalyze the decarbonylation of formate and formamide
derivatives which are specifically designed for decarbonylation
and carbonylation using the resulting carbonyl moiety through the
CO-relay from a ruthenium to a palladium species, respectively.
The present catalysis represents the first example of a transfer
carbonylation in which simple (non-designed) aldehydes are used
as CO donors through a CO-relay between two discrete transition
metal complexes.
Our previous reports on the CO gas-free cyclocarbonylation
of haloarenes having a carbon-nucleophile moiety with aldehydes
clarified that the use of a single rhodium(I) complex, [RhCl(cod)]2,
catalyzes the transfer a carbonyl group from 2-naphthaldehyde to
the iodobenzene derivative 1a to give the cyclocarbonylated
product 2 and more available bromo-derivative 1b is not
carbonylated (Scheme 1a and b).[11],[12] We began our study with
the reaction of bromobenzene 1b containing a malonate-
nucleophile with an aldehyde with the goal of achieving CO gas-
free cyclocarbonylation. The use of Pd(dppp)2 as a singly catalyst
resulted in no formation of 2, similar to that for of
[RhCl(cod)]2/dppp (b and c). Taking into account that Rh(I) and
Pd(0) complxes are effective for the decarbonylation of aldehydes
and the carbonylation of haloarenes, such as Heck-type
amidation and esterification reactions, respectively, we adopted a
strategy in which Rh(I) and Pd(0) complexes are used
simultaneously as cooperative catalysts. Catalytic conditions
consisting of [RhCl(cod)]2, Pd(dppp)2, and dppp (1,3-
bis(diphenylphosphino)propane) catalysed the reaction of 1b with
2-naphthaldehyde to give the indanone derivative 2 in 85% yield
(d). The carbonylation was found to be catalyzed only by the
mixed complexes of [RhCl(cod)]2/dppp and Pd(dppp)2. In addition,
under the above catalytic conditions, chlorobenzene 1c, which is
the most available but most unreactive substrate among the
analogues, could be catalytically transformed into 2 although in
low yield (23%) (e). The use of large excess of the aldehyde (5
eq) is not essential for the catalysis. Thus, although the reaction
of 1b (0.50 mmol) with 2 eq of 2-naphthaldehyde (1.0 mmol)
under the above catalytic conditions for 6 h did not complete, the
desired product 2 in 60% yield was obtained.
Transition-metal-catalyzed carbonylation is a powerful method for
the straightforward construction of a wide variety of carbonyl
functionalities.[1] Recent notable progress in the field is the
elimination of the need for the direct use of carbon monoxide, and,
novel substitutes for CO continue to grow.[2],[3] Thus, the use of
various organic and inorganic carbonyl-containing compounds as
a substitute for carbon monoxide (CO) allows CO gas-free
carbonylation reactions to be carried out. These reactions involve
the in and ex situ-generation of a carbonyl unit from the
substituent (decarbonylation) followed by the incorporation of the
resulting carbonyl unit into
a
carbonylated substrate
(carbonylation). Aldehydes, including formaldehyde, represent
one of the more interesting substitutes for CO in such transfer
carbonylation reactions, from the aspect of the availability and the
ease of handling of the donor molecule.[4],[5] The methodology is
based on two cooperative catalytic processes, the
decarbonylation of aldehydes by a transition metal catalyst, such
as Rh(I), Ir(I), Ru(II), or a Pd(0) complex, and the subsequent
introduction of the resulting carbonyl moiety into a substrate by
the catalyst. Single catalysts have been used for both the
decarbonylation and the carbonylation processes. The
simultaneous use of two discrete catalysts suitable for each
process, however, permits the the transfer carbonylation method
using aldehydes to be extended to wider type of carbonylation
reactions. We have also reported on other catalyst systems that
can be used in this type of reaction. These include a combination
of a phosphine-ligated rhodium(I) for decarbonylation and a
phosphine-free rhodium(I) for carbonylation,[6] two types of
rhodium(I) catalysts that contain two discrete phosphines,[7] and
[a]
Prof. Dr. T. Morimoto, M. Yamashita, A. Tomiie, Prof. Dr. K. Kakiuchi
Division of Materials Science
Nara Institute of Science and Technology (NAIST)
Ikoma, Nara 630-0192, Japan
E-mail: morimoto@ms.naist.jp
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the document.
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a carbonyl source was investigated. When atmospheric CO was
used, the rhodium catalyst system, [RhCl(cod)]2/dppp, gave no
cyclocarbonylated product 2 (Scheme 2a), while the palladium
complex, Pd(dppp)2, catalyzed the same transformation efficiently
to give the product 2 in a similar yield as was obtained when both
of them were simultaneously used in the reaction with 2-
naphthaldehyde as a carbonyl source (b).[11] These results
indicate that the presence of a carbonyl moiety, carbon monoxide
itself, or a carbonyl ligand enables the palladium complex to
catalyze the cyclocarbonylation process.
Scheme 1. Rh(I)/Pd(0)-Hybrid Catalyst Leads to Transfer Carbonylation of 1
with 2-naphthaldehyde.
The ability of various aldehydes to donate their carbonyl group
was also investigated: pentafluorobenzaldehyde (entry 2), p-
trifluoromethylbenzaldehyde (entry 3), benzaldehyde (entry 4), p-
anisaldehyde (entry 5), trans-cinnamaldehyde (entry 6),
hydrociinamaldehyde (entry 7), and paraformaldehyde (entry 8)
and the results are summarized in Table 1. Regardless of the
electronic nature of the substituent in the aromatic ring of the
aromatic aldehyde, all of the examined aldehydes functioned as
a carbonyl donor.[13] The CO-donation ability from each aldehyde
should depend on both how easy it is decarbonylated and it
suffers from the nucleophilic attack by the malonate moiety to give
an alcohol, which cannot be decarbonylated. As a result, the
electronic and/or steric property of aldehydes does not directly
contribute to their CO-donation ability. It is particularly noteworthy
that the use of 2-naphthaldehyde and paraformaldehyde as
carbonyl sources led to the formation of 2 in high yields (Table 1,
entries 1 and 8).
Scheme 2. Reactions of 1b with CO (1 atm).
It was found that the abstracted CO is incorporated effectively
into the product. The reaction of the bromobenzene derivative 1b
(0.50 mmol) with 2-naphthaldehyde (2.5 mmol) afforded the
carbonylated product 2 (0.41 mmol) in 80% yield (83% GC yield),
along with the decarbonylated product, naphthalene (0.49 mmol)
(Scheme 3). The majority (84%) of the CO groups that were
abstracted from the aldehyde were utilized in the carbonylation
step. The profile of this reaction also showed that the transfer of
the carbonyl moiety from the aldehyde to the substrate takes
place efficiently (Figure 1).[14]
Table 1. Investigation on Ability of Aldehydes as a CO Source[a]
Entry
Aldehyde
Conversion
Yield of 2[b]
1
2
3
4
5
6
7
8
2-Naphthaldehyde
C6F5CHO
100%
33%
100%
57%
65%
61%
84%
96%
85%
22%
15%
41%
47%
19%
38%
58%
p-CF3-C6H4CHO
PhCHO
Scheme 3. Transfer Cyclocarbonylation of 1b with 2-naphthalene.
p-MeO-C6H4CHO
(E)-PhCH=CHCHO
PhCH2CH2CHO
(CH2O)n
[a] Reaction conditions: 1b (0.5 mmol), aldehyde (2.5 mmol), [RhCl(cod)]2
(2.5 mol%), dppp (5.5 mol%), Pd(dppp)2 (5.0 mol%), and K2CO3 (1.0 mmol)
in xylene (2 mL) at 130 °C for 6 h. [b] Isolated yield.
In order to elucidate role of rhodium and palladium in the
catalytic process, carbonylation reactions of 1b using CO gas as
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We next examined the Rh(I)-catalyzed reactions of various
substrates with 2-naphthaldehyde or paraformaldehyde as a
carbonyl source under the standard conditions: bromide (0.5
mmol), aldehyde (2.5 mmol), [RhCl(cod)]2 (0.0125 mmol), dppp
(0.0275 mmol), Pd(dppp)2 (0.0250 mmol), and K2CO3 (1.0 mmol)
in xylene (2 mL) at 130 °C and the results are summarized in
Table 2. Only a malonate derivative could be used as a carbon-
nucleophile in the present catalysis, and the exchange of the
nucleophilic moiety to acetoacetate, benzenesulfonyl acetate, or
cyanoacetate afforded no corresponding cyclocarbonylated
product. The elongation of the carbon-chain linking a malonate-
nucleophilic part and a bromobenzene framework by one- or two
carbons (3 and 5) resulted in the formation of the corresponding
cyclic ketones 4 and 6, respectively (entries 3 and 5). The
0,5
0,4
0,3
0,2
0,1
0
Bromide 1b
Product 2
Naphthalene
0
100
200
300
400
500
Reaction Time (min)
Figure 1. Reaction Profile for the cyclocarbonylation of 1b with 2-naphthalene
to yield 2. Plots are the GC yields of 1b, 2, and naphthalene that are determined
using octadecane as an internal standard.
cyclocarbonylation of bromobenzene
7
having
a
MeO-
functionality on the aromatic ring proceeded smoothly to give the
indanone derivative 8 in 79% yield (entry 7). The present
transformation is not limited to bromobenzene derivatives as a
substrate. Bromoacene (naphthalene) 9, an alkene (cyclohexene)
11, and a heterocycle (thiophene) 13 having a malonate-
nucleophile were tolerated to the reaction conditions and were
transformed to the corresponding cyclocarbonylated products 10,
12, and 14, respectively (entries 9, 11, and 13). Although
paraformaldehyde was applicable as a carbonyl source instead of
2-bromonaphthalene to give the desired cyclocarbonylated
products, the reactions showed lower chemical yields than when
2-bromonaphthalene was used because reduced compounds of
the bromide were produced as byproducts (even number of
entries).
A possible reaction pathway for the present reaction, which
rationalizes the above results, is outlined in Scheme 4. The
reaction proceeds via the abstraction of a carbonyl moiety from
aldehydes by the Rh(I) catalyst, followed by the incorporation of
the resulting carbonyl group into bromobenzene 1b catalyzed by
Pd(0). The rhodium-catalyzed decarbonylation process begins
with the oxidative addition of the aldehyde C-H to a CO ligand-
free rhodium(I) complex, followed by the migratory extrusion of
the carbonyl in the acyl ligand and the reductive elimination of the
organic ligand to give the rhodium(I) carbonyl species, Rh-CO,
and the decarbonylated product, ArH.[15] According to the above
results (Scheme 3 and Figure 1), Rh-CO would relay its CO ligand
directly to a palladium complex in most cases (83%) and would
release it in the form of free carbon monoxide in other cases
(17%) to regenerate a CO ligand-free rhodium(I) complex, which
has the ability to decarbonylate aldehydes. On the other hand, the
palladium(0)-loaded complex is transformed to a five-membered
palladacyle via the oxidative addition of a C-Br bond of 1b and the
subsequent intramolecular transmetalation of the deprotonated
malonate part. It receives the CO ligand from the rhodium-
catalyzed decarbonylation process, followed by its insertion into a
C(sp3)-Pd bond,[16] to afford an acyl-palladium intermediate.
Finally, product 2 is reductively eliminated, accompanied by the
regeneration of a palladium(0) complex. During the overall
catalysis, these two processes that involve two discrete types of
transition metals function cooperatively without interfering with
each other, resulting in a CO gas-free cyclocarbonylation reaction.
Table 2. Rh(I)/Pd(0)-Catalyzed CO gas-free Cyclocarbonylation of Various
Bromides[a]
Entry
1
Bromide
RCHO[b]
A
Time
6 h
Product
Yield[c]
85%
1 (E = CO2Et)
2
2
2
3
1
B
A
8 h
6 h
65%
83%
4
4
3
3
4
5
B
A
12 h
4 h
44%
57%
5
5
6
6
6
7
B
A
10 h
5 h
22%
79%
7
7
8
8
8
9
B
A
11 h
15 h
47%
74%
9
10
Scheme 4. Outline of a Plausible Reaction Pathway.
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Keywords: transfer carbonylation • dual catalysis •
intramolecular cyclocarbonylation • aldehydes • indanones
10
9
B
12 h
6 h
10
57%
80%
11
A
[1]
For recent books and reviews on carbonylation, see: a) M. Beller,
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Sasikumar, K. V. radhakrishnan, P. Das, Org. Biomol. Chem. 2019, 17,
5212-5222.
11
11
12
12
12
13
B
A
8 h
5 h
67%
74%
13
13
14
14
14
B
10 h
8%
[2]
[a] Reaction conditions: bromide (0.5 mmol), aldehyde (2.5 mmol),
[RhCl(cod)]2 (2.5 mol%), dppp (5.5 mol%), Pd(dppp)2 (5.0 mol%), and K2CO3
(1.0 mmol) in xylene (2 mL) at 130 °C for 6 h. [b] A: 2-naphthaldehyde; B
paraformaldehyde. [c] Isolated yield.
In conclusion, we report on the CO gas-free
cyclocarbonylation reaction of haloarenes having a carbon-
nucleophile using aldehydes as a carbonyl source. The reaction
is catalysed by two discrete complexes, Rh(I) and Pd(0), which
are responsible for the decarbonylative degradation of aldehydes
and the introduction of the resulting carbonyl moiety via the CO-
relay from Rh(I) to Pd(0), respectively. These two catalysts
function cooperatively without interfering with each other,
resulting in an overall CO gas-free carbonylation. This represents
the first successful demonstration of a CO gas-free carbonylation
reaction including a CO-relay between discrete transition-metal
complexes in carbonylation reactions using aldehydes as a
carbonyl source. The present findings, showing that a number of
readily available carbonyl sources can be used, indicate that this
[3]
For recent reports on catalytic carbonylation without the direct use of CO,
see: a) B. Bartal, G. Mike, L. Kollár, P. Pongrácz, Mol. Catal. 2019, 467,
143-149 (fomic acid); b) D. P. Chen, J. Z. Yao, L. L. Chen, L. F. Hu, X.-
F. Li, H. W. Zhou, Org. Chem. Forntiers, 2019, 6, 1403-1408 (formate);
c) Shaifali, S. Ram, V. Thakur, P. Das, Org. Biomol. Chem. 2019, 17,
7036-7041 (oxalic acid); d) V. V. Gaikwad, P. A. Mane, S. Dey, B. M.
Bhanage, Chemistryselect, 2019, 4, 8269-8276 (Co2(CO)8); e) R.
Pittaway, P. Dingwall, J. A. Fuentes, M. L. Clarke, Adv. Synth. Catal.
2019, 361, 4334-4341 (formaldehyde); f) D. Z. Yu, F. N. Xu, D. Li, W.
Han, Adv. Synth. Catal. 2019, 361, 3102-3107 (N-formylsaccharin); g) L.
Y. Fu, J. Ying, X.-F. Wu, J. Org. Chem. 2019, 84, 12648-12655 (formate).
Our first report on transfer carbonylation using aldehydes as a substitute
for CO, see: T. Morimoto, K. Fuji, K. Tsutsumi, K. Kakiuchi, J. Am. Chem.
Soc. 2002, 124, 3806-3087.
is
a straightforward process for producing a variety of
carbonylative transformations.
[4]
[5]
[6]
Experimental Section
General Procedure for the Cyclocarbonylation of Bromoarenes with
Aldehydes: To a 10 mL two-necked flask equipped with a reflux
condenser and a 2 L gas-bag were placed [RhCl(cod)]2 (0.0125 mmol,
6.21 mg), dppp (0.0275 mmol, 11.70 mg), Pd(dppp)2 (0.025 mmol, 23.29
mg), K2CO3 (1.0 mmol, 138.21 mg), an aldehyde (2.5 mmol), the substrate
(0.5 mmol), and xylene (2 mL) under a flow of nitrogen. The mixture was
degassed by three freeze-pump-thaw cycles, and purged with nitrogen.
The mixture was stirred at 130 °C in an oil-bath until the substrate was
consumed. The progress of the reaction was monitored by GC or TLC.
After the substrate was consumed, water was added to the reaction
mixture and the organic solution was separated. The aqueous solution was
extracted with Et2O, and the combined organic solution was dried over
MgSO4. After removing the MgSO4 by filtration, the filtrate was
concentrated in vacuo, and the residue was purified by column
chromatography on silica-gel.
Shibata et al. reported the similar method for transfer carbonylation using
aldehydes as a substitute for CO at the almost same time with us, see:
T. Shibata, N. Toshida, K. Takagi, Org. Lett. 2002, 4, 1619-1621.
a) T. Morimoto, K. Yamasaki, A. Hirano, K. Tsutsumi, N. Kagawa, K.
Kakiuchi, Y. Harada, Y. Fukumoto, N. Chatani, T. Nishioka, Org. Lett.
2009, 11, 1777-1780; b) C. Wang, T. Morimoto, H. Kaneshiro, H.
Tanimoto, Y. Nishiyama, K. Kakiuchi, L. Artok, Synlett, 2014, 25, 1155-
1159.
[7]
a) G. Makado, T. Morimoto, Y. Sugimoto, K. Tsutsumi, N. Kagawa, K.
Kakiuchi, Adv. Synth. Catal. 2010, 352, 299-304; b) J. Pan, T. Morimoto,
H. Kobayashi, H. Tanimoto, K. Kakiuchi, Heterocycles, 2019, 98, 519-
533.
[8]
[9]
T. Furusawa, T. Morimoto, K. Ikeda, H. Tanimoto, Y. Nishiyama, K.
Kakiuchi, N. Jeong, Tetrahedron, 2015, 71, 875-881.
It was reported that a similar transformation using phenyl formate as a
CO source is catalysed by only a palladium catalyst. In this method, the
singly loaded palladium catalyst captures free CO to which phenyl
formate is decarbonylatively decomposed under the strong basic
conditions, and carbonylates a substrate. H. Konishi, K. Manabe, Chem.
Commun. 2015, 51, 1854-1857.
Acknowledgements
This work was financially supported, in part, by a Grant-in-Aid for
Scientific Research on Innovative Area “Molecular Activation
Directed toward Straightforward Synthesis” (No. 25105737) from
the Ministry of Education, Culture, Sports, Science, and
Technology (MEXT). We wish to thank Ms. Mika Yamamura, Ms.
Yuriko Nishiyama, and Ms. Yoshiko Nishikawa for assistance in
obtaining HRMS.
[10] a) S. Ko, C. Lee, M.-G. Choi, Y. Na, S. Chang, J. Org. Chem. 2003, 68,
1607-1610; b) S. Ko, H. Han, S. Chang, Org. Lett. 2003, 5, 2687-2690.
[11] a) E.i. Negishi, Y. Zhang, I. Shimoyama, G. Wu, J. Am. Chem. Soc. 1989,
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Y. Zhang, G. Wu, J. M. Tour, Tetrahedron, 1994, 50, 425-436; c) E.i.
Negishi, H. Makabe, I. Shimoyama, G. Wu, Y. Zhang, Tetrahedron, 1998,
54, 1095-1106.
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[12] T. Morimoto, M. Fujioka, K. Fuji, K. Tsutsumi, K. Kakiuchi, J. Organomet.
Chem. 2007, 692, 625-634.
[13] Our previous report showed that aldehydes having higher electron-
withdrawing substituents donate their carbonyl more efficiently. See ref.
3 and the following papers: a) F. Calderazzo, Angew. Chem. 1977, 89,
283-350; Angew. Chem. Int., Ed. Engl. 1977, 16, 299-311; b) P. Fristrup,
M. Kreis, A. Palmelund, P.-O. Norrby, R. Madsen, J. Am. Chem. Soc.
2008, 130, 5206-5215.
[14] Similar findings were found in the transfer cyclocarbonylation reaction of
enynes with 2-naphthaldehyde. See ref. 3.
[15] For the first report on stoichiometric decarbonylation of aldehydes, see:
a) J. Tsuji, K. Ohno, Tetrahedron Lett. 1965, 3969-3971; for recent
papers on catalytic decarbonylation of aldehydes, see: b) T. C. Fessard,
S. P. Andrews, H. Motoyoshi, E. M. Carreira, Angew. Chem. 2007, 119,
9492-9495; Angew. Chem. Int. Ed. 2007, 46, 9331-9334; c) T. Iwai, T.
Fujiwara, Y. Tsuji, Chem. Commun. 2008, 6215-6217; d) A. Modak, A.
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4253-4255.
[16] P. E, Garrou, R. F. Heck, J. Am. Chem. Soc. 1976, 98, 4115-4127.
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Tsumoru Morimoto,* Mana Yamashita,
Ai Tomiie, Hiroki Tanimoto, Kiyomi
Kakiuchi
Page No. – Page No.
CO Gas-free Intramolecular
Cyclocarbonylation Reaction of
Haloarenes Having a C-Nucleophile
through CO-Relay between Rhodium
and Palladium
Rh(I)/Pd(0)-hybrid catalytic system catalyzes the transfer carbonylation reaction of
haloarenes having a carbon-nucleophile using aldehydes as a substitute for CO,
leading to the formation of indanone derivatives. Rh(I) and Pd(0) are responsible for
the decarbonylation of aldehydes and the subsequent carbonylation of haloarenes
using the resulting carbonyl moiety, respectively. The majority of the abstracted CO
is ransferred directly to the product via CO-relay from the rhodium to the palladium.
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