Rhodium(I)-Catalyzed Carbonylative Annulation of Iodobenzenes with Strained Olefins and 4-Octyne in the Presence of Furfural Involving ortho-C–H Bond Cleavage

Article abstract of DOI:10.1002/adsc.201601056

The rhodium(I)-catalyzed carbonylative annulation of iodobenzenes with strained olefins in the presence of furfural as a carbonyl source, accompanied by ortho-C–H bond cleavage, is reported. The use of 4-octyne in place of strained olefins also leads to the formation of the corresponding inden-9-one. The timely release of the carbonyl moiety via the rhodium-catalyzed decarbonylation of furfural plays a decisive role in this reaction. (Figure presented.).

Full text of DOI:10.1002/adsc.201601056

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DOI: 10.1002/adsc.201601056
Rhodium(I)-Catalyzed Carbonylative Annulation of Iodoben-
zenes with Strained Olefins and 4-Octyne in the Presence of
Furfural Involving ortho-C–H Bond Cleavage
a
a
a
Takuma Furusawa, Hiroki Tanimoto, Yasuhiro Nishiyama,
a,
a,
Tsumoru Morimoto, * and Kiyomi Kakiuchi *
Graduate School of Materials Science, Nara Institute of Science and Technology (NAIST), 8916-5 Takayama-cho, Ikoma,
Nara 630-0192, Japan
a
Fax : (+81)-743-72-6081; e-mail: morimoto@ms.naist.jp or kakiuchi@ms.naist.jp
Received: September 23, 2016; Revised: October 24, 2016; Published online: && &&, 0000
Supporting information for this article can be found under: http://dx.doi.org/10.1002/adsc.201601056.
Abstract: The rhodium(I)-catalyzed carbonylative
annulation of iodobenzenes with strained olefins in
the presence of furfural as a carbonyl source, ac-
companied by ortho-C–H bond cleavage, is report-
ed. The use of 4-octyne in place of strained olefins
also leads to the formation of the corresponding
inden-9-one. The timely release of the carbonyl
moiety via the rhodium-catalyzed decarbonylation
of furfural plays a decisive role in this reaction.
these procedures have a problem from the viewpoint
of atom- and step-economy, and waste generation;
the preparation of 2-halophenylboronic acids is gener-
[
6]
ally a multistep process. Therefore, the straightfor-
ward functionalization at a C–H bond of simple hal-
[
7]
oarenes is an ideal method. In this context, Grigg in
fact reported that 2-iodothiophene reacts with 2-nor-
bornene and carbon monoxide in the presence of
a palladium catalyst to furnish the cyclic carbonyl
compound through C–H metallation at the C-3 posi-
[8]
Keywords: carbonylative annulation; C–H function-
alization; furfural; rhodium catalyst; three-compo-
nent reactions
tion of the thiophene [Scheme 1A, Eq. (1)]. Even
though the palladacycle formation and the subsequent
[9]
transformation have been extensively studied, the
reaction of halobenzene and 2-norbornene with
carbon monoxide failed to produce an annulated car-
[
10]
bonyl compound [Eq. (2)].
To the best of our
knowledge, the carbonylative annulation of haloben-
The transition metal-catalyzed three-component car- zenes via C–H bond cleavage remains an undevel-
bonylative annulation of ortho-functionalized aryl hal- oped area.
ides, p-unsaturated compounds, such as alkynes and
During the course of our studies on the direct cata-
[11]
olefins, and carbon monoxide is an attractive method lytic carbonylation reactions of C–H bonds, we fo-
[
1]
for preparing cyclic carbonyl-containing compounds
cused on the fact that the following rhodium species, I
which are found in a wide variety of natural products and II, can cyclize, along with the cleavage of a C–H
[
2]
and pharmaceutically important compounds. While bond, followed by the insertion of a carbonyl moiety,
significant efforts have been devoted to developing to form benzene ring-fused cyclopenta(e)none frame-
the concise synthesis of heterocyclic carbonyl com- works. An elegant work by Miura and co-workers
pounds, only a few examples of three-component car- showed that the rhodium complex catalyzes the direct
bonylative annulation for the synthesis of carbocyclic C–H cyclization of benzoyl chlorides with internal al-
[
12]
carbonyl compounds such as indenones and inda- kynes and 2-norbornene (Scheme 1B).
In that
[
3]
nones have been reported in the literature. In 2007, report, the complex I was proposed as the key inter-
the first report, the rhodium-catalyzed carbonylative mediate. We recently developed the intramolecular
cyclization of 2-halophenylboronic acids with alkynes carbonylative coupling of 2-iodobiphenyl with furfural
[
13]
or 2-norbornene under atmospheric carbon monoxide, produced from biomass resources
as a carbonyl
[
4]
was published by Chataniꢀs group. Later, our group source via the formation of 2-rhodabiphenyl II, which
demonstrated that paraformaldehyde can be used as is analogous to complex I, to give fluoren-9-one
[
5]
[11b]
a carbonyl source in this transformation. Although (Scheme 1C).
These findings encouraged us to in-
high yields of the desired products could be achieved, vestigate the three-component carbonylative annula-
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[a]
Table 1. Optimization of the reaction conditions.
[b]
Entry
Deviation from standard conditions
Yield
1
2
3
4
5
6
7
8
9
none
no [RhCl(C H )]
[RhCl(cod)] as catalyst precursor
no BINAP
10 mol% of BINAP
(R)-BINAP
DPPP as ligand
BIPHEP as ligand
no base
80%
0%
31%
15%
6%
78%
62%
72%
20%
60%
70%
65%
40%
77%
31%
2
4
2
2
c]
[
[c]
[c]
[d]
[
e]
[f]
10
11
12
13
14
15
Na CO as base
2
3
MesCO Na as base
no LiCl
dioxane as solvent
1008C in toluene
2
(CH O) as carbonyl source
2
n
[a]
Standard reaction conditions: 1a (0.5 mmol), 2a
(
2.5 mmol),
furfural
(2.5 mmol),
[RhCl(C H ) ]
2 4 2 2
(
0.025 mmol), BINAP (0.025 mmol), NaOPiv (1.0 mmol),
LiCl (0.1 mmol), and xylene (1 mL) at 1308C for 20 h.
b]
[
[
[
[
[
Isolated yield.
c]
d]
e]
f]
2
2
1
2
,2’-Bis(diphenylphosphino)-1,1’-binaphthyl.
% ee.
,3-Bis(diphenylphosphino)propane.
,2’-Bis(diphenylphosphino)-1,1’-biphenyl.
(
1
1.0 mmol), and LiCl (0.1 mmol) in xylene (1 mL) at
308C for 20 h to afford 3aa in 80% yield (Table 1,
Scheme 1. Carbonylative annulation involving C–H bond
cleavage.
entry 1). Removing the rhodium catalyst from the cat-
alytic system resulted in no formation of the desired
tion of iodobenzenes, unsaturated hydrocarbons, and product (entry 2). When using [RhCl(cod)] instead of
2
a
carbonyl moiety using
a
rhodium catalyst [RhCl(C H ) ] , the product yield remarkably dimin-
2 4 2 2
[12a]
(
Scheme 1D). The present paper describes the suc- ished (entry 3).
The addition of 0.5 equivalent of
BINAP to the rhodium center gave the highest yield
cessful realization of this transformation.
Our initial studies focused on the carbonylative an- of 3aa, suggesting that both BINAP-ligated and
nulation of iodobenzene (1a) with 2-norbornene (2a). BINAP-free rhodium species play a crucial role in the
In this examination, we used, not gaseous carbon decarbonylation of furfural and the subsequent car-
monoxide, but rather furfural as the carbonyl source, bonylative annulation of 1a with 2a, respectively (en-
[
5,12]
because of the difficulty arising from the chemical tries 1, 4, and 5).
The use of (R)-BINAP gave
[
14]
[15]
and physical properties of carbon monoxide. In ad- quite low enantiomeric excess (2% ee).
Other bi-
dition, it was anticipated that large amounts of carbon dentate phosphanes also showed activity as a ligand,
monoxide in the reaction system would interfere with albeit the yield of 3aa was slightly lower (entries 7
the coordination and the oxidative addition of sub- and 8). In sharp contrast to Miuraꢀs report, it was nec-
[
11b]
strates to a rhodium center.
tigations of reaction parameters, we determined the reaction (entry 9).
following optimal reaction conditions: 1a (0.5 mmol), ined, NaOPiv was found to be the best choice (en-
a (2.5 mmol), furfural (2.5 mmol), [RhCl(C H )] tries 10 and 11). The absence of LiCl retarded the
NaOPiv progress of the reaction (entry 12). It can be assumed
After extensive inves- essary to add a base in order to achieve an efficient
[
15]
[12a]
Among the various bases exam-
2
2
4
2
(
0.025 mmol),
BINAP
(0.025 mmol),
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that the rhodate species generated by the coordina- Table 2. Scope of the rhodium-catalyzed carbonylative annu-
[a]
lation.
tion of a chloride to the rhodium center permits
a more facile oxidative addition of the C–I bond.
[
16]
Changing the solvent away from xylene led to a signif-
icant loss in the efficiency of the reaction (entry 13).
The reaction also proceeded smoothly in toluene at
1008C to afford the corresponding compound in 77%
yield (entry 14). Paraformaldehyde, which has great
advantages in terms of cost and atom economy in
comparison with other reported carbonyl surro-
[17,18]
gates,
was tested as a carbonyl source (entry 15).
However, the formation of substantial amounts of
side products, such as biphenyl, benzophenone, and
benzoic acid, caused a low yield of the desired prod-
uct 3aa.
Having optimized the reaction conditions, we inves-
tigated the scope and limitations of halobenzenes and
strained olefins (Table 2). Bromobenzene (1b)
showed a much lower reactivity for this carbonylation
(
entry 2). 4-Substituted iodobenzenes (1c–e) were
able to react with 2a to produce the corresponding in-
danones in moderate to good yields (entries 3–5). The
carbonylative annulation of 3-substituted iodoben-
zenes (1f and g) also proceeded efficiently with exclu-
sive site selectivity (entries 6 and 7). On the other
hand, 2-substituted iodobenzenes such as 2-iodoto-
luene (1h) and 2-iodoanisole (1i) were barely convert-
ed into the desired products under the standard reac-
tion conditions, probably due to steric hindrance. The
use of Na CO , which is an effective base for the in-
2
3
[
11]
tramolecular carbonylation of 2-iodobiphenyls,
in
place of NaOPiv gave 3ha in 16% yield. Furthermore,
when 2-substituted iodobenzenes were reacted with
2a and furfural at 1508C, 3ha and 3ia were obtained
in moderate yields (entries 8 and 9). Benzonorborna-
diene (2b) was applicable to the transformation to
afford 3ab in 74% yield (entry 10). Unfortunately, the
reaction of 1a with 2,5-norbornadiene (2c) provided
an unidentified and inseparable complex mixture
(
entry 11). With cyclohexene and styrene, Mizoroki–
Heck-type reactions occurred leading to no formation
[
12a,16b]
of indanone products.
The synthesis of 2,3-dipropylinden-1-ones (5aa and
ca) was also achieved when 4-octyne (4a) was em-
ployed in place of 2a (Scheme 2). However, the for-
[
12b,19]
mation of naphthalene derivatives
as side reac-
[a]
Reaction conditions: 1 (0.5 mmol), 2 (2.5 mmol), furfural
tion products led to moderate yields of the desired in-
denones. The use of diphenylacetylene (4b) dramati-
cally lowered the efficiency of the reaction, and 63%
of 4b was recovered from the reaction mixture, al-
though 2-iodo-1,1,2-triphenylethylene reacted with
(
2.5 mmol), [RhCl(C H ) ]
(0.025 mmol), BINAP
2
4 2 2
(
0.025 mmol), NaOPiv (1.0 mmol), LiCl (0.1 mmol), and
xylene (1 mL) at 1308C for 20 h.
Isolated yield.
[
[
b]
c]
The reaction was carried out at 1508C using Na CO in-
2
3
[
20]
furfural to produce 5ab in 72% yield. This can be
attributed to the stronger back donation from rhodi-
um to 4b than with 2a and 4a resulting in the stabili-
zation of the rhodium(I) complex and the inhibition
stead of NaOPiv.
[
d]
2
b (1.5 mmol) was employed.
[
21]
of the oxidative addition of iodobenzene.
We then conducted some experiments to determine
the active catalyst for the carbonylative annulation.
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Scheme 2. Synthesis of inden-1-ones. Reaction conditions:
(0.5 mmol), 4a (1.0 mmol), furfural (2.5 mmol),
RhCl(C H ) ] (0.025 mmol), BINAP (0.025 mmol),
NaOPiv (1.0 mmol), LiCl (0.1 mmol), and xylene (1 mL) at
408C. Isolated yields are given.
Scheme 4. Deuterium labelling experiment.
1
[
2
4 2 2
A plausible catalytic cycle for the present reaction
1
[
11,12]
with 2-norbornene is illustrated in Scheme 5.
Rh(III) species B is generated via the oxidative addi-
The P NMR spectrum of the mixture containing tion of an iodobenzene to Rh(I) A, which is generat-
RhCl(C H ) ] and BINAP (0.5 equivalent to rhodi- ed in situ from [RhCl(C H ) ] and NaOPiv in the
The
31
[
2
4
2 2
2
4 2 2
um center) in toluene-d showed a sole signal at d= presence of 2-norbornene. The migratory insertion of
8
5
0.7 which correspond to [RhCl(binap)] . Thus, the the norbornene, followed by the transfer of a carbonyl
2
carbonylative annulation of 1a and 2a under a partial moiety via the decarbonylation of furfural catalyzed
[
25]
pressure of 0.5 atm of CO and 0.5 atm of N was ex- by the [Rh(OPiv)(binap)] complex, generates the
2
2
amined using [RhCl(C H ) ] and [RhCl(binap)]2 key intermediate C. This undergoes cleavage of a C–
2
4 2 2
(
Scheme 3). While [RhCl(C H ) ] gave the desired H bond at the ortho-position, furnishing the five-
2 4 2 2
membered rhodacycle D. Although details of the C–
[26]
H bond dissociation are unclear at present,
it is
likely that the pivalate as a ligand assists in the cleav-
[
27]
age of the C–H bond. The incorporation of the car-
bonyl moiety into D gives the acyl species E. Finally,
the annulated carbonyl product is liberated from E to
complete the catalytic cycle.
Scheme 3. Reaction with carbon monoxide.
product 3aa in 38% yield, [RhCl(binap)] , which has
2
higher activity for the decarbonylation of aldehydes
[
22]
than the phosphine-free rhodium complex,
was
found to be catalytically ineffective for this reaction.
According to our initial expectations, the reaction
under atmospheric carbon monoxide catalyzed by
[
RhCl(C H ) ] was considerably slower. This phe-
2 4 2 2
nomenon suggests that the timely release of the car-
bonyl moiety from furfural plays a decisive role in the
efficient reaction, consistent with findings in a previ-
[11b]
ous report.
The kinetic isotope effect (KIE) was investigated
by means of an intermolecular competition experi-
ment between 1a and 1a-d (Scheme 4). A KIE value
5
(
[P ]/[P ]) of 1.0 was obtained, indicating that cleav-
H D
age of the C–H bond is not the rate-determining
[
23,24]
step.
Considering our experimental observations
[
11b]
and a previous report,
we propose that oxidative
addition of the C–I bond is involved in the rate-deter-
mining step.
Scheme 5. Plausible catalytic cycle.
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In summary, we reported on the carbonylative an-
nulation of iodobenzenes, strained olefins or 4-octyne,
and using furfural as the carbonyl source, via ortho-
C–H bond cleavage leading to the formation of inda-
none and indenone derivatives. This carbonylative an-
nulation represents the first example of the three-
component carbonylative annulation of iodobenzenes
with unsaturated hydrocarbons involving C–H cleav-
age. Importantly, furfural rather than gaseous carbon
monoxide served as the carbonyl source. We expect
that the carbonylation method depending on the alde-
hydes will serve as a unique protocol for the develop-
ment of novel carbonylation reactions which are diffi-
cult to achieve by the traditional method using gas-
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[
28]
eous carbon monoxide.
[
6] Although some concise methods for preparing 2-halo-
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Experimental Section
Typical Procedure for the Rh-Catalyzed
Carbonylative Annulation of Iodobenzene, 2-
Norbornene, and Furfural
A 10-mL dry sealed tube equipped with a stir bar was
charged with [RhCl(C H ) ] (0.025 mmol, 9.72 mg), BINAP
2
4 2 2
(
0.025 mmol, 15.57 mg), NaOPiv (1.0 mmol, 124.11 mg),
LiCl (0.1 mmol, 4.24 mg), and 2-norbornene (2.5 mmol,
35.40 mg) under an N flow. Xylene (1 mL), iodobenzene
[
2
2
(
0.5 mmol, 102.01 mg), and furfural (2.5 mmol, 240.23 mg)
were then added. After degassing the reaction mixture by
the freeze-pump-thaw method three times, the tube was
filled with N . The mixture was then placed in an oil bath
2
that had been preheated to 1308C for 20 h. After cooling to
room temperature, the resulting solution was filtered
through a celite pad, and the filtrate was concentrated
under vacuum. The resulting crude product was purified by
flash column chromatography on silica gel (hexane/
EtOAc=20/1) to afford 3aa.
Acknowledgements
This study was partially supported by the NAIST Presidential
Special Fund.
[
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(0.25 mmol), furfural (1.25 mmol), [RhCl(cod)]2
(0.0125 mmol),
DPPP
(0.0125 mmol),
Na CO3
2
2
; c) S. Peleteiro, S. Rivas, J. A. Alonso, V. Santos, J. C.
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06, 94.
ylative coupling of 2-iodobiphenyls. See: ref.
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[21] The fact that the reaction of 1a (0.5 mmol) and 2a
(2.5 mmol) with furfural (2.5 mmol) in the presence of
5b (2.5 mmol) gave 18% yield of 3aa and trace amount
of 5ab supports our conclusions.
5
580; b) M. Larhed, L. Odell, F. Russo, Synlett 2012,
2
3, 685; c) L. Wu, Q. Liu, R. Lackstell, M. Beller,
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1
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15] See the Supporting Information for details.
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[
[
[25] After the solution of [RhCl(binap)] [d=50.7 (d, J
=
2
Rh,P
194.93 Hz)] in toluene-d was treated with NaOPiv and
8
the resulting solution allowed to stand at 1008C for 4 h,
3
1
the P NMR spectrum showed the appearance of
a new complex which corresponded to [Rh(OPiv)(bi-
nap)] [d=56.3 (d, J =194.93 Hz)].
4
820; Angew. Chem. Int. Ed. 2003, 42, 4672.
[
[
17] X.-F. Wu, Adv. Synth. Catal. 2015, 357, 3393.
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Rh,P
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E
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1
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6
1
0410. Rh: f) S. P. Midya, M. K. Sahoo, V. G. Landge,
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2
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Adv. Synth. Catal. 0000, 000, 0 – 0
6
ꢁ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

COMMUNICATIONS
Rhodium(I)-Catalyzed Carbonylative Annulation of
Iodobenzenes with Strained Olefins and 4-Octyne in the
Presence of Furfural Involving ortho-C–H Bond Cleavage
7
Adv. Synth. Catal. 2017, 359, 1 – 7
Takuma Furusawa, Hiroki Tanimoto, Yasuhiro Nishiyama,
Tsumoru Morimoto,* Kiyomi Kakiuchi*
Adv. Synth. Catal. 0000, 000, 0 – 0
7
ꢁ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!