Phosphine-free NiBr2-catalyzed synthesis of unsymmetrical diaryl ketones via carbonylative cross-coupling of aryl iodides with Ph3SnX (X = Cl, OEt)

Article abstract of DOI:10.1016/j.jorganchem.2015.05.038

Abstract The convenient nickel-catalyzed carbonylative coupling of aryl iodides with Ph₃SnCl or Ph₃SnOEt for synthesis of unsymmetrical diaryl ketones under phosphine-free condition is reported. The reaction occurs efficiently in the presence of Cr(CO)₆ as an easy handling solid source of carbon monoxide at atmospheric pressure and 100 °C in DMF under air to deliver the desired ketones in high yield.

Full text of DOI:10.1016/j.jorganchem.2015.05.038

Accepted Manuscript
Phosphine-Free NiBr -Catalyzed Synthesis of Unsymmetrical Diaryl Ketones via
2
Carbonylative Cross-Coupling of Aryl Iodides with Ph SnX (X = Cl, OEt)
3
Nasser Iranpoor, Habib Firouzabadi, Elham Etemadi-Davan
PII:
S0022-328X(15)30008-5
10.1016/j.jorganchem.2015.05.038
JOM 19079
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 5 February 2015
Revised Date: 8 May 2015
Accepted Date: 23 May 2015
Please cite this article as: N. Iranpoor, H. Firouzabadi, E. Etemadi-Davan, Phosphine-Free NiBr -
2
Catalyzed Synthesis of Unsymmetrical Diaryl Ketones via Carbonylative Cross-Coupling of Aryl
Iodides with Ph SnX (X = Cl, OEt), Journal of Organometallic Chemistry (2015), doi: 10.1016/
3
j.jorganchem.2015.05.038.
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ACCEPTED MANUSCRIPT
Graphical Abstract Synopsis
Phosphine-Free NiBr -Catalyzed Synthesis of Unsymmetrical Diaryl Ketones
2
via Carbonylative Cross-Coupling of Aryl Iodides with Ph SnX (X = Cl, OEt)
3
Nasser Iranpoor*, Habib Firouzabadi*, Elham Etemadi-Davan
Department of Chemistry, College of Sciences, Shiraz University, Shiraz, Iran
Corresponding author: Tel.: +98-711-2287600; fax: +98-711-2280926;
E-mail: iranpoor@chem.susc.ac.ir (N. Iranpoor); firouzabadi@chem.susc.ac.ir (H. Firouzabadi)
The convenient nickel-catalyzed carbonylative coupling of aryl iodides with organostannanes for
synthesis of unsymmetrical diaryl ketones under phosphine-free condition is reported. The
reaction occurs efficiently applying Cr(CO) as an easy handling solid source of carbon
6
monoxide at atmospheric pressure in DMF to deliver the desired ketones in high yield.

ACCEPTED MANUSCRIPT
Phosphine-Free NiBr -Catalyzed Synthesis of Unsymmetrical Diaryl Ketones
2
via Carbonylative Cross-Coupling of Aryl Iodides with Ph SnX (X = Cl, OEt)
3
Nasser Iranpoor*, Habib Firouzabadi*, Elham Etemadi-Davan
Department of Chemistry, College of Sciences, Shiraz University, Shiraz, Iran
Corresponding author: Tel.: +98-711-2287600; fax: +98-711-2280926;
E-mail: iranpoor@chem.susc.ac.ir (N. Iranpoor); firouzabadi@chem.susc.ac.ir (H. Firouzabadi)
Abstract: The convenient nickel-catalyzed carbonylative coupling of aryl iodides with Ph SnCl
3
or Ph SnOEt for synthesis of unsymmetrical diaryl ketones under phosphine-free condition is
3
reported. The reaction occurs efficiently in the presence of Cr(CO) as an easy handling solid
6
o
source of carbon monoxide at atmospheric pressure and 100 C in DMF under air to deliver the
desired ketones in high yield.
Keywords:
Cr(CO)6
NiBr2
Ph SnCl or Ph SnOEt
3
3
Unsymmetrical Ketone
Aryl halide

ACCEPTED MANUSCRIPT
1
.
Introduction:
The catalytic cross-coupling reaction between aryl electrophiles and organometallic nucleophiles
accompanied by insertion of carbon monoxide offers symmetrical or unsymmetrical diaryl
ketones [1]. Typical strategies for synthesizing diaryl ketones includes the reaction of activated
carboxylic acid derivatives with organostannanes and Grignard reagents[2]; cross-coupling of
aromatic aldehydes with aryl halides [3]; and the Friedel-Crafts acylation [4]. The Friedel-Crafts
acylation gives isomeric mixtures, and also requires more than stoichiometric amount of a Lewis
acid to perform the reaction. In this regard, the reactions in which several bonds could be formed
in one operation without the need for several steps of protection/deprotection or isolating the
intermediates is of great importance [5]. Therefore, carbonylative cross-coupling is a cascade
process and has the advantage of high chemoselectivity and high efficiency which eliminates the
application of carboxylic acid derivatives as carbon electrophiles, thus delivers
polyfunctionalized ketones [6].
Carbonylative Stille reaction is the three-component reaction of diverse organostannanes with
aryl or vinyl electrophiles which have been applied in the presence of carbon monoxide to give
unsymmetrical diaryl ketones [7]. Pd-catalyzed cross-coupling of various aryl, and vinyl
electrophiles with organostannanes in the presence of carbon monoxide have been reported [8].
In this reaction, the stoichiometric amount of organnostanes with the molecular formula of
n
RSnR’ (R : 2-naphthyl, Ph, pyrazinyl, alkenyl, alkynyl; R’ : Bu, Me) is needed for the reaction
3
to be completed [9], therefore it is valuable to substitute the organostannanes with a compound
that has the stoichiometric economy as a carbon nucleophile source. In addition, due to the
difficulty of handling of gaseous CO, a suitable substituent for CO is of great interest [10]. In
this regard, the application of metal carbonyls [11] and organic compounds [12] having carbonyl
in their structure have been developed. Recently, Nilsson have applied a Pd-catalyzed procedure
applying Mo(CO)
for synthesizing unsymmetrical ketones [13]. They used more than equimolar amount of the
Bu SnR as a carbon nucleophile for the cross-coupling with long reaction times (16 h). In
6
as the solid source of carbonyl in carbonylative Stille cross-coupling reaction
3
addition, all of the mentioned reactions are Pd-catalyzed transformation except the Ni(acac)2-
catalyzed carbonylative Stille reaction of aryl tri-n-buthylstannates with aryliodonium
tetraflouroborate as hypervalent iodine substrates[14].

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Lately, we reported Ph
3
SnCl as a new source of stoichiometric-economy carbon nucleophile
group for coupling with phenols, amines, and thiols and also for the Stille coupling of aryl
halides [15]. In continuation of our research on carbonylation reactions [16], we introduce a Ni-
catalyzed Stille carbonylative coupling of aryl halides with metal carbonyls as solid source of
CO. In these reactions, Ph SnX ( X= Cl, OEt) are used as stoichiometric-economy tin reagents.
3
2
.
Experimental:
3
Typical procedure for Ni-catalyzed Stille carbonylation of iodotoluene with Ph SnCl using
Cr(CO) in DMF at 100 ˚C:
6
4
-Iodotoluene (1.0 mmol, 0.21 g) was added to a flask equipped with Ph SnCl (0.4 mmol, 0.15
3
g), NiBr
2
(16.0 mol%, 0.034g), K
2
CO
3
(3.0 mmol, 0.29 g), and Cr(CO)
6
(1.0 mmol, 0.22g) in
DMF (3.0 mL) and the resulting mixture was heated in an oil bath at 100 ˚C and stirred for 2.7 h.
Progress of the reaction was monitored by TLC. After completion, the reaction mixture was
cooled to room temperature, then H
separatory funnel. The aqueous phase was further washed with EtOAc (3×10 mL) and the
combined organic phases were dried over anhydrous Na SO and then filtered. Column
2
O (10 mL) was added and the mixture was transferred to a
2
4
chromatography of the obtained residue on silica gel (n-hexane/EtOAc = 20:1) gave the desired
1
ketone in 89% yield (0.11 g) (Table 4, entry 2). H-NMR (250 MHz, CDCl ) δ(ppm):7.70-7.61
3
1
3
(
4H, m), 7.47-7.44 (m, 1H), 7.40-7.34 (m, 2H), 7.24-7.16 (m, 2H), 2.33 (s, 3H); C-NMR (62.9
MHz, CDCl ): δ 196.4, 143.2, 137.9, 133.6, 132.5, 129.9, 129.7, 128.9, 127.2, 21.0
3
3
.
Results and discussion:
To optimize the reaction condition, we run the reaction of 4-iodotoluene, NiCl , Cr(CO) ,
2
6
2 3 3
K CO , and Ph SnCl in PEG400 at 100 °C without inert gas protection under the conditions
shown in entry 1, Table 1. The corresponding diaryl ketone (1a) was obtained in low yield along
with the formation of the Stille coupling product (2a) as the major product (Table 1, entry 1).
Applying different bases in PEG400 did not have significant effect on the yield of 1a (Table 1,
entries 2-4). Changing the solvent to DMF led to an increase in the yield of 1a (Table 1, entry5).
Screening other solvents showed that the reaction is performed well in DMF (Table 1, entries 6-

ACCEPTED MANUSCRIPT
8
). Changing the catalyst to NiBr
2
increased the isolated yield of 1a to 89% (Table 1, entry 9).
When we performed the reaction in the presence of Ph P as ligand or pre-prepared NiCl (Ph P) ,
3
2
3
2
the result is almost the same as when we conducted the reaction under ligand-free conditions
Table 1, entry 16, 17). Consequently, the ligand is not essential for the reaction as the ligand-
(
free conditions gave good yield of the product. Therefore, NiBr was applied as the catalyst for
2
this transformation. Applying different bases in DMF showed that the reaction worked well in
the presence of K CO (Table 1, entries 10-12). The efficient amount of Ph SnCl was found to be
2
3
3
0
.4 equiv for 1.0 mmol of 4-iodotoluene. Decreasing the temperature to 70 ˚C showed the low
conversion of 4-iodotoluene to 1a which is due to the inefficient liberation of the carbon
monoxide from Cr(CO) (Table 1, entry 13). Decreasing the amount of NiBr to 6.0 mol%
6
2
required longer reaction time and decreased in the yield of the product (Table 1, entry14).
Table1
We also investigated on the application of other suitable organotin compounds such as Ph SnOH,
3
Ph SnOEt, and Ph Sn for this transformation. As the results of Table 2 show, we surmised
3
4
Ph SnCl or Ph SnOEt as the promising organtin candidates for the reaction. We set up the
3
3
reactions with 0.4 equiv of Bh SnCl or Ph SnOEt. This point revealed the stoichiometric-
3
3
economy of these reagents with regard to the reported organotin reagents in literature for Stille
and carbonylative Stille cross-coupling. In order to check the applicability of other carbon
nucleophile instead of Ph SnCl (0.4 eqiuv), we performed the reaction with PhB(OH) (1.2
3
2
equiv) and we observed that even after 5 h, the reaction did not go to completion (Table 2).
Table 2
In order to have a comparison between the efficiency of Cr(CO) with other metal carbonyls, we
6
6 6 6 5
replaced Cr(CO) with other metal carbonyls such as Mo(CO) , W(CO) , Fe(CO) , and
Co (CO) . From these reactions, it was found that the highest yield of 1a was obtained in the
2
8

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6 6
presence of Cr(CO) . Therefore, Cr(CO) was selected as the most suitable solid source of carbon
monoxide for our further studies under the obtained optimized conditions (Table 3).
Table 3
When we employed the reaction for bromobenzene and phenyl triflate under the optimized
reaction conditions of aryl iodides, the starting material was recovered after 24h. Performing the
reaction of 4-iodotoluene in the presence of NiCl
2 2 3 2 2 3 2 3
(dppf) , NiCl (Ph P) , and NiCl (Ph P) /Ph P
were also ineffective and 4-methylbenzophenone was obtained only in 17-20% yield.
We therefore applied our optimized conditions to various aryl iodides. It was observed that aryl
iodides having electron-withdrawing or electron-donating groups give their corresponding
unsymmetrical ketones in good yields (Table 4). In addition, electron-poor aryl iodides which are
prone to give homo-coupling by-product reacted well under these conditions and produced their
corresponding ketones in high yields. The substrate bearing -NO functionality was converted to
2
a mixture of side products due to the reduction of –NO group. Sterically hindered substrates
2
reacted efficiently under this condition and delivered the corresponding products in good yield.
Table 4
1
13
All the products were characterized with H-NMR and C-NMR and were compared to known
samples [17].
In order to understand the plausible reaction pass way, we study the UV-Vis spectrum of the
three mixtures. A solution of NiBr
were stirred separately at 100 ˚C. Comparison of the UV-Vis spectrum showed that the Ni(II)
peaks at 415, 571, 616 nm which exist in a solution of NiBr in DMF were vanished in the
reaction mixture and also in the solution of NiBr and Cr(CO) in DMF. This observation
2 6 2
in DMF; Cr(CO) and NiBr in DMF; and reaction mixture
2
2
6
elucidates that in the reaction mixture in the presence of Cr(CO) , Ni(II) can be reduced to Ni(0).
6

ACCEPTED MANUSCRIPT
Figure 1
For the plausible reaction mechanism, it is suggested that the Ni(II) pre-catalyst is first reduced
by the generated CO to Ni(0). Oxidative addition of the carbon-iodide bond to the generated
Ni(0) generates the intermediate (I) which followed by CO insertion to generate the intermediate
(
II). Attack of base to Ph SnX followed by migration of a phenyl group generates the
3
intermediate (III) which after the reductive elimination, the corresponding unsymmetrical diaryl
-
ketones and Ni(0) are produced. In addition, a base such as K
2
CO
3
or OH reacts with Ph
3
SnCl to
migrate a Ph group (Scheme 1).
Scheme 1
4
.
Conclusion:
In conclusion, we have introduced the efficient Nickel-catalyzed reaction of Ph SnCl and
3
3
Ph SnOEt as new sources of stoichiometric-economy phenyl nucleophile with aryl iodides for
the cabonylative Stille cross-coupling to synthesize unsymmetrical diaryl ketones under mild
conditions. This methodology excludes the use of any ligand. More importantly, this protocol is
microwave-free and employ Cr(CO) as a solid source of CO which makes it applicable
6
especially for the laboratory scale. Consequently, application of Ni-catalyst over Pd-catalyst has
the advantage of being cheaper, easily available and less toxic.
Acknowledgments
We gratefully acknowledge the financial support of this study by the Shiraz University Research
Council and a grant from Iran National Elite Foundation. Thanks also to Mr. Arash Nematollahi
for his help during this study.
References
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2] (a) X.-J. Wang, L. Zhang, X. Sun, Y. Xu, D. Krishnamurthy, C. H. Senanayake Org. Lett. 7
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6] K. Kobayashi, Y. Nishimura, F. Gao, K. Gotoh, Y. Nishihara, K. Takagi J. Org. Chem. 76
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(
[7] Stille J. K. Angew. Chem. Int. Ed. Engl. 25 (1986) 508-524
[8] (a) J. K. Stille Pure & Appl. Chem. 57 (1985) 1771-1780; (b) P. Caldirola, R. Chowdhury, A.
M. Johansson, U. Hacksell Organometallics14 (1995) 3897-3900
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Lindh, A. Fardost, M. Almeida, P. Nilsson Tetrahedron Lett. 51 (2010) 2470-2472
[
[
[
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10] M. Iizuka, Y. Kondo Eur. J. Org. Chem. (2007) 5180-5182
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Chem. 740 (2013) 123-130
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Supplementary Section:
Spectral data of carbonylative Stille reaction of iodoarenes:
1
Benzophenone (Table 4, entry 1). H-NMR (CDCl , 250 MHz): δ 7.74-7.70 (m, 4H), 7.51-7.48
3
1
3
(
m, 2H), 7.43-7.37 (m, 4H); C-NMR (CDCl , 62.9 MHz): δ 196.7, 137.5, 132.4, 130.0, 128.2
3
1
4
-Methylbenzophenone (Table 4, entry 2). H-NMR (CDCl
3
, 250 MHz): δ 7.78 (d, J = 8.2 Hz,
2
H), 7.72 (d, J = 7.1 Hz, 2H), 7.54-7.50 (m, 1H), 7.49-7.46 (m, 2H), 7.27 (d, J = 7.5 Hz, 2H),

ACCEPTED MANUSCRIPT
13
2
1
.43 (s, 3H); C-NMR (CDCl
28.9, 128.2, 21.6
3
, 62.9 MHz): δ 195.5, 143.2, 137.9, 134.8, 132.1, 130.3, 130.1,
1
4
2
3
1
-Methoxybenzophenone (Table 4, entry 3). H-NMR (CDCl , 250 MHz): δ 7.87-7.85 (m,
3
H), 7.77-7.74 (m, 2H), 7.53-7.51 (m, 1H), 7.45-7.42 (m, 2H), 6.80 (d, J = 8.5 Hz, 2H), 3.60 (s,
1
3
H); C-NMR (CDCl , 62.9 MHz): δ 195.1, 163.0, 137.9, 132.0, 131.3, 129.7, 129.0, 127.8,
3
12.8, 54.2
1
4
7
1
-Cholorobenzophenone (Table 4, entry 4). H-NMR (CDCl , 250 MHz): δ 7.72-7.70 (m, 2H),
3
1
3
.60-7.55 (m, 2H), 7.45-7.41 (m, 1H), 7.38-7.33 (m, 4H); C-NMR (CDCl , 62.9 MHz): δ
3
95.3, 139.2, 136.9, 135.5, 132.3, 131.0, 129.4, 128.0, 127.8
1
4
-Bromobenzophenone (Table 4, entry 5). H-NMR (CDCl , 250 MHz): δ7.75 (d, J = 8.1 Hz,
3
1
3
2
3
H), 7.69-7.67 (m, 2 H), 7.63-7.59 (m, 3 H), 7.46-7.44 (m, 2 H); C-NMR (CDCl , 62.9 MHz):
δ 195.4, 137.0, 136.3, 131.9, 131.5, 130.5, 129.5, 128.7, 127.4

ACCEPTED MANUSCRIPT
1
4
7
2
-Fluorobenzophenone (Table 4, entry 6). H-NMR (CDCl
3
, 250 MHz): δ 7.85-7.77 (m, 4H),
1
3
.58-7.50 (m, 3H), 7.26-7.16 (m, 2H); C-NMR (CDCl , 62.9 MHz): δ 195.4, 166.0 (d, J =
3
52.0 Hz), 137.3, 133.5, 133.0 (d, J = 7.2 Hz), 132.7, 129.5, 128.0, 115.7 (d, J = 20.6 Hz)
1
4
-Trifluoromethylbenzophenone (Table 4, entry 8). H-NMR (CDCl , 250 MHz): δ 8.10 (d, J
3
1
3
=
7.8 Hz, 2H), 7.98-7.97 (m, 2H), 7.71-7.69 (m, 2H), 7.32-7.30 (m, 1H), 7.28-7.27 (m, 2H); C-
, 62.9 MHz): δ 196.0, 140.9, 137.0, 132.9 (q, J = 32.3 Hz), 132.3, 130.0, 129.7,
28.3, 125.1 (q, J = 3.6 Hz), 123.1 (q, J = 272.7 Hz)
NMR (CDCl
3
1
1
1
1
7
1
-Naphthylphenone (Table 4, entry 9). H-NMR (CDCl , 250 MHz): δ 8.07 (d, J = 8.1 Hz,
3
H), 8.03 (d, J = 8.0 Hz, 1H), 7.87-7.83 (m, 1H), 7.78-7.75 (m, 2H), 7.47-7.38 (m, 2 H), 7.35-
1
3
.27 (m, 5 H); C-NMR (CDCl
3
, 62.9 MHz): δ 195.7, 138.2, 136.3, 133.6, 133.2, 131.2, 130.7,
30.0, 128.4, 128.3, 127.8, 127.2, 126.5, 125.6, 124.3

ACCEPTED MANUSCRIPT
1
2
-Methylbenzophenone (Table 4, entry 10). H-NMR (CDCl
3
, 250 MHz): δ 7.82-7.78 (m, 2H),
1
3
7
.58-7.55 (m, 1H), 7.48-7.38 (m, 3H), 7.30-7.21 (m, 3H), 2.29 (s, 3H); C-NMR (CDCl , 62.9
3
MHz): δ 198.6, 138.6, 137.7, 136.7, 133.1, 131.4, 130.9, 130.2, 130.1, 128.5, 125.1, 19.9
1
3
-Methylbenzophenone (Table 4, entry 11). H-NMR (CDCl
3
, 250 MHz): δ 7.82-7.80 (m, 2H),
1
3
7
.65-7.64 (m, 1H), 7.63-7.58 (m, 2H), 7.50-7.45 (m, 2H), 7.41-7.35 (m, 2H), 2.40 (s, 3H); C-
NMR (CDCl , 62.9 MHz): δ 197.1, 138.3, 137.7, 137.5, 133.3, 132.2, 130.7, 130.0, 128.3, 128.0,
3
1
27.2, 21.5

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a
3
Table 1. Optimization of different parameters for the reaction of 4-iodotoluene with Ph SnCl.
o
Entry
[Ni]
Solvent
PEG400
PEG400
PEG400
PEG400
DMF
Base
Temp ( C)
100
100
100
100
100
100
100
90
Time (h)
1a(%)
45
40
40
33
82
-
2a(%)
50
55
55
60
10
40
30
35
8
1
2
3
4
5
6
7
8
9
NiCl2
K CO3
2
3.5
5
NiCl
2
3
Et N
NiCl2
NiCl2
NiCl2
NiCl2
KOAc
4.5
7
K PO4
3
K CO3
2
3
Dioxane
Diglyme
K CO3
2
10
10
10
2.7
4
NiCl
2
K
2
CO
3
20
15
89
10
65
25
70
60
0
NiCl2
NiBr2
NiBr2
NiBr2
CH CN
K CO3
2
3
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
K CO3
2
100
100
100
100
70
1
1
1
1
1
1
1
1
0
1
2
3
4
5
6
7
Et N
40
40
50
20
15
0
3
KOAc
5
NiBr
2
DABCO
8
NiBr2
K CO3
2
7
b
NiBr2
-
K CO3
2
100
100
100
100
8.5
10
3.2
3.0
K CO3
2
NiCl /Ph P
K CO3
2
85
88
10
8
2
3
NiCl
2
(Ph
3
P)
2
2 3
K CO
a
All the reactions were performed under air. Recation condition: iodotoluene (1.0 mmol), Cr(CO) (1.0 mmol),
6
b
Ph
3
SnCl (0.4 mmol), [Ni]: (16.0 mol%), base (3.0 mmol), solvent (3 mL). NiBr
2
(6.0 mol%).

ACCEPTED MANUSCRIPT
a
Table 2. The effect of organotin reagents on the carbonylative Stille reaction of 4-iodotoluene.
Entry
Nucleophile
Ph SnCl
Time (h)
Yield of 1a(%)
1
2
3
4
5
3
2.7
5
89
70
85
10
60
Ph SnOH
3
Ph SnOEt
3
3
Ph
4
Sn
5
PhB(OH)2
5
a
Recation condition: iodotoluene (1.0 mmol), Cr(CO) (1.0 mmol), organotin (0.4 mmol), NiBr :
16.0 mol%), K CO (3.0 mmol), DMF (3 mL) at 100 C.
2 3
6
2
o
(

ACCEPTED MANUSCRIPT
a
Table 3. The effect of metal carbonyl on the carbonylative Stille reaction of 4-iodotoluene.
Entry
M(CO)
n
Time (h)
Yield of 1a(%)
1
2
3
4
5
Mo(CO)6
Cr(CO)6
W(CO)6
Fe(CO)5
4
2.7
5
85
89
10
0
5
Co
2
(CO)
8
6
40
a
Recation condition: iodotoluene (1.0 mmol), M(CO) (1.0 mmol), Ph SnCl (0.4 mmol),
n
3
o
2 2 3
NiBr : (16.0 mol%), K CO (3.0 mmol), DMF (3 mL) at 100 C.

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Table 4
Ni-catalyzed stille carbonylative cross-coupling of aryl iodides with Ph
DMF at 100 ˚C
3 3
SnCl or Ph SnOEt in
Entry
1
Aryl iodide
Time (h)
Product
Yield (%)
A : 2.4
B : 2.4
A : 87
B :82
A : 2.7
B : 3.0
A : 89
B : 85
2
3
A : 3.5
B : 3.3
A : 80
B : 83
A : 2.8
B : 3
A : 85
B : 85
4
5
A : 2.5
B : 2.5
A : 85
B : 80
A : 2
B : 2
A : 80
B : 78
6
7
A : 3
B : 3
A : -
B : -
-

ACCEPTED MANUSCRIPT
A : 3
A : 80
B : 83
8
9
B : 2.7
A : 6
B : 6
A : 75
B : 70
A : 6.5
B : 6
A : 68
B : 70
10
A : 2
A : 78
B : 70
1
1
2
B : 2.3
A : 5
A : -
B :-
1
-
B : 6
a
Recation condition: aryl iodide (1.0 mmol), Cr(CO) (1.0 mmol), Ph SnCl (0.4 mmol), NiBr : (16.0 mol%),
6
3
2
o
K CO (3.0 mmol), DMF (3 mL) at 100 C under air.
2
3

ACCEPTED MANUSCRIPT
Figure 1. UV-Vis spectrum

ACCEPTED MANUSCRIPT
Scheme 1. The plausible mechanism for the carbonylative Stille reaction of aryl iodides

ACCEPTED MANUSCRIPT
Highlights
•
•
•
Ph SnX (X : Cl, OEt) used for the carbonylative Stille reaction
3
NiBr as the catalyst and phosphine-free condition were applied
2
Cr(CO) employed as the solid source of CO
6