Nickel-Catalyzed Molybdenum-Promoted Carbonylative Synthesis of Benzophenones

Article abstract of DOI:10.1021/acs.joc.8b00806

A nickel-catalyzed molybdenum-promoted carbonylative coupling reaction for the synthesis of benzophenones from aryl iodides has been developed. Various substituted diaryl ketones were synthesized in moderate to excellent yields under CO-gas-free conditions. A synergetic effect of both nickel and molybdenum has been observed, which is also responsible for the success of this transformation.

Full text of DOI:10.1021/acs.joc.8b00806

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Note
Nickel-Catalyzed Molybdenum-Promoted
Carbonylative Synthesis of Benzophenones
Jin-Bao Peng, Fu-Peng Wu, Da Li, Xinxin Qi, Jun Ying, and Xiao-Feng Wu
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b00806 • Publication Date (Web): 25 May 2018
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The Journal of Organic Chemistry
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Nickel-Catalyzed Molybdenum-Promoted Carbonylative Synthesis of
Benzophenones
,
†
†
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†
†
, ,‡
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JinꢀBao Peng,* FuꢀPeng Wu, Da Li, Xinxin Qi, Jun Ying and XiaoꢀFeng Wu*
†
Department of Chemistry, Zhejiang SciꢀTech University, Hangzhou, Zhejiang 310018, People’s Republic of China
LeibnizꢀInstitut für Katalyse e.V. an der Universität Rostock, AlbertꢀEinsteinꢀStraße 29a, Rostock 18059, Germany
‡
Supporting Information Placeholder
ABSTRACT: A nickelꢀcatalyzed molybdenumꢀpromoted carbonylative coupling reaction for the synthesis of benzophenones from aryl
iodides has been developed. Various substituted diaryl ketones were synthesized in moderate to excellent yields under CO gas free condiꢀ
tions. A synergetic effect of both nickel and molybdenum has been observed, which is also responsible for the success of this transformation.
Benzophenones represent an important and versatile structure
motif that is frequently present in natural products, materials,
pharmaceuticals and other biologically active molecules. Owing to
acids for the synthesis of symmetric diaryl ketones by employing
1
1
DMF as an abundant and lowꢀcost CO source (Scheme 1, b). Our
research group has been interested in developing new carbonylaꢀ
tion reactions during the last few years. Recently, we developed a
palladium catalyzed carbonylative homoꢀcoupling of aryl iodides
with formic acid as the CO source and sodium formate as the reꢀ
1
their importance, various synthetic methodologies for the synthesis
of diarylketones have been developed. Among them, transition
metal catalyzed carbonylative coupling reactions have now
emerged as one of the most powerful tools for the preparation of
1
2
ductant. In order to avoid the disadvantages from palladium
catalysts, we become interested in developing a nonꢀnoble metal
catalyzed carbonylation system.
2
various functionalized ketones. Many impressive improvements
have been realized during the past decades since the pioneering
3
works from Heck and coꢀworkers. However, most of the researchꢀ
es on carbonylative coupling reactions were based on palladium
catalysts. Although palladium catalyst systems showed higher
reactivity and efficiency, their high price and the demand of expenꢀ
sive phosphine ligands usage limited their wider applications, espeꢀ
cially in large scales. In this aspect, nonꢀnoble metals, especially the
Scheme 1. Non-Noble Metal Promoted Carbonylative Homo-
Coupling Reactions of Aryl Halides.
4
firstꢀrow transition metals, turned out to be attractive alternatives.
Nonꢀnoble metals, such as nickel and cobalt, have already been
reported to promote carbonylative coupling reactions (Scheme 1,
a). Carbonylative homoꢀcoupling of organomercuric halides RHgX
5a,5b
5c
with stoichiometric cobalt and nickel carbonyls were reported
in late 1960s. Knochel’s group reported a cobalt mediated carꢀ
6
bonylative homoꢀcoupling of organozinc reagents in 1995. In
2003, Larhed and colleagues developed a Co
2
(CO) mediated
8
ultrafast carbonylative coupling of aryl halides under microwave
7
irradiation. Brunet and Taillefer developed a metal carbonylꢀ
catalyzed carbonylation of aryl halides which lead to symmetric
8
diaryl ketones production. On the other hand, owing to the high
toxicity of carbon monoxide, CO gasꢀfree carbonylation reactions
9
have been developed based on various CO surrogates. Gosmini
and coꢀworkers developed a cobalt catalyzed carbonylative homoꢀ
coupling reaction for the synthesis of symmetrical diaryl ketones
However, in general, one main issue for applying nickel catalyst
1
0
from aryl bromides and ethyl chloroformate. Liu, Lu and their coꢀ
workers reported a nickel catalyzed carbonylation of arylboronic
in cabonylation reactions is the formation of Ni(CO)
4
. Ni(CO)
a highly toxic liquid (boiling point = 43 C) and mainly applied in
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Mond process for the purification of nickel metal. From catalyst
point of view, Ni(CO) is fully coordinated, due to the high affinity
group (Table 2, 2aꢀ2h) and electronꢀwithdrawing group (Table 2,
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2i, 2j, 2l, 2m) substituted iodobenzenes were well tolerated and
delivered the corresponding diaryl ketones in 57ꢀ93% yields. It
should be mentioned that fluoroꢀ and chloroꢀsubstituted iodobenꢀ
zenes were well tolerated in this transformation (Table 2, 2i, 2j and
2m). However, when 4ꢀbromoꢀiodobenzene was used in this reacꢀ
tion, only trace amount of desired product could be detected from
the reaction mixture (Table 2, 2k). Moreover, heteroaryl iodides
such as 3ꢀiodothiophene was also subjected to the carbonylative
homoꢀcoupling reaction, and the corresponding ketone was conꢀ
veniently generated in 61% yield (Table 2, 2n). Besides, 1ꢀ
iodonaphthalene was tolerated and the corresponding product was
produced in 73% yield (Table 2, 2o).
4
between CO and nickel, which limited the oxidative addition of Cꢀ
X bond to nickel center and also the migratory insertion of CO.
Hence, the choice of proper ligand and the right pressure of CO
usually play an important role in the success of a nickel catalyzed
carbonylation reaction. Herein, we report a new nickelꢀcatalyzed
carbonylative coupling of aryl iodides for the synthesis of benzoꢀ
phenones. With molybdenum carbonyl as the promoter and CO
source, good yields of the desired benzophenones can be produced.
Interestingly, the synergetic effect of both metals has found to be
crucial.
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Initially, iodobenzene was selected as the model substrate. To
our delight, stirring a solution of iodobenzene, Mo(CO)
6
and zinc
a
powder in the presence of NiCl and dtbbpy (4,4'ꢀdiꢀtertꢀbutylꢀ2,2'ꢀ
2
Table 1. Optimization of the reaction conditions.
o
bipyridine) in 1,4ꢀdioxane at 120 C, the carbonylative homoꢀ
coupling reaction proceeded successfully and the desired product
diphenyl ketone was obtained in 64% yield (Table 1, entry 1). The
yield was improved slightly to 70% when NiBr
catalyst (Table 1, entry 2). Other nickel catalysts, such as NiI
Ni(cod) and Ni(acac) , resulted in decreased yields (Table 1,
2
was used as the
2
,
2
2
entries 3ꢀ5). The electronic and steric effect of the ligand played an
important role on the reactivity. Generally, electronꢀrich ligands
facilitate the oxidative addition of the metal to the CꢀX bonds.
Thus, when less electronꢀrich ligands such as bipyridine and 1,10ꢀ
phenanthroline was used, the desired ketone was obtained in 63%
and 50% yields, respectively (Table 1, entries 6 and 8). Using 6,6'ꢀ
dimethylꢀ2,2'ꢀbipyridine L1 as the ligand gave a moderate yield of
b
entry
[Ni] (mol%)
ligand (mol%)
dtbbpy (5)
dtbbpy (5)
dtbbpy (5)
dtbbpy (5)
dtbbpy (5)
solvent
dioxane
dioxane
dioxane
dioxane
dioxane
yield
1
2
3
4
5
NiCl
2
2
(5)
(5)
64
NiBr
70
NiI
Ni(cod)
Ni(acac)
2
(5)
69
6
2%, which might be resulted from the steric hindrance effect
(Table 1, entry 7). Notably, tridentate ligand L3 gave similar reacꢀ
2
(5)
(5)
21
tivity to dtbbpy since the strong tridentate bonding of L3 to nickel
2
57
might prevent the bonding of multiple CO to the catalyst center
1
3
(
Table 1, entry 9). However, considering the cost of L3, we deꢀ
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NiBr
NiBr
NiBr
NiBr
NiBr
2
2
2
2
2
(5)
(5)
(5)
(5)
(5)
bpy (5)
dioxane
dioxane
dioxane
dioxane
THF
63
62
50
70
17
17
74
cided choosing dtbbpy for further studies. The use of phosphine
ligand turned out to be less effective (see details in SI). Screening of
the solvents, such as THF and toluene failed to improve the yields
L1 (5)
L2 (5)
(Table 1, entries 10 and 11, also see details in SI). The concentraꢀ
tion of the substrates also affected the yields significantly. The yield
was further improved to 74% when the reaction was performed at a
higher concentration (Table 1, entry 12). Further screening of the
reaction time revealed that prolonged reaction time would result
decompose of the product (see details in SI). The best result was
obtained when the reaction mixture was stirred at 120 ℃ for 6
hours and the diphenyl ketone was isolated in 86% yield (Table 1,
L3 (5)
1
0
dtbbpy (5)
dtbbpy (5)
dtbbpy (2.5)
dtbbpy (2.5)
dtbbpy (2.5)
11
NiBr (5)
2
toluene
dioxane
dioxane
dioxane
dioxane
dioxane
c
1
2
2
NiBr (2.5)
c,d
e
1
3
NiBr
2
(2.5)
90 (86 )
entry 13). Furthermore, in addition to Mo(CO)
metal carbonyl complexes in this reaction. Cr(CO)
6
, we tested other
was also effecꢀ
c,d,f
1
1
4
NiBr
2
(2.5)
35
24
0
6
tive for this transformation, despite in a low yield (Table 1, entry
14). It should be noted that when the reaction was conducted
without nickel catalyst, the desired product was obtained in 24%
c,d
5
c,d,g
a
16
NiBr
2
(2.5)
dtbbpy (2.5)
yield (Table 1, entry 15). However, when Mo(CO)
with 2 bar of CO gas, only trace amount of ketone was detected
Table 1, entry 16). These reactions indicate that Mo(CO) not
6
was replaced
Reaction condition: iodobenzene (0.5 mmol), catalyst, ligand,
(1 equiv), Zn (3 equiv), solvent (2 mL), 120 ºC, 16 h.
Mo(CO)
6
(
6
b
c
GC yield, with dodecane as the internal standard. iodobenzene (1
mmol), Mo(CO) (0.5 equiv), Zn (1.5 equiv). 6 h. Isolated yield.
Cr(CO)
only acted as a CO surrogate, but also as a coꢀcatalyst in this reacꢀ
tion. It’s also important to mention that no reaction occurred in the
absence of zinc or replace zinc by metallic manganese.
d
e
6
f
g
6
was used instead of Mo(CO) . 2 bar of gaseous CO was
6
used instead of Mo(CO)
6
.
With the optimized reaction conditions in hand (Table 1, entry
1
3), we began to investigate the substrates scope of the reaction
Then, we turned our attention to test this procedure for the
carbonylative crossꢀcoupling reaction. When a mixed substrates
with various substituted aryl iodides. As summarized in Table 2, a
series of substituted aryl iodides were successfully applied to the
carbonylative homoꢀcoupling reaction. Both electronꢀdonating
(
0.5 mmol 1ꢀfluoroꢀ4ꢀiodobenzene 1i and 0.5 mmol 1ꢀiodoꢀ4ꢀ
methoxybenzene 1e) were subjected to the optimized conditions,
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The Journal of Organic Chemistry
2
i, crossꢀcoupling products 2ei and 2e were obtained in 1.4 : 2.5 : 1
possible mechanism for palladiumꢀcatalyzed amide formation
involving transmetalation between carbamoylmetal complex and
1
2
3
4
5
6
7
8
9
selectivity (Table 3, entry 1). This is different from the previous
1
2
work, where the homoꢀcoupling product was the major product.
In addition, no matter 1i or 1e was used excessively, the amount of
crossꢀcoupling product 2ei was somehow larger than that of homoꢀ
coupling products 2i and 2e, despite with poor selectivity (Table 3,
entries 2 and 3). A TEMPO testing was performed as well, and 74%
yield of the desired benzophenone can be produced in the presence
of 2 equivalents of TEMPO under our standard conditions
arylpalladium(II) intermediate. Mo(CO) was also reported to
6
1
5
promote the aminocarbonylation reaction of aryl halides. Altꢀ
hough the direct oxidative addition of molybdenum to carbonꢀ
1
6
halogen bond has been reported, high reaction temperature was
o
usually needed (120–160 C). Although the detailed mechanism is
still not clear at this stage, based on our results and the previous
4
,13ꢀ17
literatures,
a possible reaction mechanism is proposed in
0
(Scheme 2). This result can exclude the involvement of radical
Scheme 3. First, oxidative addition of Ni with the aryl iodide to
intermediates in this transformation.
give the aryl nickel complex 3, which underwent a CO transmission
1
1
1
1
1
1
1
1
1
1
2
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with Mo(CO) to give an aryl nickelꢀcarbonyl complex 4. Then,
6
a
Table 2. Ni-catalyzed carbonylative benzophenones synthesis.
insertion of a carbonyl ligand of 4 would generate an acyl nickel
complex 5. After oxidative addition with another molecular of
substrate, complex 6 will be produced as the key intermediate
which can produce the final ketone product after reductive eliminaꢀ
0
tion and Ni been regenerated with zinc as the reducing reagent. In
this catalytic system, the generated acyl nickel complex 5 is very
electron deficient and more tend to coordinate with electron rich
substrates via πꢀcoordination model. This can also explain why
carbonylative crossꢀcoupling product is always the main product as
shown in Table 3, which also makes it different from palladium
1
2
chemistry.
Scheme 3. Plausible Reaction Mechanism.
NiBr2
Zn
Ni0L
O
ArI
1
Ar
Ar'
2
Zn
L
II
Ni
Ar
I
O
Ar'
3
IV
Ar
Ni
I
6
L
Mo(CO)6
I
L
II
Ni
I
Ar
O
CO
Ar'I
L
Ni
I
II
Ar
4
a
Reaction condition: aryl iodides (1 mmol), NiBr
2
(0.025
(0.5 mmol), Zn (1.5
5
mmol), dtbbpy (0.025 mmol), Mo(CO)
mmol), 1,4ꢀdioxane (2 mL), 120 ºC, 6 h, isolated yield.
6
In conclusion, we have developed a nickelꢀcatalyzed molybꢀ
denumꢀpromoted carbonylative coupling reaction of aryl iodides
for the synthesis of benzophenones. A series of substituted diaryl
ketones were synthesized in moderate to excellent yields. A synerꢀ
getic effect of both nickel and molybdenum had been observed
which proven crucial for the success of this transformation.
Table 3. Carbonylative cross-coupling testings.
EXPERIMENTAL SECTION
1
i
1e
(mmol)
0.5
2i
(mmol)
0.13
2ei
(mmol)
0.23
2e
(mmol)
0.09
entry
General information: All reactions were carried out under a nitroꢀ
gen atmosphere. All reagents were from commercial sources and
used as received without further purification. All solvents were
dried by standard techniques, and distilled prior to use. Column
chromatography was performed on silica gel (200ꢀ300 meshes)
(mmol)
0.5
1
2
3
0.5
1.0
1.0
0.5
0.07
0.31
0.32
0.37
0.24
0.06
Scheme 2. Control experiment with TEMPO.
o
using petroleum ether (bp. 60~90 C) and ethyl acetate as eluent.
1
13
H and C NMR spectra were taken on 400 MHz instruments and
spectral data were reported in ppm relative to tetramethylsilane
1
13
(
TMS) as internal standard and CDCl ( H NMR δ 7.26, C NMR
3
δ 77.0) as solvent. All coupling constants (J) are reported in Hz
with the following abbreviations: s = singlet, d = doublet, dd =
double doublet, ddd = double doublet of doublets, t = triplet, dt =
double triplet, q = quatriplet, m = multiplet, br = broad. Gas chroꢀ
Concerning the reaction mechanism, Yamane and Ren reportꢀ
ed a palladiumꢀcatalyzed carbamoylation of aryl halides by tungsten
1
4
carbonyl amine complex, where they proposed an alternative
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matography (GC) analyses were performed on a Shimadzu GCꢀ
2014C chromatograph equipped with a FID detector. Mass spectra
MS) were measured on spectrometer by direct inlet at 70 eV.
General procedure: NiBr (5.5 mg, 0.025 mmol), dtbbpy (6.7 mg,
0.025 mmol), Mo(CO) (132 mg, 0.5 mmol) and zinc power (98
chromatography (petroleum ether / EtOAc = 50:1, Rf = 0.25) the
1
1 1
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
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3
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4
4
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desired compound was isolated as a yellow solid (82.2 mg, 69%).
H
NMR (400 MHz, CDCl ) δ 7.61 (s, 2H), 7.52 (d, J = 7.7 Hz, 2H), 7.22
3
(
1
3
(
d, J = 7.8 Hz, 2H), 2.34 (d, J = 8.4 Hz, 12H). C NMR (101 MHz,
2
CDCl ) δ 196.7, 141.6, 136.6, 135.8, 131.1, 129.3, 127.9, 19.9, 19.7.
3
6
Bis(4ꢀfluorophenyl)methanone (2i) Prepared from 1ꢀfluoroꢀ4ꢀ
iodobenzene (118 uL, 1.0 mmol). After purification by column chroꢀ
matography (petroleum ether / EtOAc = 50:1, Rf = 0.25) the desired
mg, 1.5 mmol) were transferred into an 15 mL tube which was
filled with nitrogen. 1,4ꢀDioxane (2 mL) and iodobenzene (114 uL,
1
.0 mmol) were added to the reaction tube. Then the tube was
12 1
compound was isolated as a white solid (101.3 mg, 93%). H NMR
sealed and the mixture was stirred at 120 °C for 6 h. After the reacꢀ
tion was completed, the reaction mixture was filtered and concenꢀ
trated under vacuum. The crude product was purified by column
chromatography on silica gel to afford the corresponding product.
13
(
400 MHz, CDCl
3
) δ 7.85 – 7.77 (m, 4H), 7.16 (t, J = 8.6 Hz, 4H). C
NMR (101 MHz, CDCl
3
) δ 193.7, 166.3 (d, J = 52.5 Hz), 133.6, 132.5
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(d, J = 9.0 Hz), 115.5 (d, J = 22.2 Hz).
Bis(4ꢀchlorophenyl)methanone (2j) Prepared from 1ꢀchloroꢀ4ꢀ
iodobenzene (238.5 mg, 1.0 mmol). After purification by column
chromatography (petroleum ether / EtOAc = 50:1, Rf = 0.25) the
Spectroscopic Data of the Products
Benzophenone (2a) Prepared from iodobenzene (114 uL, 1.0 mmol).
After purification by column chromatography (petroleum ether /
EtOAc = 50:1, Rf = 0.25) the desired compound was isolated as a
12
desired compound was isolated as a light yellow solid (94.7 mg, 76%).
1
H NMR (400 MHz, CDCl
3
) δ 7.71 (d, J = 8.5 Hz, 2H), 7.45 (d, J = 8.5
) δ 194.1, 139.1, 135.5, 131.3,
13
Hz, 2H). C NMR (101 MHz, CDCl
28.7.
3
1
2 1
yellow oil (78.4 mg, 86%). H NMR (400 MHz, CDCl
7.2 Hz, 4H), 7.63 (t, J = 7.4 Hz, 2H), 7.52 (t, J = 7.6 Hz, 4H). C NMR
101 MHz, CDCl ) δ 196.7, 137.6, 132.4, 130.1, 128.3.
Diꢀoꢀtolylmethanone (2b) Prepared from 1ꢀiodoꢀ2ꢀmethylbenzene
3
) δ 7.84 (d, J =
1
1
3
Bis(4ꢀ(trifluoromethyl)phenyl)methanone (2l) Prepared from 1ꢀiodoꢀ
4ꢀ(trifluoromethyl)benzene (150 uL, 1.0 mmol). After purification by
column chromatography (petroleum ether / EtOAc = 50:1, Rf = 0.25)
(
3
(
(
128 uL, 1.0 mmol). After purification by column chromatography
petroleum ether / EtOAc = 50:1, Rf = 0.25) the desired compound
12
the desired compound was isolated as a white solid (90.4 mg, 57%).
1
H NMR (400 MHz, CDCl
3
) δ 7.91 (d, J = 8.2 Hz, 4H), 7.78 (d, J = 8.2
) δ 194.3, 139.7, 134.3 (q) ,
1
2 1
was isolated as a yellow oil (82.2 mg, 78%). H NMR (400 MHz,
CDCl ) δ 7.39 (td, J = 7.5, 1.1 Hz, 1H), 7.30 (dd, J = 12.9, 7.3 Hz, 2H),
7
2
13
Hz, 4H). C NMR (101 MHz, CDCl
30.2, 125.6 (d, 3 Hz), 122.2.
Bis(2,4ꢀdifluorophenyl)methanone (2m) Prepared from 2,4ꢀdifluoroꢀ
ꢀiodobenzene (123 uL, 1.0 mmol). After purification by column
chromatography (petroleum ether / EtOAc = 50:1, Rf = 0.20) the
3
3
1
13
.21 (t, J = 7.4 Hz, 1H), 2.46 (s, 3H). C NMR (101 MHz, CDCl
00.8, 139.0, 138.2, 131.4, 131.1, 130.3, 125.4, 20.7.
3
) δ
1
Diꢀmꢀtolylmethanone (2c) Prepared from 1ꢀiodoꢀ3ꢀmethylbenzene
(130 uL, 1.0 mmol). After purification by column chromatography
11 1
desired compound was isolated as a white solid (100.4 mg, 79%).
NMR (400 MHz, CDCl ) δ 7.75 (dd, J = 14.9, 8.2 Hz, 1H), 7.03 – 6.96
(m, 1H), 6.89 – 6.80 (m, 1H). C NMR (101 MHz, CDCl
166.9 (d, J = 12 Hz), 164.4 (d, J = 12 Hz), 163.1 (d, J = 12 Hz), 160.5
H
(
petroleum ether / EtOAc = 50:1, Rf = 0.25) the desired compound
3
1
2 1
was isolated as a yellow solid (69.2 mg, 66%). H NMR (400 MHz,
CDCl ) δ 7.63 (s, 1H), 7.57 (d, J = 7.3 Hz, 1H), 7.37 (dt, J = 14.9, 7.5
Hz, 2H), 2.42 (s, 3H). C NMR (101 MHz, CDCl
37.8, 133.1, 130.4, 128.0, 127.4, 21.4.
Diꢀpꢀtolylmethanone (2d) Prepared from 1ꢀiodoꢀ4ꢀmethylbenzene
13
3
) δ 186.9,
3
1
3
3
) δ 197.2, 138.1,
(
(
d, J = 12 Hz), 132.6 (d, J = 10 Hz), 123.9 (dd, J = 13 Hz, 3 Hz) 115.7
d, J = 22 Hz) 112.1 (d, J = 22 Hz), 104.5 (t).
1
Di(thiophenꢀ3ꢀyl)methanone (2n) Prepared from 3ꢀiodothiophene
(
(
222.5 mg, 1.0 mmol). After purification by column chromatography
petroleum ether / EtOAc = 50:1, Rf = 0.25) the desired compound
(106 uL, 1.0 mmol). After purification by column chromatography
(
petroleum ether / EtOAc = 50:1, Rf = 0.25) the desired compound
1
2 1
was isolated as a white solid (82.3 mg, 78%). H NMR (400 MHz,
CDCl ) δ 7.63 (d, J = 8.1 Hz, 2H), 7.24 – 7.18 (m, 2H), 2.37 (s, 3H).
C NMR (101 MHz, CDCl ) δ 196.3, 142.9, 135.2, 130.2, 128.9, 21.6.
12 1
was isolated as a brown solid (59.2 mg, 61%). H NMR (400 MHz,
3
CDCl ) δ 8.01 (dd, J = 2.8, 1.1 Hz, 1H), 7.60 (dd, J = 5.0, 1.0 Hz, 1H),
3
1
3
3
13
7.38 (dd, J = 5.0, 2.9 Hz, 1H). C NMR (101 MHz, CDCl
3
) δ 183.3,
Bis(4ꢀmethoxyphenyl)methanone (2e) Prepared from 1ꢀiodoꢀ4ꢀ
methoxylbenzene (234.0 mg, 1.0 mmol). After purification by column
chromatography (petroleum ether / EtOAc = 20:1, Rf = 0.3) the
142.0, 132.7, 128.3, 126.3.
Di(naphthalenꢀ1ꢀyl)methanone
iodonaphthalene (150 uL, 1.0 mmol). After purification by column
chromatography (petroleum ether / EtOAc = 50:1, Rf = 0.20) the
(2o)
Prepared
from 1ꢀ
7
1
desired compound was isolated as a yellow solid (85.2 mg, 71%).
H
NMR (400 MHz, CDCl ) δ 7.79 (d, J = 8.8 Hz, 2H), 6.96 (d, J = 8.8
3
7
desired compound was isolated as a redꢀbrown solid (102.2 mg, 73%).
13
Hz, 2H), 3.88 (s, 3H). C NMR (101 MHz, CDCl
32.2, 130.8, 113.5, 55.5.
3
) δ 194.4, 162.8,
1
H NMR (400 MHz, CDCl
3
) δ 8.66 – 8.49 (m, 1H), 8.04 (d, J = 8.2 Hz,
1
1
13
H), 7.98 – 7.93 (m, 1H), 7.64 – 7.57 (m, 3H), 7.44 (t, J = 7.7 Hz, 1H).
C NMR (101 MHz, CDCl
Bis(4ꢀethylphenyl)methanone (2f) Prepared from 1ꢀethylꢀ4ꢀ
iodobenzene (145 uL, 1.0 mmol). After purification by column chroꢀ
matography (petroleum ether / EtOAc = 50:1, Rf = 0.25) the desired
3
) δ 199.8, 137.2, 133.9, 132.5, 131.2,
1
30.5, 128.5, 127.8, 126.6, 125.9, 124.4.
(4ꢀFluorophenyl)(4ꢀmethoxyphenyl)methanone (2ei) Prepared from
1ꢀfluoroꢀ4ꢀiodobenzene (59 uL, 0.5 mmol) and 1ꢀiodoꢀ4ꢀ
methoxybenzene (117.0 mg, 0.5 mmol). After purification by column
1
2 1
compound was isolated as a yellow solid (84.8 mg, 71%). H NMR
400 MHz, CDCl ) δ 7.74 (d, J = 8.0 Hz, 2H), 7.30 (d, J = 8.0 Hz, 2H),
(
2
3
1
3
.74 (q, J = 7.6 Hz, 2H), 1.29 (t, J = 7.6 Hz, 3H). C NMR (101 MHz,
chromatography (petroleum ether / EtOAc = 30:1, Rf = 0.25) the
CDCl
3
) δ 196.3, 149.1, 135.5, 130.3, 127.7, 28.9, 15.3.
12 1
desired compound was isolated as a white solid (51.5 mg, 45%).
NMR (400 MHz, CDCl
H
Bis(4ꢀ(tertꢀbutyl)phenyl)methanone (2g) Prepared from 1ꢀ(tertꢀ
butyl)ꢀ4ꢀiodobenzene (181 uL, 1.0 mmol). After purification by colꢀ
umn chromatography (petroleum ether / EtOAc = 50:1, Rf = 0.25) the
3
) δ 7.89 – 7.78 (m, 4H), 7.19 (t, J = 8.6 Hz,
13
2
H), 7.01 (d, J = 8.7 Hz, 2H), 3.93 (s, 3H). C NMR (101 MHz,
CDCl ) δ 194.1, 165.0 (d, J = 253 Hz), 163.3, 134.4, 132.39, 132.3 (d, J
3
1
2 1
desired compound was isolated as a yellow solid (123.5 mg, 84%).
H
=
9.1 Hz), 130.0, 115.3 (d, J = 22.2 Hz), 113.6, 55.5.
NMR (400 MHz, CDCl ) δ 7.77 (d, J = 8.3 Hz, 4H), 7.49 (d, J = 8.3
3
1
3
Hz, 4H), 1.37 (s, 18H). C NMR (101 MHz, CDCl
35.2, 130.0, 125.2, 35.1, 31.2.
3
) δ 196.2, 155.9,
1
Bis(3,4ꢀdimethylphenyl)methanone (2h) Prepared from 4ꢀiodoꢀ1,2ꢀ
dimethylbenzene (232.1 mg, 1.0 mmol). After purification by column
ASSOCIATED CONTENT
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Page 5 of 5
The Journal of Organic Chemistry
Supporting Information
(7) Enquist, P.ꢀA.; Nilsson, P.; Larhed, M. Ultrafast chemistry:ꢀ cobalt
carbonylꢀmediated synthesis of diaryl ketones under microwave irradiation.
Org. Lett. 2003, 5, 4875ꢀ4878.
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The Supporting Information is available free of charge on the ACS
Publications website.
(
8) (a) Brunet, J.ꢀJ.; Taillefer, M. Bimetallic catalysis: Synthesis of benꢀ
zophenones through carbonylation of aryl iodides catalysed by
Fe(CO) ·Co (CO) systems. J. Organomet. Chem. 1990, 384, 193ꢀ197. (b)
Brunet, J.ꢀJ.; Zaizi, A. E. Synthesis of benzophenone by carbonylation of
Optimization detail and NMR spectrums (PDF)
5
2
8
AUTHOR INFORMATION
Corresponding Author
iodobenzene with [Bu
275ꢀ277.
4
nN][HFe(CO) ]. J. Organomet. Chem. 1995, 486,
4
(
9) For selected reviews on carbonylation using CO surrogates, see: (a)
*
*
Eꢀmail: pengjb_05@zstu.edu.cn
Eꢀmail: xiaoꢀfeng.wu@catalysis.de
Morimoto, T.; Kakiuchi, K. Evolution of carbonylation catalysis: no need
for carbon monoxide. Angew. Chem. Int. Ed. 2004, 43, 5580ꢀ5588. (b)
Odell, L. R.; Russo, F.; Larhed, M. Molybdenum hexacarbonyl mediated
CO gasꢀfree carbonylative reactions. Synlett 2012, 685ꢀ698. (c) Konishi,
H.; Manabe, K. Formic acid derivatives as practical carbon monoxide
surrogates for metalꢀcatalyzed carbonylation reactions. Synlett 2014, 1971ꢀ
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Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
1
986. (d) Gautam, P.; Bhanage, B. M. Recent advances in the transition
The authors thank the financial supports from NSFC (21472174,
metal catalyzed carbonylation of alkynes, arenes and aryl halides using CO
surrogates. Catal. Sci. Technol. 2015, 5, 4663ꢀ4702. (e) Friis, S. D.;
Lindhardt, A. T.; Skrydstrup, T. The development and application of twoꢀ
chamber reactors and carbon monoxide precursors for safe carbonylation
reactions. Acc. Chem. Res. 2016, 49, 594ꢀ605. (f) Peng, J.ꢀB.; Qi, X.; Wu, X.ꢀ
F. Recent achievements in carbonylation reactions: a personal account.
Synlett 2017, 28, 175ꢀ194.
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1602201, 21602204, 21772177), education department of Zhejiang
Province (Y201636555), Zhejiang SciꢀTech University (16062095ꢀY)
and Zhejiang Natural Science Fund for Distinguished Young Scholars
(LR16B020002)
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