Pd-tetraethyl tetra-t-butylcalixarene-tetra(oxyacetate) complex catalyzed acylodeboronation of arylboronic acids with benzoyl chloride or acetic anhydride

Article abstract of DOI:10.3998/ark.5550190.p007.750

The palladium-tetraethyl tetra-t-butylcalixarene-tetra(oxyacetate) complex, in the form of [NaL]⁺[PdCl3]^-, exhibited high catalytic efficiency for the acylodeboronation reaction of arylboronic acids with benzoyl chloride or acetic anhydride, producing the corresponding ketones in good to excellent yields under mild reaction conditions. Various arylboronic acids, benzoyl chlorides and acetic anhydrides were tolerated in this method. Moreover, a typical method for synthesis of acetyl aryl ketones was obtained.

Full text of DOI:10.3998/ark.5550190.p007.750

General Papers
ARKIVOC 2013 (iv) 251-271
Pd-tetraethyl tetra-t-butylcalixarene-tetra(oxyacetate) complex
catalyzed acylodeboronation
of arylboronic acids with benzoyl chloride or acetic anhydride
Jinli Zhang, Zixing Han, Junmiao Li, and Yangjie Wu*
The College of Chemistry and Molecular Engineering, Henan Key Laboratory of Chemical
Biology and Organic Chemistry, Key Laboratory of Applied Chemistry of Henan Universities,
Zhengzhou University, Zhengzhou, 450052, P. R. China
E-mail: wyj@zzu.edu.cn
Abstract
The palladium-tetraethyl tetra-t-butylcalixarene-tetra(oxyacetate) complex, in the form of [NaL]+
[PdCl3]–, exhibited high catalytic efficiency for the acylodeboronation reaction of arylboronic
acids with benzoyl chloride or acetic anhydride, producing the corresponding ketones in good to
excellent yields under mild reaction conditions. Various arylboronic acids, benzoyl chlorides and
acetic anhydrides were tolerated in this method. Moreover, a typical method for synthesis of
acetyl aryl ketones was obtained.
Keywords: Tetraethyl tetra-t-butylcalixarene-tetra(oxyacetate), palladium catalyst, aryl ketone,
carbonylation
Introduction
Due to the wide occurrence of aryl ketone moiety in a large number of biologically active
compounds1, natural products,2 cosmetics,3 pharmaceutical, fragrance, dye, agrochemicals and
functional material industries as well as in organic synthesis,4 considerable efforts have been
made for its synthesis. Aromatic ketones can be effectively prepared by palladium catalyzed
carbonylation reaction of acyl chlorides with boronic acid.5-7 Such method can avoid the
restrictions of the regioselectivity limitation of para position (traditional Friedel-Crafts
acylation8), using of toxic carbon monoxide and the formation of biaryl side products
(carbonylative Suzuki-Miyaura cross-coupling9), the requirement of directing group
(carbonylative C-H activation10), harsh reaction conditions (oxidation of benzyl alcohols11 and
addition of organometallic reagents to carboxylic derivatives or nitriles12) and incompatibility
with electron-deficient groups etc.7,13-15
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However, there are still some limitations for the synthesis of aliphatic acyl phenone using
aliphatic acyl chloride or acetic anhydride as acyl reagent, especially for the synthesis of various
acetophenone from acetic chloride or anhydride.5c,5f,6g,7a The coupling between phenylboronic
acid and acetic anhydride were scatteredly reported5c,5f,6d and only Gooben5f obtained satisfactory
results. Thus, it is challenging to develop catalytic carbonylation of aliphatic acyl chloride or
acetic anhydride with high efficiency.
Nowadays, calixarenes are emerging as a versatile family of ancillary ligands in a variety of
catalytic processes.16 For example, calixarenes bearing phosphines or NHCs functional groups
have been reported to exhibit notably high catalytic activities in transition metal catalyzed C-C
bond formation reactions.17 In addition, calix[4]aryl acetates showed remarkably high sodium
ion affinity and selectivity owing to the “size fitting effect”.18a-18c Recently, our group reported
the synthesis of a kind of tetraethyl tetra-t-butylcalixarene-tetra(oxyacetate) and its catalytic
activity in Suzuki cross-coupling reaction.18d In this paper, we wish to report the palladium-
tetraethyl tetra-t-butylcalixarene-tetra(oxyacetate) complex catalyzed acylodeboronation reaction
of arylboronic acids with benzoyl chloride or acetic anhydride respectively for the easy
preparation of aryl ketones. To the best of our knowledge, this is the first report on the coupling
of carboxylic anhydride or acyl chloride catalyzed by 0.5% catalyst loading of palladium
complex based on tetraethyl tetra-t-butylcalixarene-tetra(oxyacetate).
Results and Discussion
Synthesis of the catalyst and its characterization
Tetraethyl tetra-t-butylcalixarene-tetra(oxyacetate) (L) was synthesized according to the general
procedure.19 Palladium complex was obtained according to the literature and characterized by X-
ray18d analysis.
rt
2Na2PdCl4
+
2NaLPdCl3
1
2L
+
2NaCl
OEt
EtO
But
tBu
O
O
O
Cl
Cl
Cl
Cl
O
EtO
HO
OEt
O
tBu
tBu
Pd
O
O
But
But
O
O
Na
Na
O
O
4
Pd
O
EtO
OEt
O
O
O
Cl
O
Cl
tBu
But
L
EtO
O
OEt
EtO
Cat. 1
Scheme 1. Synthesis of catalyst 1.
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o
1
The red solid of L was obtained in a 65% yield. mp >280 C (dec). NMR spectra: H NMR
(CDCl3, 400 MHz):
12.2 Hz), 1.47 (12H, t, J 7.1 Hz), 1.11 (36H, s). C NMR:
δ
7.07 (8H, s), 4.48-4.43 (16H, m), 4.26 (4H, d, J 12.2 Hz), 3.37 (4H, d, J
13
δ
171.0, 149.6, 148.2, 134.3, 125.7,
73.2, 62.4, 34.0, 31.2, 29.8, 14.4. As shown in Scheme 1, the Na2Pd2Cl6 complex with tetraethyl
tetra-t-butyl-calixarene-tetra(oxyacetate) shows clearly a “cone” structure.
Catalytic survey
Studies on acylodeboronation reaction of arylboronic acid with benzoyl chloride
The coupling reaction of phenyl boronic acid and benzoyl chloride was chosen as a model
reaction (Table 1) to test the reactivity of Cat. 1. To compare the catalytic activities, Pd(OAc)2
and PdCl2 were used under the same reaction conditions, and relatively lower yields were
obtained respectively (entries 2-5). Yamamoto’s and Goossen’s studies have showed that the
phosphine ligands played key roles in the successful execution of the reactions.20 Gratifyingly,
the carbonylation coupling proceeded smoothly and gave benzophenone in 68% isolated yield
o
when Cat. 1 was used as a catalyst in the presence of PPh3 and K3PO4 in toluene at 90 C under
air (Table 1, entry 7). These results indicated that the combination of tetraethyl tetra-t-
butylcalixarene-tetra(oxyacetate) and PPh3 promoted the procedure of acylodeboronation.
Inspired by these results, we then screened the bases and reaction temperatures by using 0.5
mol% Cat. 1. The carbonylation yield as high as 95% was obtained when the reaction was
o
conducted at 70 C under air (entry 10), which was much higher than the yields obtained by
Pd(PPh3)4.5c,7a Under the proper reaction conditions, other phosphine ligands were also applied
and gave lower carbonylation yields (entries 11-14). Cat. 1 showed slight catalytic activities
under lower temperature and concentration (entries 15-16). The results showed that the “size
fitting effect” between tetraethyl tetra-t-butylcalixarene-tetra(oxyacetate) and palladium anion
played key roles for the reaction (entry 18).
Table 1. Study on acylodeboronation reaction of phenyl boronic acid with benzoyl chloride
O
O
Cl
Cat. 1,
Solvent, T, Base
PPh3
B(OH)2
1a
2a
3a
Entrya
1
Catalyst
Bases
T, oC Time, h
Yield % b
Trace
<5
--
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
90
90
90
90
90
90
90
12
12
12
12
12
12
12
Na2PdCl4+PPh3
Pd(OAc)2
Pd(OAc)2+PPh3
PdCl2
PdCl2+PPh3
Cat. 1
2
3
4
5
6
50
31
16
35
Trace
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Table 1. Continued
Entrya
7
Catalyst
Cat. 1+PPh3
Cat. 1+PPh3
Cat. 1+PPh3
Cat. 1+PPh3
Pd(OAc)2+dppe
Pd(OAc)2+dppf
PdCl2+dppe
PdCl2+dppf
Cat. 1+PPh3
Cat. 1+PPh3
Cat. 1+PPh3
L+ NaCl + PdCl2
Bases
K3PO4
K2CO3
Na2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
T, oC Time, h
Yield % b
68
98
Trace
95
90
90
90
70
70
70
70
70
40
70
70
70
12
12
12
12
12
12
12
12
12
12
12
12
8
9
10
11
12
13
14
15
16
17
18 e
56
48
77
71
38
76c
92d
-
a benzoyl chloride (1.0 mmol), phenyl boronic acid (0.5 mmol), base (1.0 mmol), complex 1 (0.5
o
b
c
mol%, 3.1 mg), PPh3 (0.01 mmol) and toluene (2.0 mL), 70 C. isolated yields. 0.25 mol%
complex 1 was used and the acylodeboronation yield was determined by GC analysis using 3a as
internal standard substances. d 1 mol% complex 1 was used and the acylodeboronation yield was
e
determined by GC analysis using 3a as internal standard substances. tetraethyl tetra-t-
butylcalixarene-tetra(oxyacetate) L (0.005 mmol), NaCl (0.005 mmol), PdCl2(0.005 mmol), and
the acylodeboronation yield could not be repeated (20-60%).
With the standard conditions in hand, we then examined the scope and limitation of Cat. 1 in
the acylodeboronation reaction. Various arylboronic acids and benzoyl chloride were applied to
this system (Table 2, entries 1-14). The results listed in Table 2 showed that this catalytic system
tolerated various functional groups, such as CH3, CH3O, Br, Cl, F, CHO, and CH3CO. Both
electron-rich and electron-deficient arylboronic acids could provide the desired products in
moderate to excellent yields (Table 2, entries 1-10). 1-Naphthyl and 2-thienyl boronic acids also
reacted smoothly with benzoyl chloride, yielding the corresponding aryl ketones in 89% and
95% yields, respectively (Table 2, entries 11-12). Some ketones, such as 3b, 3f, 3i and 3j,
usually difficult to obtain from traditional Friedel-Crafts methods by using benzoyl chloride as
substrate,8 were produced successfully with moderate to good yields in this protocol (Table 2,
entries 2, 6, 9, 10).
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Table 2. Complex 1 catalyzed acylodeboronation reaction of arylboronic acids with benzoyl
chloride
O
Cat. 1 (0.5 mol%)
O
PPh3 (1 mol%)
R2
B(OH)2
R1
R1
K2CO3 (2 eq), 70 oC
Toluene, air
R2
Cl
1a-l
2a-c
3a-m
Entrya
1
Arylboronic acids
Benzoyl chlorides
Products
Yield, % b
95
O
O
O
O
O
O
O
O
O
O
B(OH)2
1a
Cl
3a
2a
O
Cl
2
3
4
5
6
7
8
9
84
90
90
93
75
73
78
67
B(OH)2
1b
3b
2a
O
1c
H3CO
B(OH)2
Cl
2a
3c
O
Br
O
Br
Cl
Cl
B(OH)2 1d
2a
3d
Cl
O
Cl
B(OH)2
B(OH)2
1e
2a
3e
O
Cl
Cl
Cl
1f
3f
2a
O
Cl
B(OH)2
B(OH)2
B(OH)2
Cl
1g
3g
2a
Cl
F
O
F
Cl
1h
3h
2a
O
Ac
Cl
1i
3i
2a
Ac
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Table 2. Continued
Entrya
Arylboronic acids
Benzoyl chlorides
Products
Yield, % b
62
O
O
OHC
B(OH)2
1j
Cl
10
3j
2a
OHC
O
B(OH)2
O
1k
Cl
11
12
13
14
89
95
84
88
3k
2a
O
O
S
1l
Cl
B(OH)2
S
3l
2a
O
O
B(OH)2
B(OH)2
1a
1a
Cl
2b
3m
O
O
Cl
2c
3c
O
O
a
reaction conditions: benzoyl chloride (1.0 mmol), arylboronic acid (0.5 mmol), base (1.0
o
b
mmol), complex 1 (0.5 mol%), PPh3 (0.01 mmol) and toluene (2.0 mL), 70 C, 12h. isolated
yields.
Studies on the acylodeboronation reaction of arylboronic acid with acetic anhydride
When Na2CO3 was used as base (Table 1, entry 9), trace amount of benzophenone was observed.
Benzoic acid anhydride was obtained as main product (determined by GC analysis). Treating the
obtained benzoic acid anhydride with phenylboronic acid (new added), the desired
benzophenone was isolated in 96% yield. These results revealed that the formation of ketone
may proceed via the intermediate of benzoic acid anhydride, and Cat. 1 was also an efficient
catalyst for the carbonylation reaction of arylboronic acid with acid anhydride (Scheme 2).
Acetophenone derivatives are useful intermediates in industry as well as in organic synthesis.
Carbonylation reaction of acetyl chloride or anhydride with boronic acid could also be used for
6g
its synthesis. Bandgar has reported the reaction of arylboronic acid with benzoyl chloride by
using PdCl2 as catalyst and Na2CO3 as base. But the catalyst loading is high (3.3%) and the
6g,7a
coupling between acetyl chloride with boronic acid remains unsuccessful
or only in
moderate yields.5c Also the coupling between acetic anhydride with arylboronic acid has been
reported by Gooben by using Pd(OAc)2 as catalyst, expensive P(p-MeOPh)3 as ligand, and
5f
excess of arylboronic acid.
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PhB(OH)2 1a
Yield 96%
[Pd]
O
O
B(OH)2
O
O
[Pd]
Ph
O
Ph
Ph
Cl
Ph
1a
2a
4c
3a
Major
1
Trace
Air
N2
Na2CO3
:
5
K3PO4
K2CO3
Air
Air
1
:
4.5
Trace
Major
Scheme 2. Study on the effect of Na2CO3 as base for acylodeboronation reaction of
phenylboronic acid with benzoic acid chloride.
We then choose acetic anhydride as reagent to test the reactivity of Cat.1. Initially, the cross-
coupling reaction conditions of phenylboronic acid with acetic anhydride were screened (listed in
Table 3). The best yield of 85% was obtained when KHCO3 was used as base in toluene at 110
oC under nitrogen (Table 3, entry 6).
Tabel 3. Study on acylodeboronation reaction of phenyl boronic acid with acetic anhydride
O
Cat. 1,
PPh3
B(OH)2
Ac2O
Solvent, T, Base
1a
4a
5a
Entrya
1
Catalyst
Solvent
Base
T, oC Time, h Gas Yield, % b
Cat. 1+PPh3
Cat. 1+PPh3
Cat. 1+PPh3
Cat. 1+PPh3
Cat. 1+PPh3
Cat. 1+PPh3
Cat. 1+PPh3
PdCl2+PPh3
PdCl2+dppe
PdCl2+dppf
Toluene
Toluene
Toluene
Toluene
Toluene Na2CO3
Toluene KHCO3
Toluene NaHCO3
Toluene Na2CO3
K2CO3
K2CO3
K2CO3
K3PO4
70
12
12
3
Air
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
N2
15
48
2
3
4
5
70
110
110
110
110
110
110
110
110
110
110
110
110
67
42
40
85
3
3
6
3
7
8
9
10
11
12
13
14
3
3
3
3
3
3
3
3
17
52
Toluene
Toluene
KHCO3
KHCO3
KHCO3
KHCO3
KHCO3
KHCO3
Trace
Trace
40
Trace
Trace
Trace
Pd(OAc)2+ PPh3 Toluene
Pd(OAc)2+dppe
Pd(OAc)2+dppf
Cat. 1
Toluene
Toluene
Toluene
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Table 3. Continued
o
Entrya
15
16
17c
Catalyst
Solvent
THF
DMF
Base
T, C Time, h Gas Yield, % b
Cat. 1+PPh3
Cat. 1+PPh3
L +NaCl+ PdCl2 Toluene NaHCO3
KHCO3
KHCO3
60
110
110
3
3
3
N2
N2
N2
77
Trace
-
a
acetic anhydride (1.0 mmol), arylboronic acid (0.5 mmol), base (1.0 mmol), complex 1 (0.5
b
c
mol%), PPh3 (0.01 mmol) and solvent (2.0 mL). isolated yields. yields could not be repeated
(20-40%).
Under the optimal conditions, the scope of arylboronic acids and anhydrides for this
acylodeboronation transformation was investigated. As shown in Table 4, the carbonylation
yields were influenced by electron effect. Arylboronic acids with electron-rich groups such as
CH3 or CH3O, as well as 1-naphthyl motif could be coupled with acetic anhydride in moderate to
good yields (Table 4, entries 1-5). When arylboronic acids bearing electron-deficient groups
were applied, moderate yields were still obtained (Table 4, entries 6-8). Other kinds of
anhydrides were also applied, yielding the corresponding ketones in lower yields (Table 4,
entries 9-10).
Table 4. Complex 1 catalyzed acylodeboronation reaction of arylboronic acids with acetic
anhydride
Cat. 1 (0.5 mol%)
O
O
O
PPh3 (1 mol%)
B(OH)2
R
R'
O
R'
KHCO3 (2 eq), 110
Toluene, N2, 3 h
R'
1a-m
4a-c
5a-i
Entrya
1
Arylboronic acids
Anhydrides
Products
Yield, % b
O
O
O
O
O
O
O
4a
4a
4a
B(OH)2
1a
O
O
O
85
76
5a
O
2
3
4
B(OH)2
1b
5b
O
1c
B(OH)2
H3CO
69
79
5c
O
O
O
O
4a
B(OH)2 1m
O
5d
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Table 4. Continued
Entrya
Arylboronic acids
B(OH)2
Anhydrides
Products
Yield, % b
89
O
O
O
1k
5
4a
O
O
5e
O
Cl
O
O
Cl
6
7
4a
62
61
1f
B(OH)2
B(OH)2
5f
O
O
O
Cl
1g
4a
O
5g
Cl
Cl
O
Cl
O
O
O
O
8
9
4a
59
56
B(OH)2
B(OH)2
1e
O
5h
O
1a
1a
4b
O
O
5i
O
O
10
59 (96 c)
B(OH)2
O
4c
3a
a
reaction conditions: acetic anhydride (1.0 mmol), arylboronic acid (0.5 mmol), base (1.0
o
b
mmol), complex 1 (0.5 mol%), PPh3 (0.01 mmol) and toluene (2.0 mL), 110 C, 3 h. isolated
yields. c Na2CO3 was used as base.
Mechanistic study
In order to provide evidence that the enhanced yields using Cat. 1 were not due to the use of a
Na2PdCl4 instead of Pd(OAc)2 or PdCl2, the carbonylation reaction of benzoyl chloride with
phenylboronic acid was conducted by using the mixture of Na2PdCl4 pre-catalyst and
triphenylphosphine. It is clear that the high catalytic efficiency were attributed to the “size fitting
effect” between tetraethyl tetra-t-butylcalixarene-tetra(oxyacetate) L and palladium anion (Table
5, entries 1-4). Furthermore, a investigation on the catalytic activity of Na2PdCl4 with different
phosphine ligands such as PPh3, dppe or dppf was undertaken to clarify the role of tetraethyl p-
tert-butyl-calix[4]aryl tetraacetate (L) in the formation of the catalytically active species (Table 5,
entries 5-7). Na2PdCl4 with the mixture of L and different phosphine as ligands showed slightly
lower activity under the same reaction conditions. Except the ligand dppe, the mixture of
Na2PdCl4, L and PPh3 or dppf resulted in the homo-coupling of phenylboronic acid.
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Table 5. Studies on the role of tetraethyl tetra-t-butylcalixarenetetra(oxyacetate) L
O
Catalyst
O
B(OH)2
K2CO3 (2 eq), 70 oC
Toluene, air
Cl
1a
2a
3a
Entrya
Catalyst
Cat.1+PPh3
Na2PdCl4+PPh3
PdCl2+PPh3
Pd(OAc)2+ PPh3
Na2PdCl4+L+PPh3
Na2PdCl4+L+dppe
Na2PdCl4+L+dppf
Yiled % of 3a b
1
2
3
4
5
6
7
98
65
81
82
10 c
78
15 c
a benzoyl chloride (1.0 mmol), phenyl boronic acid (0.5 mmol), K2CO3 (1.0 mmol), complex 1
(0.5 mol%), tetraethyl tetra-t-butylcalixarene-tetra(oxyacetate) L (0.005 mmol), NaCl (0.005
mmol), PdCl2 (0.005 mmol), Pd(OAc)2 (0.005 mmol), phosphine ligand (0.01 mmol) and toluene
(2.0 mL), 70 oC, 24 h. b GC yields by using 3a as internal standard substances. c the side product
(~70% GC yield) was determined by using biphenyl as internal standard substances.
Cat. 1 (Na2Pd2L2Cl6)
tBu
But
tBu
tBu
Pd(II) precatalyst
O
pre-activation
O
O
Ar
R
R
O
R
O
O
O
O
O
O
PdL'2
or
Na
R
Cl
EtO
O
O
EtO
OEt
reductive
elimination
O
oxidative
addition
OEt
Cl
Cl
Cl
Cl
Cl
Cl
Pd
L'
L'
Ar Pd L'
L'
or
Pd
O
O
L'
Cl
L'
R
Pd
R
O
EtO
O
O
R
O
OEt
O
R
EtO
HO
Na
OEt
O
O
O
O
O
transmetallation
OH
O
B
HO
O
R
L'=PPh3
ArB(OH)2
OH
B
But
tBu
tBu
or
But
HO
Cl
Cat. 1 (Na2Pd2L2Cl6)
Catalytic cycle
Scheme 3. Possible mechanism.
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Based on the ligature and results obtained above, a possible reaction mechanism was
proposed as outlined in Scheme 3. Firstly, Pre-activation of Cat.1 generated the active palladium
-
catalyst PdL’2 in the anion of Pd2Cl6 . We hypothesized that the active palladium catalyst
covered on the anion as shown in Scheme 4. The benzoyl chloride 2a was transported one by one
through the cage of tetraethyl tetra-t-butylcalixarene-tetra(oxyacetate) L to access the active
palladium catalyst from two side (Scheme 4). Fast oxidative addition gave the intermediate.
After the completion of transmetallation of phenylboronic acid 1a, the catalytic cycle was
finished followed by the reductive elimination finally.
PdL'2
O
O
PdL'2
PdL'2
PdL'2
PdL'2
R
Cl
R
Cl
EtO
O
O
O
OEt
O
EtO
O
OEt
O
O
O
L
But
But
But
But
Scheme 4. The role of the tetraethyl p-tert-butyl-calix[4]aryl tetraacetate.
-
It is reliable that the catalytic cycle was finished in the anion part of Pd2Cl6 since the
biphenyl was observed as main product when the ligand L was mixed with 1a and 2a (Table 5,
entry 5). We resumed that the efficiency of Pd-tetraethyl tetra-t-butylcalixarene-tetra
(oxyacetate) complex in the carbonylation reaction could be attributed to its surface properties,
and its capacity to bind strongly to benzoyl chloride into its hydrophobic pocket, which enhanced
the ability to interact with the reagents and palladium (Scheme 4).18d
Conclusions
In summary, Pd-tetraethyl tetra-t-butylcalixarene-tetra(oxyacetate) complex, in the form of
[NaL]+[PdCl3]-, catalyzed cross-coupling reactions of various arylboronic acids with benzoyl
chloride or acetic anhydride were successfully achieved with low catalyst loading of 0.5 mol%.
This protocol has the advantages of straightforward, easy handling and cheap substrates as
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coupling partner. Most important, the advantage of high functional group tolerance made this
method possible to obtain several acetophenones difficult to access by traditional Friedel-Crafts
reaction. Moreover, this study provides a particular method to synthesize methyl aryl ketones by
acetylation using acylodeboronation reactions.
Experimental Section
General. Melting points were measured on a XT-5 microscopic apparatus. GC analyses were
1
performed on Agilent 4890D gas chromatograph. H NMR and 13C NMR spectra were recorded
on a Bruker DPX 400 instrument using CDCl3 or DMSO-d6 as the solvent and TMS as the
internal standard.
Palladium complex based on a tetraethyl tetra-t-butylcalixarene-tetra(oxyacetate) was
synthesized according to the literature.3d All solvents were tried by the standard methods. The
chemicals were reagent grade and used without further treatment.
General procedure for the acylodeboronation reaction of arylboronic acids with benzoyl
chloride. A 5 mL flask charged with benzoyl chloride (1.0 mmol), arylboronic acid (0.5 mmol),
K2CO3 (1.0 mmol), complex 1 (0.5 mol%, 3.1 mg), PPh3 (0.01 mmol, 1.3 mg) and toluene (2.0
mL) was put into a preheated 70 oC oil bath for an appropriate period of time under air. After the
reaction was finished, the reaction mixture was cooled to room temperature, filtered through a
short silica column and washed with ethyl acetate. Then the combined filtrates were concentrated
in vacuo and the residue was purified by flash chromatography (eluent: ethylacetate/petroleum
1
ether). All the products were known compounds and characterized by comparing mp, H NMR
and 13C NMR spectra with literature.
Benzophenone (3a, Table 2, entry 1). White solid, mp 47-48 oC (lit.21 47-49 oC). 1H NMR (400
13
Mz, CDCl3):
CDCl3): 196.7, 137.4, 132.3, 129.9, 128.1.
3-Methyl-benzophenone (3b, Table 2, entry 2). Light yellow oil . H NMR (400 Mz,
CDCl3): 7.79-7.77 (m, 2H), 7.62 (s, 1H), 7.57-7.54 (m, 2H), 7.47-7.44 (m, 2H), 7.37-7.34 (m,
δ
7.81-7.78 (m, 4H), 7.59-7.54 (m, 2H), 7.49-7.45 (m, 4H); C NMR (100 Mz,
δ
22
1
δ
13
2H), 2.40 (s, 3H); C NMR (100 Mz, CDCl3):
130.0, 128.4, 128.1, 127.2, 21.2.
δ
196.8, 138.0,137.6, 137.5, 133.4, 132.2, 130.3,
4-Methoxybenzophenone (3c, Table 2, entry 3 and entry 14). White solid, mp 59-60 oC (lit.23
61-62 oC). H NMR (400 Mz, CDCl3):
1
δ
7.83-7.80 (m, 2H), 7.76-7.73 (m, 2H), 7.54-7.45 (m,
13
3H), 6.96-6.93 (m, 2H), 3.86 (s, 3 H). C NMR (100 Mz, CDCl3):
δ
195.4,163.0, 138.1, 132.4,
131.7, 130.0, 129.6, 128.0,113.4, 55.34.
24
1
2-bromobenzophenone (3d, Table 2, entry 4). light yellow oil . H NMR (400 Mz, CDCl3):
δ
7.80-7.78 (m, 2H), 7.62-7.56 (m, 2H), 7.45. 13C NMR (100 Mz, CDCl3):
δ
195.7, 140.5,
136.0, 133.7, 133.1, 131.1,130.1, 128.8, 128.5, 127.1, 119.4.
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o
1
2-Chlorobenzophenone (3e, Table 2, entry 5). White solid, mp 42-43 oC (lit.10b 43-45 C). H
NMR (400 Mz, CDCl3): 7.79-7.77 (m, 2 H), 7.55-7.53 (m, 1 H), 7.44-7.38 (m, 4 H), 7.31-7.23
δ
13
(m, 2 H). C NMR (100 Mz, CDCl3):
128.5, 126.6.
δ
195.4, 138.4, 136.3, 133.6, 131.1, 131.0,130.0, 129.0,
3-Chlorobenzophenone (3f, Table 2, entry 6). White solid, mp 81-83 oC (lit.25. 84 oC). 1H NMR
(400 Mz, CDCl3):
δ
7.79-7.77 (m, 3H), 7.66-7.64 (m, 1H), 7.59-7.50 (m, 2H), 7.48-7.46 (m,
2H), 7.43-7.40 (m, 1H). 13C NMR (100 Mz, CDCl3):
130.1, 129.9, 129.7, 129.5, 128.5, 128.3, 128.0.
δ
195.0, 139.1, 136.8, 134.4, 132.7, 132.2,
4-Chlorobenzophenone (3g, Table 2, entry 7). White solid, mp 73-74 C (lit.26 73-74 C). H
o
o
1
NMR (400 Mz, CDCl3):
(100 Mz, CDCl3):
δ
7.77-7.73 (m, 4H),7.58-7.56 (m, 1H), 7.51-7.45 (m, 4H). 13C NMR
δ
195.3, 138.7, 137.0, 135.7, 132.5, 131.1, 129.8, 128.5, 128.2.
4-Fluoro-benzophenone (3h, Table 2, entry 8). White solid, mp 48-49 C (lit.27 47-49 C). 1H
o
o
13
NMR (400 Mz, CDCl3):
(100 Mz, CDCl3):
128.2, 115.9, 115.2.
4-Acetobenzophenone (3i, Table 2, entry 9). White solid, mp 83-84 oC (lit.28 83-84 oC). 1H
NMR (400 Mz, CDCl3): 8.07-8.04 (m, 2H), 7.87-7.85 (m, 2H), 7.82-7.79 (m, 2H), 7.62-7.50
(m, 3H), 2.67 (s, 3H). C NMR (100 Mz, CDCl3):
130.1, 130.0, 128.5, 128.3, 26.8.
4-Formyl-benzophenone (3j, Table 2, entry 10). White solid, mp 57-59 oC (lit.29 58-60 oC). 1H
δ
7.85-7.75 (m, 4H), 7.58-7.45 (m, 3H), 7.16-7.12 (m, 2H); C NMR
δ
195.1, 166.5, 164.0, 137.3, 133.7, 133.6, 132.6, 132.5, 132.3, 130.0, 128.5,
δ
13
δ
197.5, 195.9, 141.1, 139.4, 136.7, 133.8,
NMR (400 Mz, CDCl3):
δ
10.1( s, 1H), 7.95-7.92 (m, 2H), 7.91-7.89 (m, 2H), 7.81-7.79 (m,
2H), 7.62-7.58 (m, 1H), 7.52-7.44 (m, 2H); 13C NMR (100 Mz, CDCl3):
138.3, 133.0, 130.1, 129.7, 129.2, 128.4.
δ
195.6, 191.6, 142.4,
1-Benzoylnaphthalene (3k, Table 2, entry 11). White solid, mp 74-75 C (lit.30 74-76 oC). H
o
1
NMR (400 Mz, CDCl3):
7.38 (m, 7H). 13C NMR (100 Mz, CDCl3):
130.3, 128.7, 128.4, 127.7, 127.2, 126.4, 125.6, 124.3.
2-Benzoylthiophene (3l, Table 2, entry 12). White solid, mp 54-55 C (lit.31 56-57 C). H
NMR (400 Mz, CDCl3): 7.85-7.87 (m, 2H), 7.72-7.71 (m, 1H), 7.64-7.63 (m, 1H), 7.61-7.58
δ
8.10-8.08 (m, 1H), 7.94 (d, J 8.4 Hz, 1H), 7.93-7.82 (m, 3H), 7.53-
δ
197.9, 138.2, 136.2, 133.6, 133.2, 131.2, 130.8,
o
o
1
δ
13
(m, 1H), 7.50-7.48 (m, 2H), 7.16-7.14 (m, 1H). C NMR (100 Mz, CDCl3):
δ
188.1, 143.5,
138.0, 134.8, 134.2, 132.2, 130.0, 129.0, 128.3, 127.9.
1
4-Methyl-benzophenone (3m, Table 2, entry 13). light yellow oil32. H NMR (400 Mz,
CDCl3):
δ
8.10-8.08 (d, J 8.0 Hz, 2H), 7.79-7.71 (d, J 7.6 Hz, 2H), 7.59-7.55 (m, 1H), 7.20 (m,
13
5 H), 2.43 (s, 3 H); C NMR (100 Mz, CDCl3):
δ
196.5, 165.3, 151.0, 144.4, 143.3, 132.2,
130.3, 130.2, 130.0, 129.5, 129.3, 129.0, 128.2, 126.8, 125.8, 121.8, 21.7.
General procedure for the acylodeboronation reaction of arylboronic acids with acetic
anhydride. A 5 mL flask charged with acetic anhydride (1.0 mmol), arylboronic acid (0.5
mmol), KHCO3 (1.0 mmol), complex 1 (0.5 mol%, 3.1 mg), PPh3 (0.01 mmol, 1.3 mg) and
toluene (2.0 mL) was evacuated and backfilled with N2 for three times before the reaction was
o
put into a preheated 110 C oil bath. After the reaction was finished in 3h, the reaction mixture
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ARKIVOC 2013 (iv) 251-271
was cooled to room temperature, filtered through a short silica column and washed with ethyl
acetate. Then the combined filtrates were concentrated in vacuo and the residue was purified by
flash chromatography (eluent: ethylacetate/petroleum ether). All the products were known
compounds and characterized by comparing mp, 1H NMR and 13C NMR spectra with literature.
Acetophenone (5a, Table 4, entry 1). Light yellow oil33 1H NMR (400 Mz, CDCl3):
7.94 (m, 2H), 7.58-7.54 (m, 1H), 7.48-7.45 (m, 2H), 2.58 (s, 3H); C NMR (100 Mz, CDCl3):
δ
7.97-
13
δ
198.5, 137.6, 133.5, 129.0, 128.7, 26.9.
3-Methylacetophenone (5b, Table 4, entry 2). Light yellow oil14 1H NMR (400 Mz, CDCl3):
δ
7.76-7.73 (m, 2H), 7.35-7.33 (m, 2H), 2.60 (s, 3H), 2.40 (s, 3H). 13C NMR (100 Mz, CDCl3):
198.4, 138.3, 137.1, 133.8, 128.7, 128.4, 125.5, 26.6, 21.3.
δ
4-Methoxyacetophenone (5c, Table 4, entry 3). Light yellow oil33 1H NMR (400 Mz, CDCl3):
δ
7.91 (d, J 8.80 Hz, 2H), 6.93 (d, J 8.80 Hz, 2H), 3.84 (s, 3H), 2.52 (s, 3H). 13C NMR (100 Mz,
CDCl3): 196.7, 163.5, 130.5, 130.3, 113.6, 55.4, 26.3.
4-Methylacetophenone (5d, Table 4, entry 4). Light yellow oil33 1H NMR (400 Mz, CDCl3):
7.84 (d, J 8.04 Hz, 2H), 7.23 (d, J 8.04 Hz, 2H), 2.55 (s, 3H), 2.39 (s, 3H). 13C NMR (100 Mz,
δ
δ
CDCl3):
δ
197.8, 143.8, 134.7, 129.2, 128.4, 26.5, 21.6.
1-Acetonaphthone (5e, Table 4, entry 5). Light yellow oil33 1H NMR (400 Mz, CDCl3):
δ
8.74
13
(d, J 8.60 Hz, 1H), 7.85 (m, 3H), 7.57 (m, 1H), 7.45 (m, 2H), 2.69 (s, 3H). C NMR (100 Mz,
CDCl3):
3-Chloroacetophenon (5f, Table 4, entry 6). light yellow oil
CDCl3): 7.93-7.92 (m, 1H), 7.84-7.82 (m, 1H), 7.55-7.53 (m, 1H), 7.43-7.39 (m, 1H), 2.60 (s,
δ
201.8, 135.4, 134.0, 133.0, 130.2, 128.7, 128.4, 128.0, 126.4, 126.0, 124.3, 30.0.
[34]
1H NMR (400 Mz,
δ
3H); 13C NMR (100 Mz, CDCl3):
δ
196.7, 138.6, 134.9, 133.0, 129.9, 128.4, 126.4, 26.6.
4-Chloroacetophenone (5g, Table 4, entry 7). light yellow oil34 1H NMR (400 Mz,
13
CDCl3):
CDCl3):
δ
7.88 (d, J 8.8 Hz, 2H), 7.42 (d, J 8.8 Hz, 2H), 2.58 (s, 3H); C NMR (100 Mz,
196.8, 139.5, 135.4, 129.7, 129.4, 128.9, 122.9, 26.5.
δ
2-Chloroacetophenone (5h, Table 4, entry 8). Llight yellow oil34 1H NMR (400 Mz, CDCl3):
13
δ
7.56-7.54 (m, 1H), 7.41-7.31 (m, 3 H), 2.65 (s, 3H); C NMR (100 Mz, CDCl3):
δ
200.4,
139.1, 132.0, 131.2, 130.6, 129.4, 126.9, 30.7.
1-phenylpropan-1-one (5i, Table 4, entry 9). Light yellow oil33 1H NMR (400 Mz, CDCl3):
8.00-7.96 (m, 1H), 7.56-7.44 (m, 2H), 7.09-7.07 (m, 2H), 3.0 (m, 2H), 1.22-1.24 (m, 3H); 13C
δ
NMR (100 Mz, CDCl3):
δ
198.5, 137.6, 133.5, 129.0, 128.7, 26.9.
Acknowledgements
We are grateful to the National Science Foundation of China (Project 21102132, 21172200,
20772114) and the Innovation Fund for Outstanding Scholar of Henan Province (Project
0621001100) for the financial support given to this research.
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