Palladium-catalyzed alkoxycarbonylation of aryl halides with phenols employing formic acid as the CO source

Article abstract of DOI:10.1039/c5cy01957e

An efficient palladium-catalyzed alkoxycarbonylation of aryl halides with phenols has been developed. Various aryl benzoates have been isolated in good to excellent yields with formic acid as the CO source. The reaction proceeds smoothly under mild conditions and good functional group tolerance was observed.

Full text of DOI:10.1039/c5cy01957e

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Palladium-catalyzed alkoxycarbonylation of aryl
halides with phenols employing formic acid as the
CO source†
Cite this: DOI: 10.1039/c5cy01957e
Xinxin Qi,a Chong-Liang Li,a Li-Bing Jiang,a Wan-Quan Zhanga
ab
Received 16th November 2015,
Accepted 3rd December 2015
*
and Xiao-Feng Wu
An efficient palladium-catalyzed alkoxycarbonylation of aryl halides with phenols has been developed. Vari-
ous aryl benzoates have been isolated in good to excellent yields with formic acid as the CO source. The
reaction proceeds smoothly under mild conditions and good functional group tolerance was observed.
DOI: 10.1039/c5cy01957e
www.rsc.org/catalysis
source.13,14 In our continued efforts to explore this catalytic sys-
Introduction
tem, herein, we wish to describe
a palladium-catalyzed
Carboxylic ester derivatives play a very important role in a
large number of organic compounds and appear to be a key
structure in many natural products, pharmaceutical com-
pounds, and so on.1 Regarding their importance, consider-
able efforts have been devoted to explore new synthetic
methods for the preparation of these kinds of compounds.
One of the most conventional approaches is the direct esteri-
fication of alcohols or phenols with the corresponding acid
analogues.2 In these procedures, disadvantages include a long
reaction time, harsh reaction conditions, and the requirement
of additives, which limit the application of these strategies.
One of the alternative protocols is the palladium-catalyzed
carbonylation reactions of organic halides with alcohols.3,4 In
the known procedures, aliphatic alcohols are more often stud-
ied than phenols with carbon monoxide as the carbonyl
source.5
In recent years, the development of CO gas-free carbonylation
procedures has become interesting, as the odourless, flammable
and highly toxic properties of CO gas has limited the application
of CO gas-based carbonylation procedures on a lab scale. Various
CO sources have been explored and applied, including alde-
hydes,6 formamides,7 formates,8 MoIJCO)6,9 WIJCO)6,10 MeOH,11d
etc.11 More recently, Skrydstrup and co-workers developed various
carbonylation procedures based on the ex situ generation of CO
gas employing a two chamber reactor.12 In this regard, we recently
developed convenient palladium-catalyzed one-pot carbonylative
Sonogashira and Suzuki reactions with formic acid as the CO
alkoxycarbonylation reaction of aryl halides and phenols using
formic acid as the CO precursor to provide a series of aryl benzo-
ates and their derivatives. Here, it is also important to mention
that Tsuji and Manabe developed palladium-catalyzed carbonyla-
tion of aryl halides with aryl formates to produce esters indepen-
dently in 2012.8f,i Aryl formates were applied as the sources of CO
and phenols. Good yields of esters can be produced. Cacchi and
co-workers applied acetic formic anhydride as the CO source for
the hydroxycarbonylation of aryl and vinyl halides.14a The acetic
formic anhydride was produced from lithium formate and acetic
anhydride, and good yields of carboxylic acids were prepared.
Results and discussion
At the beginning, we chose iodobenzene and phenol as the
model substrates, formic acid as the CO source and acetic an-
hydride as the activator, PdIJOAc)2 as the catalyst, PPh3 as a li-
gand with Et3N as a base in toluene at 80 °C. To our delight,
phenyl benzoate was formed in 46% yield (Table 1, entry 1).
Encouraged by this result, we next went on our examination
with different solvents (Table 1, entries 2–6). Toluene was
shown to be the optimal solvent. Then various bases were
screened. DBU and DABCO provided the desired product in
lower yields (Table 1, entries 7–8). No product was observed
when K2CO3 or NaOH was used as the base (Table 1, entries
9–10). Furthermore, a series of phosphine ligands were stud-
ied. For monodentate ligands, PCy3 gave a decreased yield
(Table 1, entry 11), while XPhos gave a higher yield (Table 1,
entry 12). Bidentate ligands, such as DPPF, DPPPe and DPPE,
provided similar yields compared to PPh3 (Table 1, entries
13–15). A 31% yield was observed when BINAP was applied as
the ligand (Table 1, entry 16). Gratifyingly, a 70% yield of
phenyl benzoate can be formed when using xantphos as the
ligand (Table 1, entry 17).
a Department of Chemistry, Zhejiang Sci-Tech University, Xiasha Campus,
Hangzhou 310018, People's Republic of China. E-mail: xiao-feng.wu@catalysis.de
b Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-
Strasse 29a, 18059 Rostock, Germany
† Electronic supplementary information (ESI) available: NMR spectrums.
See DOI: 10.1039/c5cy01957e
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Table 1 Screening of reaction conditionsa
Entry
Ligand
Base
Solvent
Yieldb (%)
1
2
3
4
5
6
7
8
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PCy3
XPhos
DPPPe
DPPE
DPPF
BINAP
Xantphos
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
DBU
DABCO
K2CO3
NaOH
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Toluene
THF
DMAc
DMSO
DCM
CH3CN
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
46
35
44
31
35
27
39
17
0
9
10
11
12
13c
14c
15c
16c
17c
0
9
59
44
41
44
31
70
a
Reaction conditions: iodobenzene (1.0 mmol), phenol (2.0 mmol), PdIJOAc)2 (3 mol%), ligand (6 mol%), base (5 equiv.), HCOOH (2.0 mmol),
b
acetic anhydride (2.0 mmol), solvent (2 mL), 12 h. GC yield, with dodecane as the internal standard and calculated based on iodobenzene.
c
Ligand (3 mol%). XPhos: 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl. DPPPe: 1,5-bisIJdiphenylphosphino)pentane. DPPE: 1,2-
bisIJdiphenylphosphino)ethane. DPPF: 1,1′-ferrocenediyl-bisIJdiphenylphosphine). BINAP: ( )-2,2′-bisIJdiphenylphosphino)-1,1′-binaphthalene.
Xantphos: 4,5-bisIJdiphenylphosphino)-9,9-dimethylxanthene.
With the optimized reaction conditions in hand, we then
studied various reactions of aryl iodides with phenol (Table 2).
Substrates with both electron-rich and electron-poor groups
were tolerated well and provide the corresponding phenyl ben-
zoates in moderate to good yields (Table 2, entries 2–11). Re-
markably, compounds with a methyl group substituted at the
ortho-, meta- and para-position all worked well and gave the
desired products in good yields (Table 2, entries 2 vs. 3–4).
Additionally, aryl iodides with other halide substitutions,
such as fluoro and chloro groups, could also smoothly afford
the target products in good yields (Table 2, entries 12–17).
Poly-fluoro substituted aryl iodides resulted in lower yields
than with mono-substitution (Table 2, entries 12–13 vs. 14).
In a difference from the methyl group, ortho-chloro substitu-
When different phenols were tested, moderate to good yields
of the corresponding products can be successfully isolated from
the tested substrates without further optimization (Table 4).
Then, we turned our attention to aliphatic alcohols, as
shown in Table 5, however, no benzoic acid esters were ob-
served. Only benzoic acid was produced in good to excellent
yields in these cases. This phenomenon can be explained by
the alcohols reacting with the in situ formed acetic acid and
releasing water. Then, the in situ produced water reacts with
the acylpalladium complex to give the obtained benzoic acid.
Aniline, as a representative example of a nitrogen nucleophile,
was tested in place of phenol, but no product was detected. For
the cases of a sulfur nucleophile, 2-methylpropane-2-thiol and
4-methylbenzenethiol were also tested. S-(tert-Butyl) benzo-
thioate was formed in 63% yield under identical conditions
(Scheme 1). However, only phenylIJp-tolyl)sulfane was obtained
when thiophenol was utilized.
tion gave
a similar yield to those bearing meta- and
para-chloro groups (Table 2, entries 15–16 vs. 17). 57% and
61% yields of the corresponding products were generated
when biphenyl and naphthalene iodides were used as the
substrates (Table 2, entries 18–19). Furthermore, heteroaryl
groups were also investigated; 3-iodothiophene and
3-iodopyridine afforded the desired products in high yields,
while 49% of ester was formed from 6-iodobenzopyridine (Ta-
ble 2, entries 20–22).
Taking the advantages of aryl bromides compared with
aryl iodides into account, various aryl bromides were tested
as well. As shown in Table 3, both electron-donating and
electron-deficient groups worked well and give the corre-
sponding products in moderate to good yields (Table 3, en-
tries 2–6). We note that a very good yield of phenyl nicotinate
was obtained by using 3-bromopyridine as the substrate un-
der our conditions (Table 3, entry 7).
Conclusions
In conclusion, we have developed a convenient palladium-
catalyzed alkoxycarbonylation of aryl halides and phenols with
formic acid as the CO precursor. This carbonylation process
represents a practical protocol for the synthesis of aryl benzo-
ates with good to excellent yields under mild reaction condi-
tions, and a wide range of functional groups are tolerated.
Experimental section
Typical reaction procedure: PdIJOAc)2 (3 mol%) and xantphos
(3 mol%) were transferred into an oven-dried tube which was
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Table 2 Carbonylation reaction of aryl iodides and phenola
Entry
1
Aryl iodides
Phenyl benzoates
Yieldb (%)
69
2
3
4
5
63
73
81
54
6
88
7
8
70
68
9
66
73
10
11
12
13
14
55
59
54
81
15
16
62
63
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Table 2 (continued)
Entry
17
Aryl iodides
Phenyl benzoates
Yieldb (%)
69
18
57
19
20
21
61
78
77
22
49
a
Reaction conditions: aryl iodides (1.0 mmol), phenol (2.0 mmol), PdIJOAc)2 (3 mol%), xantphos (3 mol%), Et3N (5 equiv.), HCOOH (2.0
b
mmol), acetic anhydride (2.0 mmol), toluene (2 mL), 12 h. Isolated yield.
filled with nitrogen. Toluene (2.0 mL), aryl halides (1.0
mmol), and phenols (2.0 mmol) were added to the reaction
tube. Then a mixture of formic acid (2.0 mmol) and acetic an-
hydride (2.0 mmol), which was stirred for 1.5 h at 30 °C, was
added dropwise to the reaction tube. After that, Et3N (5.0
mmol) was added. The mixture was stirred for 12 h at 80 °C.
After the reaction was complete, the reaction mixture was fil-
tered and concentrated, and column chromatography on sil-
ica gel (petroleum ether/ethyl acetate 50 : 1) was carried out
to give the pure product.
GC-MS (EI, 70 eV): m/zIJ%) = 212.0 ([M]+, 5), 119.0 (100),
91.0 (48), 65.0 (20).
Phenyl 3-methylbenzoate
1H NMR (400 MHz, CDCl3) δ 7.91 (d, J = 8.1 Hz, 2H), 7.31
(dd, J = 15.4, 7.7 Hz, 4H), 7.15 (dd, J = 12.7, 5.3 Hz, 1H), 7.11
(d, J = 8.2 Hz, 2H), 2.33 (s, 3H).
13C NMR (101 MHz, CDCl3) δ 165.24, 150.94, 138.31,
134.26, 130.58, 129.42, 129.39, 128.38, 127.24, 125.75, 121.65,
21.19.
GC-MS (EI, 70 eV): m/zIJ%) = 212.0 ([M]+, 7), 212.0 (11),
119.1 (100), 91.1 (43), 65.0 (15).
Phenyl benzoate
1H NMR (400 MHz, CDCl3) δ 8.21 (d, J = 8.1 Hz, 2H), 7.62 (t,
J = 7.3 Hz, 1H), 7.50 (t, J = 7.7 Hz, 2H), 7.43 (t, J = 7.7 Hz,
2H), 7.28 (d, J = 7.3 Hz, 1H), 7.22 (d, J = 8.3 Hz, 2H).
13C NMR (101 MHz, CDCl3) δ 165.10, 150.89, 133.51,
130.09, 129.50, 129.42, 128.50, 125.81, 121.65.
Phenyl 4-methylbenzoate
1H NMR (400 MHz, CDCl3) δ 7.98 (d, J = 7.9 Hz, 2H), 7.29 (d,
J = 7.6 Hz, 2H), 7.17 (d, J = 8.0 Hz, 2H), 7.10 (d, J = 8.2 Hz,
3H), 2.31 (s, 3H).
13C NMR (101 MHz, CDCl3) δ 165.12, 150.95, 144.29,
130.11, 129.35, 129.19, 126.74, 125.68, 121.68, 21.63.
GC-MS (EI, 70 eV): m/zIJ%) = 212.0 ([M]+, 6), 212.0 (15),
119.1 (100), 91.1 (79), 65.0 (39).
GC-MS (EI, 70 eV): m/zIJ%) = 198.0 ([M]+, 6), 198.0 (11),
105.0 (100), 77.0 (42), 51.0 (10).
Phenyl 2-methylbenzoate
1H NMR (400 MHz, CDCl3) δ 8.19 (d, J = 7.8 Hz, 1H), 7.53–
7.40 (m, 3H), 7.36–7.27 (m, 3H), 7.23 (d, J = 7.9 Hz, 2H), 2.70
(s, 3H).
Phenyl 4-ethylbenzoate
1H NMR (400 MHz, CDCl3) δ 8.14 (d, J = 8.1 Hz, 2H), 7.43 (t,
J = 7.8 Hz, 2H), 7.34 (d, J = 8.0 Hz, 2H), 7.28 (d, J = 7.4 Hz,
1H), 7.22 (d, J = 7.8 Hz, 2H), 2.75 (q, J = 7.6 Hz, 2H), 1.29 (t,
J = 7.6 Hz, 3H).
13C NMR (101 MHz, CDCl3) δ 165.74, 150.87, 141.22,
132.64, 131.89, 131.09, 129.41, 128.50, 125.85, 125.74, 121.76,
21.88.
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Table 3 Carbonylation reaction of aryl bromides and phenola
Entry
1
Aryl bromides
Phenyl benzoates
Yieldb (%)
84
2
3
51
52
4
5
58
69
6
7
50
79
a
Reaction conditions: aryl bromides (1.0 mmol), phenol (2.0 mmol), PdIJOAc)2 (3 mol%), xantphos (3 mol%), Et3N (5 equiv.), HCOOH (2.0
b
mmol), acetic anhydride (2.0 mmol), toluene (2 mL), 12 h. Isolated yield.
13C NMR (101 MHz, CDCl3) δ 165.17, 150.98, 150.52,
130.27, 129.39, 128.05, 126.96, 125.72, 121.71, 28.98, 15.19.
GC-MS (EI, 70 eV): m/zIJ%) = 226.0 ([M]+, 7), 226.0 (11),
133.0 (100), 105.0 (34), 77.0 (30).
Phenyl 4-acetylbenzoate
1H NMR (400 MHz, CDCl3) δ 8.27 (d, J = 8.2 Hz, 2H), 8.05 (d,
J = 8.2 Hz, 2H), 7.42 (t, J = 7.8 Hz, 2H), 7.26 (dd, J = 13.6, 6.1
Hz, 1H), 7.21 (d, J = 8.1 Hz, 2H), 2.65 (s, 3H).
13C NMR (101 MHz, CDCl3) δ 197.43, 164.29, 150.69,
140.66, 133.29, 130.38, 129.55, 128.32, 126.12, 121.53, 26.90.
GC-MS (EI, 70 eV): m/zIJ%) = 240.0 ([M]+, 9), 240.0 (11),
147.0 (100), 119.0 (12), 91.0 (12).
Phenyl 4-(tert-butyl)benzoate
1H NMR (400 MHz, CDCl3) δ 8.03 (d, J = 8.1 Hz, 2H), 7.40 (d,
J = 8.3 Hz, 2H), 7.29 (t, J = 7.7 Hz, 2H), 7.14 (d, J = 7.5 Hz,
1H), 7.09 (d, J = 8.4 Hz, 2H), 1.25 (s, 9H).
13C NMR (101 MHz, CDCl3) δ 165.04, 157.25, 150.96,
130.00, 129.35, 126.70, 125.67, 125.47, 121.69, 35.07, 31.02.
GC-MS (EI, 70 eV): m/zIJ%) = 254.0 ([M]+, 5), 161.1 (100),
146.0 (33), 118.0 (30), 91.0 (28).
Methyl phenyl terephthalate
1H NMR (400 MHz, CDCl3) δ 8.26 (d, J = 8.3 Hz, 2H), 8.17 (d, J =
8.3 Hz, 2H), 7.44 (t, J = 7.8 Hz, 2H), 7.31–7.21 (m, 3H), 3.96 (s, 3H).
13C NMR (101 MHz, CDCl3) δ 166.11, 164.32, 150.71,
134.42, 133.30, 130.07, 129.66, 129.52, 126.07, 121.52, 52.46.
GC-MS (EI, 70 eV): m/zIJ%) = 256.0 ([M]+, 9), 256.0 (10),
163.0 (100), 135.0 (11).
Phenyl 4-methoxybenzoate
1H NMR (400 MHz, CDCl3) δ 8.15 (d, J = 8.7 Hz, 2H), 7.40 (t,
J = 7.8 Hz, 2H), 7.24 (dd, J = 12.5, 5.4 Hz, 1H), 7.19 (d, J =
8.1 Hz, 2H), 6.96 (d, J = 8.8 Hz, 2H), 3.86 (s, 3H).
13C NMR (101 MHz, CDCl3) δ 164.82, 163.82, 151.01,
132.20, 129.35, 125.63, 121.80, 121.73, 113.76, 55.41.
GC-MS (EI, 70 eV): m/zIJ%) = 228.0 ([M]+, 8), 135.0 (100),
107.0 (20), 92.0 (32), 77.0 (36).
Phenyl 4-(trifluoromethyl)benzoate
1H NMR (400 MHz, CDCl3) δ 8.31 (d, J = 8.2 Hz, 2H), 7.76 (d,
J = 8.2 Hz, 2H), 7.44 (t, J = 7.7 Hz, 2H), 7.29 (s, 1H), 7.22 (d,
J = 7.9 Hz, 2H).
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Table 4 Carbonylation reaction of iodobenzene and phenolsa
Entry
1
Phenols
Benzoic acid esters
Yieldb (%)
78
2
3
48
64
a
Reaction conditions: iodobenzene (1.0 mmol), phenols (2.0 mmol), PdIJOAc)2 (3 mol%), xantphos (3 mol%), Et3N (5 equiv.), HCOOH (2.0
b
mmol), acetic anhydride (2.0 mmol), toluene (2 mL), 12 h. Isolated yield.
Table 5 Carbonylation reaction of iodobenzene and alcoholsa
Entry
Alcohols
Yieldb (%)
1
2
3
Methanol
Ethanol
Propanol
74
57
78
84c
63
61
64
81
4
5
6
7
Isopropanol
Butanol
Isobutanol
tert-Butanol
a
Reaction conditions: iodobenzene (1.0 mmol), alcohols (2.0 mmol), PdIJOAc)2 (3 mol%), xantphos (3 mol%), Et3N (5 equiv.), HCOOH (2.0
mmol), acetic anhydride (2.0 mmol), toluene (2 mL), 12 h. Isolated yield. c Propanol (5 mmol).
b
13C NMR (101 MHz, CDCl3) δ 164.01, 150.74, 135.03 (q, J =
32.33 Hz), 132.89, 130.58, 129.63, 126.25, 125.63 (q, J = 3.68
Hz), 123.62 (q, J = 273.60 Hz), 121.57.
GC-MS (EI, 70 eV): m/zIJ%) = 266.0 ([M]+, 9), 266.0 (29),
247.0 (10), 174.0 (21), 173.0 (100), 145.0 (83).
13C NMR (101 MHz, CDCl3) δ 163.55, 150.51, 133.40,
132.36, 130.60, 129.63, 126.33, 121.40, 117.82, 116.97.
GC-MS (EI, 70 eV): m/zIJ%) = 223.0 ([M]+, 6), 233.0 (33),
130.0 (100), 102.0 (51).
Phenyl 2,4-difluorobenzoate
Phenyl 4-cyanobenzoate
1H NMR (400 MHz, CDCl3) δ 8.12 (dd, J = 15.4, 8.1 Hz, 1H),
7.41 (t, J = 7.8 Hz, 2H), 7.26 (t, J = 7.4 Hz, 1H), 7.21 (d, J = 7.9
Hz, 2H), 7.03–6.88 (m, 2H).
1H NMR (400 MHz, CDCl3) δ 8.30 (d, J = 8.2 Hz, 2H), 7.81 (d, J =
8.2 Hz, 2H), 7.45 (t, J = 7.8 Hz, 2H), 7.30 (t, J = 7.4 Hz, 1H), 7.21
(d, J = 8.0 Hz, 2H).
13C NMR (101 MHz, CDCl3) δ 167.49 (d, J = 12.60 Hz), 164.76
(dd, J = 12.44, 33.01 Hz), 162.00 (bdd), 150.55, 134.44 (dd, J =
1.84, 10.66 Hz), 129.56, 126.16, 121.67, 114.64 (dd, J = 3.65,
9.53 Hz), 111.87 (dd, J = 4.05, 21.63 Hz), 105.52 (t, J = 25.71).
GC-MS (EI, 70 eV): m/zIJ%) = 234.0 ([M]+, 5), 234.0 (44),
141.1 (100), 113.0 (68), 63.0 (30).
Phenyl 2,3,4-trifluorobenzoate
1H NMR (400 MHz, CDCl3) δ 7.92–7.84 (m, 1H), 7.43 (t, J =
7.8 Hz, 2H), 7.28 (t, J = 7.4 Hz, 1H), 7.22 (t, J = 6.6 Hz, 2H),
7.09 (q, J = 7.4 Hz, 1H).
Scheme
nucleophiles.
1 Carbonylation reactions of iodobenzene with sulfur
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13C NMR (101 MHz, CDCl3) δ 161.28 (bs), 155.80 (m),
153.37 (m), 150.77 (m), 150.38, 129.61, 126.79 (m), 126.33,
121.49, 115.85 (m), 112347 (dd, J = 4.05, 18.01 Hz).
GC-MS (EI, 70 eV): m/zIJ%) = 252.0 ([M]+, 7), 252.0 (26),
159.0 (100), 131.0 (41), 81.0 (20).
Phenyl 2-naphthoate
1H NMR (400 MHz, CDCl3) δ 8.81 (s, 1H), 8.22 (d, J = 8.6 Hz,
1H), 8.01 (d, J = 8.1 Hz, 1H), 7.98–7.90 (m, 2H), 7.61 (dt, J =
14.9, 7.0 Hz, 2H), 7.47 (t, J = 7.8 Hz, 2H), 7.31 (t, J = 8.0 Hz, 3H).
13C NMR (101 MHz, CDCl3) δ 165.28, 151.00, 135.74,
132.43, 131.85, 129.46, 129.42, 128.55, 128.32, 127.77, 126.77,
126.71, 125.85, 125.39, 121.72.
Phenyl 4-fluorobenzoate
GC-MS (EI, 70 eV): m/zIJ%) = 248.0 ([M]+, 7), 248.0 (21),
155.0 (100), 127.0 (80).
1H NMR (400 MHz, CDCl3) δ 8.12 (dd, J = 8.5, 5.7 Hz, 2H),
7.32 (t, J = 7.8 Hz, 2H), 7.16 (dd, J = 13.7, 6.3 Hz, 1H), 7.14–
7.08 (m, 3H), 7.06 (d, J = 8.5 Hz, 1H).
Phenyl thiophene-3-carboxylate
13C NMR (101 MHz, CDCl3) δ 166.21 (d, J = 255.78 Hz),
164.80, 164.12, 150.77, 132.83 (d, J = 9.56 Hz), 129.45, 125.91,
121.59, 115.82 (d, J = 22.11 Hz).
1H NMR (400 MHz, CDCl3) δ 8.30 (d, J = 2.1 Hz, 1H), 7.66 (d,
J = 5.1 Hz, 1H), 7.41 (t, J = 7.7 Hz, 2H), 7.36 (dd, J = 4.6, 3.4
Hz, 1H), 7.28–7.23 (m, 1H), 7.20 (d, J = 7.8 Hz, 2H).
13C NMR (101 MHz, CDCl3) δ 161.00, 150.63, 133.96,
132.84, 130.12, 129.42, 128.52, 128.17, 126.32, 125.83, 121.65.
GC-MS (EI, 70 eV): m/zIJ%) = 204.0 ([M]+, 5), 204.0 (30),
111.0 (100), 83.0 (26).
GC-MS (EI, 70 eV): m/zIJ%) = 216.0 ([M]+, 8), 216.0 (46),
123.0 (100), 95.0 (79), 75.0 (34).
Phenyl 4-chlorobenzoate
1H NMR (400 MHz, CDCl3) δ 8.18–8.10 (m, 2H), 7.48 (t, J =
7.1 Hz, 2H), 7.46–7.39 (m, 2H), 7.33–7.27 (m, 1H), 7.24–7.17
(m, 2H).
Phenyl nicotinate
1H NMR (400 MHz, CDCl3) δ 9.40 (s, 1H), 8.85 (d, J = 4.7 Hz, 1H),
8.46 (d, J = 8.0 Hz, 1H), 7.54–7.39 (m, 3H), 7.32–7.17 (m, 3H).
13C NMR (101 MHz, CDCl3) δ 163.60, 153.52, 150.92,
150.35, 137.71, 129.47, 126.12, 125.60, 123.47, 121.39.
GC-MS (EI, 70 eV): m/zIJ%) = 199.0 ([M]+, 6), 199.0 (47),
106.0 (100), 78.0 (66), 51.0 (32).
13C NMR (101 MHz, CDCl3) δ 164.33, 150.75, 140.11,
131.53, 129.53, 128.93, 128.01, 126.03, 121.59.
GC-MS (EI, 70 eV): m/zIJ%) = 232.0 ([M]+, 7), 232.0 (14),
141.0 (65), 139.0 (100), 111.0 (50), 75.0 (15).
Phenyl 3-chlorobenzoate
Phenyl quinoline-6-carboxylate
1H NMR (400 MHz, CDCl3) δ 8.10–8.05 (m, 1H), 8.00–7.94 (m,
1H), 7.48 (ddd, J = 8.0, 2.0, 1.0 Hz, 1H), 7.33 (dt, J = 8.5, 6.5
Hz, 3H), 7.21–7.14 (m, 1H), 7.13–7.08 (m, 2H).
1H NMR (400 MHz, CDCl3) δ 9.06 (d, J = 3.6 Hz, 1H), 8.79 (s,
1H), 8.47 (d, J = 8.8 Hz, 1H), 8.36 (d, J = 8.3 Hz, 1H), 8.27 (d,
J = 8.8 Hz, 1H), 7.54 (dd, J = 8.3, 4.3 Hz, 1H), 7.47 (t, J = 7.8
Hz, 2H), 7.30 (dd, J = 17.1, 7.8 Hz, 3H).
13C NMR (101 MHz, CDCl3) δ 163.85, 150.63, 134.64,
133.49, 131.23, 130.06, 129.81, 129.47, 128.18, 126.01, 121.48.
GC-MS (EI, 70 eV): m/zIJ%) = 232.0 ([M]+, 6), 232.0 (40),
139.0 (100), 141.0 (71), 111.0 (69), 75.0 (36).
13C NMR (101 MHz, CDCl3) δ 164.56, 152.36, 150.82,
149.68, 137.97, 131.79, 129.60, 129.56, 129.46, 127.73, 127.47,
126.08, 122.01, 121.61.
GC-MS (EI, 70 eV): m/zIJ%) = 249.0 ([M]+, 8), 249.0 (10),
156.0 (100), 128.0 (42), 101.0 (12).
Phenyl 2-chlorobenzoate
1H NMR (400 MHz, CDCl3) δ 7.96 (d, J = 7.7 Hz, 1H), 7.46–7.39
(m, 2H), 7.39–7.28 (m, 3H), 7.19 (dd, J = 15.3, 7.5 Hz, 3H).
13C NMR (101 MHz, CDCl3) δ 164.05, 150.65, 134.32,
133.12, 131.82, 131.29, 129.50, 129.35, 126.70, 126.07, 121.57.
GC-MS (EI, 70 eV): m/zIJ%) = 232.0 ([M]+, 6), 232.0 (10),
141.0 (36), 139.0 (100), 111.0 (28), 75.0 (15).
4-(2-Methoxyethyl)phenyl benzoate
1H NMR (400 MHz, CDCl3) δ 8.24–8.18 (m, 2H), 7.63 (dd, J =
10.5, 4.3 Hz, 1H), 7.50 (t, J = 7.7 Hz, 2H), 7.28 (t, J = 7.8 Hz,
2H), 7.15 (d, J = 8.5 Hz, 2H), 3.62 (t, J = 7.0 Hz, 2H), 3.37 (s,
3H), 2.91 (t, J = 7.0 Hz, 2H).
13C NMR (101 MHz, CDCl3) δ 165.17, 149.26, 136.58,
133.45, 130.06, 129.77, 129.54, 128.46, 121.44, 73.40, 58.58,
35.54.
GC-MS (EI, 70 eV): m/zIJ%) = 256.0 ([M]+, 6), 256.0 (13),
105.0 (100), 77.0 (34).
Phenyl [1,1′-biphenyl]-4-carboxylate
1H NMR (400 MHz, CDCl3) δ 8.25–8.15 (m, 2H), 7.71–7.60 (m,
2H), 7.57 (d, J = 6.2 Hz, 2H), 7.46–7.30 (m, 5H), 7.18 (d, J =
12.2 Hz, 3H).
13C NMR (101 MHz, CDCl3) δ 165.05, 150.96, 146.28,
139.82, 130.67, 129.47, 128.95, 128.28, 128.23, 127.29, 127.20,
125.86, 121.71.
p-Tolyl benzoate
1H NMR (400 MHz, CDCl3) δ 8.24–8.18 (m, 2H), 7.63 (dd, J =
10.5, 4.3 Hz, 1H), 7.51 (t, J = 7.7 Hz, 2H), 7.22 (d, J = 8.1 Hz,
2H), 7.09 (d, J = 8.4 Hz, 2H), 2.37 (s, 3H).
GC-MS (EI, 70 eV): m/zIJ%) = 274.0 ([M]+, 6), 181.0 (100),
152.0 (41).
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13C NMR (101 MHz, CDCl3) δ 165.36, 148.68, 135.49,
133.47, 130.12, 129.97, 129.66, 128.51, 121.34, 20.88.
GC-MS (EI, 70 eV): m/zIJ%) = 212.0 ([M]+, 4), 212.0 (24),
105.0 (100), 77.0 (49), 51.0 (10).
2 (a) A. R. Katritzky, C. O. Meth-Cohn and W. R. Charles,
Comprehensive Organic Functional Group Transform ations,
Cambridge University Press, Cambridge, 1995, vol. 5; (b)
T. W. Green and P. G. M. Wuts, Protective Groups in Organic
Synthesis, John Wiley and Sons, New York, 3rd edn, 1999; (c)
R. C. Larock, Comprehensive Organic Transformations: A
Guide to Functional Group Preparations, John Wiley & Sons,
New York, 2nd edn, 1999.
3 (a) A. Brennführer, H. Neumann and M. Beller, Angew.
Chem., Int. Ed., 2009, 48, 4114–4133; (b) X.-F. Wu and H.
Neumann, ChemCatChem, 2012, 4, 447–458; (c) Q. Liu, H.
Zhang and A. Lei, Angew. Chem., Int. Ed., 2011, 50,
10788–10799; (d) B. Liu, F. Hu and B.-F. Shi, ACS Catal.,
2015, 5, 1863–1881.
4-Chlorophenyl benzoate.
1H NMR (400 MHz, CDCl3) δ 8.20 (d, J = 7.9 Hz, 2H), 7.65 (t,
J = 7.4 Hz, 1H), 7.52 (t, J = 7.7 Hz, 2H), 7.39 (d, J = 8.5 Hz,
2H), 7.18 (d, J = 8.6 Hz, 2H).
13C NMR (101 MHz, CDCl3) δ 164.82, 149.34, 133.70,
131.15, 130.10, 129.44, 129.09, 128.55, 123.03.
GC-MS (EI, 70 eV): m/zIJ%) = 232.0 ([M]+, 5), 232.0 (26),
105.0 (100), 77.0 (68), 51.0 (28).
4 For selected recent examples, see: (a) Y. Zhao, L. Jin, P. Li
and A. Lei, J. Am. Chem. Soc., 2008, 130, 9429–9433; (b) H.
Zhang, R. Shi, P. Gan, C. Liu, A. Ding, Q. Wang and A. Lei,
Angew. Chem., Int. Ed., 2012, 51, 5204–5207; (c) W. Li, C. Liu,
H. Zhang, K. Ye, G. Zhang, W. Zhang, Z. Duan, S. You and A.
Lei, Angew. Chem., Int. Ed., 2014, 53, 2443–2446; (d) L.
Wang, Y. Wang, C. Liu and A. Lei, Angew. Chem., Int. Ed.,
2014, 53, 5657–5661; (e) W. Li, Z. Duan, X. Zhang, H. Zhang,
M. Wang, R. Jiang, H. Zeng, C. Liu and A. Lei, Angew. Chem.,
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Zhou, C. Xia and H. Huang, J. Am. Chem. Soc., 2012, 134,
9902–9905.
5 For selected examples of carbonylation of aryl halides in
which phenols have also been used as nucleophiles see: (a)
H.-U. Blaser, M. Diggelmann, H. Meier, F. Naud, E.
Scheppach, A. Schnyder and M. Studer, J. Org. Chem.,
2003, 68, 3725–3728; (b) C. Ramesh, Y. Kubota, M. Miwa and
Y. Sugi, Synthesis, 2002, 2171–2173; (c) Z. Liu and R. C.
Larock, Org. Lett., 2004, 6, 99–102; (d) D. A. Watson, X. Fan
and S. L. Buchwald, J. Org. Chem., 2008, 73, 7096–7101; (e)
X.-F. Wu and H. Neumann, ChemCatChem, 2012, 2, 509–513;
( f ) X.-F. Wu, H. Neumann and M. Beller, Chem. – Eur. J.,
2012, 13, 3831–3835; (g) G. E. Akpinar, M. Kus, M. U. Cuncu,
E. Karakus and L. Artok, Org. Lett., 2011, 13, 748–751; (h)
M. A. Mercadante and N. E. Leadbeater, Org. Biomol. Chem.,
2011, 9, 6575–6578; (i) D. C. Reeves, S. Rodriquez, H. Lee, N.
Haddad, D. Krishnamurthy and C. H. Senanayake, Org. Lett.,
2011, 13, 2495–2497.
Benzoic acid
1H NMR (400 MHz, CDCl3) δ 13.03 (s, 1H), 8.14 (d, J = 8.3 Hz,
2H), 7.61 (t, J = 7.4 Hz, 1H), 7.47 (t, J = 7.7 Hz, 2H).
13C NMR (101 MHz, CDCl3) δ 172.68, 133.80, 130.19,
129.30, 128.44.
GC-MS (EI, 70 eV): m/zIJ%) = 122.0 ([M]+, 4), 122.0 (94),
105.0 (100), 77.0 (79), 51.0 (31).
S-(tert-Butyl) benzothioate
1H NMR (400 MHz, CDCl3) δ 7.91 (d, J = 7.2 Hz, 2H), 7.52 (t, J =
7.4 Hz, 1H), 7.40 (t, J = 7.7 Hz, 2H), 1.58 (s, 9H).
13C NMR (101 MHz, CDCl3) δ 192.81, 138.23, 132.86,
128.40, 126.90, 48.09, 29.96.
GC-MS (EI, 70 eV): m/zIJ%) = 194.0 ([M]+, 8), 194.0 (33),
138.0 (46), 105.0 (100), 77.0 (49), 57.1 (30).
PhenylIJp-tolyl)sulfane
1H NMR (400 MHz, CDCl3) δ 7.30 (d, J = 8.0 Hz, 2H), 7.26 (d,
J = 4.4 Hz, 4H), 7.14 (s, 1H), 7.12 (d, J = 6.5 Hz, 2H), 2.34 (s,
3H).
13C NMR (101 MHz, CDCl3) δ 137.58, 137.10, 132.25,
131.25, 130.04, 129.75, 129.02, 126.38, 21.11.
GC-MS (EI, 70 eV): m/zIJ%) = 200.0 ([M]+, 12), 201.0 (18),
200.0 (100), 199.0 (36), 185.0 (46), 184.0 (45), 91.0 (26).
Acknowledgements
6 (a) T. Morimoto, K. Fuji, K. Tsutsumi and K. Kakiuchi, J. Am.
Chem. Soc., 2002, 124, 3806–3807; (b) T. Shibata, N. Toshida
and K. Takagi, Org. Lett., 2002, 4, 1619–1621; (c) T.
Morimoto, K. Yamasaki, A. Hirano, K. Tsutsumi, N. Kagawa,
K. Kakiuchi, Y. Harada, Y. Fukumoto, N. Chatani and T.
Nishioka, Org. Lett., 2009, 11, 1777–1780; (d) W. Li and X.-F.
Wu, J. Org. Chem., 2014, 79, 10410–10416; (e) K. Natte, A.
Dumrath, H. Neumann and M. Beller, Angew. Chem., Int.
Ed., 2014, 53, 10090–10094.
7 (a) S. Ko, H. Han and S. Chang, Org. Lett., 2003, 5,
2687–2690; (b) K. Hosoi, K. Nozaki and T. Hiyama, Org. Lett.,
2002, 4, 2849–2851.
8 (a) H. Li, H. Neumann, M. Beller and X.-F. Wu, Angew.
Chem., Int. Ed., 2014, 53, 3183–3186; (b) T. Ueda, H. Konishi
The authors thank the financial support from NSFC
(21472174), the Education Department of Zhejiang Province
(Y201432060) and Zhejiang Sci-Tech University (1206838-Y;
14062015-Y). X.-F. Wu appreciates the general support from
Matthias Beller in LIKAT.
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