Tetrahedron 71 (2015) 4635e4639

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Tetrahedron
journal homepage: www.elsevier.com/locate/tet

Rhodium-catalyzed synthesis of aryl ketones from carboxylic acid

anhydrides and potassium aryltrifluoroborates in the presence of
CuI
Xia Liu a, Ze Yi a, Maocong Yi a, Jianhui Wang a, *, Guiyan Liu b, *
a
Department of Chemistry, College of Science, Tianjin University, Tianjin 300072, PR China
b
College of Chemistry, Tianjin Key Laboratory of Structure and Performance for Functional Molecules, Key Laboratory of Inorganic-Organic Hybrid
Functional Material Chemistry (Tianjin Normal University), Ministry of Education, Tianjin Normal University, Tianjin 300387, PR China

a r t i c l e i n f o a b s t r a c t

Article history: A new rhodium-catalyzed cross-coupling of carboxylic acid anhydrides and potassium aryltri-
Received 17 February 2015 fluoroborates was described. In this system CuI played a very important role. Various functionalities were
Received in revised form 30 April 2015 compatible in the reaction, and the desired products were obtained in good to excellent yields. A
Accepted 4 May 2015
mechanism of this reaction using a Rh(I) model catalyst have also been proposed.
Available online 16 May 2015
Ó 2015 Elsevier Ltd. All rights reserved.

Keywords:
Rhodium-catalyzed
Cross-coupling
Aryl ketones
Synthesis

1. Introduction
Ketones are pivotal intermediates and final products in the
synthesis of natural products and pharmaceutical compounds.1,2
FriedeleCrafts acylation reaction is the traditional method for the
synthesis of aromatic ketones, but a large amount of Lewis acid
usually are used. In addition, this method has poor functional group
compatibility. All these disadvantages limit the applications for
these reactions.3,4 Recently, Ge et al.5 and Darses et al.6 reported
a new method for constructing ketones by using cross-coupling
reactions of a-oxocarboxylic acids or arylaldehydes with potas-
sium aryltrifluoroborates under mild reaction conditions. In terms
of reaction conditions, efficiency, and functional group compati-
bility, this method is superior to previous methods.
Potassium aryltrifluoroborates are very stable non-toxic com-
pounds, which are relatively stable to moisture and water and are
tolerant to many sensitive functional groups.7 The preparation and
separation of potassium aryltrifluoroborates are simple, and these
compounds are easily stored. In the past few decades, the synthesis
of aryl ketones via metal-catalyzed reactions has frequently been
reported.8e10 However, many of these reactions must be carried out
under an inert atmosphere with rigorously dried materials. In
* Corresponding authors. Tel.: þ86 022 27892497; fax: þ86 22 27403475; e-mail
address: wjh@tju.edu.cn (J. Wang).
http://dx.doi.org/10.1016/j.tet.2015.05.008
0040-4020/Ó 2015 Elsevier Ltd. All rights reserved.
addition some of these reactions suffer from low yields and require
high reaction temperatures and long reaction times. As part of our
work in this field, we are developing cross coupling reactions to
build substituted ketones through transition metal catalysis pro-
cesses. In a previous communication, we briefly reported a conve-
nient synthetic method for aryl ketones via RhCl(PPh3)3-catalyzed
cross coupling reactions between potassium aryltrifluoroborates
and aromatic carboxylic acid anhydrides.11 Herein, a full paper with
an extension of our research on RhCl(PPh3)3-catalyzed synthesis of
aryl ketones from carboxylic acid anhydrides and potassium aryl-
trifluoroborates in the presence of CuI was presented.
2. Results and discussion
In a preliminary study of the reaction, 0.3 mmol of benzoic
anhydride (1) was reacted with 2.0 equiv of potassium phenyl-
trifluoroborate (2a), 2.0 equiv K2CO3, and 1.0 equiv CuI in THF with
1.0 mol % RhCl(PPh3)3 as the catalyst. The reaction was stopped
prior to completion. After stirring for 12 h at 60
C, the benzo-
phenone 3a was obtained as the product in good yield of 80%. The
reaction was conducted in several different solvents under the
same conditions and N-methyl pyrrolidone (NMP), toluene, xylene
and dioxane all provided high yields (82%, 83%, 85% and 79%, re-
spectively). The reactions performed in CH3CN, EtOH, DMF, DMSO
and H2O had low yields. A higher temperature of 90
C with
4636 X. Liu et al. / Tetrahedron 71 (2015) 4635e4639

a shortened reaction time of 6 h was also tested. Excellent yields of Next the scope of this reaction for the synthesis of various ke-
94% in xylene and 91% in NMP were obtained. So the temperature tone was explored (Table 2). Potassium phenyltrifluoroborates with
was further increased to 120
C and the reaction time was short- various substituents including electron-donating and -withdraw-
ened to 2 h. Under these conditions, 3a was formed in an isolated ing groups were tested. All reactions were highly efficient and
yield of 95%. After extensive solvent screening, xylene was found to generated the desired 3 in high yields. Ortho-substituted substrates
be the optimal solvent for this system. It should be noted that when (3f and 3g) gave lower yields than the meta- or para-substituted
the reaction was conducted in xylene at 60
C (or at 90
C) for 2 h, substrates (3b, 3c, 3d, 3e, 3h, 3j, 3k and 3l), which is due to steric
the desired product, 3a, did not form in good yield. Therefore, effects. In addition, potassium 1-naphthylborate and potassium
a high reaction temperature is necessary when xylene is used as the benzyltrifluoroborate also provided a good yield (3i and 3m).
solvent. However, if the reaction was conducted at 60
C instead of 120
C
After optimizing the solvent, the reaction time and the reaction for 2 h, the yield decreased greatly.
temperature, different catalysts, additives and bases were screened
(Table 1). When the reaction was catalyzed by RhCl(PPh3)3 with no Table 2
additive or base present, only a very small amount of the desired Scope of potassium aryltrifluoroboratesa,b
product was observed (entry 1). When K2CO3 was added as the
base, the yield did not improve much (entry 2). However, when
K2CO3 was used as the base in the presence of CuI as the additive,
the yield increased dramatically to 95% (entry 6). Study showed
that if the catalyst load is too small (0.5 mol % to 0.1 mol %), it is
difficult to obtain high yield (entries 19e21). When [Rh(COD)Cl]2 or
RhCl3$3H2O were used as the catalyst (entries 14 and 15), the yields
were 86% and 48%, respectively. It is important to note that with
only CuI and K2CO3 (i.e., no catalyst), a yield of only 18% was ob-
tained (entry 18). When KI (or CuCN) was used as the additive with
RhCl(PPh3)3 as the catalyst and K2CO3 as the base, a low yield was
obtained (entries 16 and 17). Using others bases like Et3N, NaOCH3,
K3PO4, Cs2CO3, t-BuOK, K2HPO4, K2SO4, Na2CO3, NaHCO3, or KOAc,
instead of K2CO3 in the presence of CuI as the additive, did not
further improve the yield (entries 3e5, 7e13). Based on these re-
sults, 1.0 equiv benzoic anhydride, 2.0 equiv potassium phenyl-
trifluoroborate, 2.0 equiv K2CO3, 1.0 equiv CuI and 1.0% (mol)
RhCl(PPh3)3 were chosen as the optimal conditions.

Table 1
c
Reaction stirred at 60
C for 2 h.
a
Optimization of bases, catalysts and additivesa Conditions: potassium aryltrifluoroborate (0.60 mmol, 2 equiv), benzoic anhy-
dride (0.30 mmol, 1 equiv), K2CO3 (0.60 mmol, 2 equiv), CuI (0.30 mmol, 1 equiv),
RhCl(PPh3)3 (1.0 mol%), xylene (1.5 mL), 120
C, 2 h.
b
Isolated yields based on benzoic anhydride.

Entry Catalyst Additive Base Yield(%)e

1 RhCl(PPh3)3 None None <5 The successful syntheses of 3 (Table 2) encouraged us to expand
2 RhCl(PPh3)3 None K2CO3 13 the scope of the reaction to include other ketones (Table 3). In
3 RhCl(PPh3)3 CuI Et3N <10 general, the reaction was highly efficient (3o, 93%; 3b, 88%; 3p, 87%;
4 RhCl(PPh3)3 CuI NaOCH3 26 3d, 81%; 3q, 92% and 3s, 90%) for carboxylic acid anhydrides (re-
5 RhCl(PPh3)3 CuI K3PO4 91
6 RhCl(PPh3)3 CuI K2CO3 95
gardless of electron-donating or -withdrawing ability) but much
7 RhCl(PPh3)3 CuI Cs2CO3 93 less efficient for 3r, o-substituted substrates (3n and 3f) and m-
8 RhCl(PPh3)3 CuI t-BuOK 87 substituted substrate 3t. Aliphatic carboxylic anhydrides did not
9 RhCl(PPh3)3 CuI K2HPO4 32 react with potassium phenyltrifluoroborate under the reaction
10 RhCl(PPh3)3 CuI K2SO4 <10
conditions.
11 RhCl(PPh3)3 CuI Na2CO3 <10
12 RhCl(PPh3)3 CuI NaHCO3 32 A plausible mechanism for the formation of ketones 3 is illus-
13 RhCl(PPh3)3 CuI KOAc 16 trated in Scheme 1. First an intermediate (PPh3)2Rh(I)X is generated
14 [Rh(COD)Cl]2 CuI K2CO3 86 in the presence of CuI, a known reagent for scavenging and
15 RhCl3$3H2O CuI K2CO3 48 reclaiming phosphines.12 The second step involve the generation of
16 RhCl(PPh3)3 KI K2CO3 17
17 RhCl(PPh3)3 CuCN K2CO3 15
phenylrhodium(I) species A by transmetalation.13 Then, oxidative
18 None CuI K2CO3 18 addition of 1 to give acylphenylrhodium(III) intermediate B fol-
19 RhCl(PPh3)3b CuI K2CO3 63 lowed by reductive elimination affords 3a.14
20 RhCl(PPh3)3c CuI K2CO3 27
21 RhCl(PPh3)3d CuI K2CO3 <10
a
Conditions: potassium phenyltrifluoroborate (0.6 mmol, 2 equiv), benzoic an- 3. Conclusions
hydride (0.3 mmol, 1 equiv), base (0.60 mmol, 2 equiv), catalyst (1.0 mol%), additive
(0.30 mmol, 1 equiv), xylene (1.5 mL), 120
C, 2 h. In conclusion, an efficient approach for the rhodium-catalyzed
b
Catalyst (0.5 mol %).
c
Catalyst (0.25 mol %).
cross coupling of carboxylic acid anhydrides and potassium aryl-
d
Catalyst (0.1 mol%). trifluoroborates has been developed. These reactions proceeded
e
Yield measured by GC-MS. smoothly with relatively low catalyst loadings at mild temperatures
 X. Liu et al. / Tetrahedron 71 (2015) 4635e4639
Table 3
Scope of carboxylic acid anhydridesa,b
a
Conditions: potassium phenyltrifluoroborate (0.60 mmol, 2 equiv), carboxylic
acid anhydrides (0.30 mmol, 1 equiv), K2CO3 (0.60 mmol, 2 equiv), CuI (0.30 mmol, 1
equiv), RhCl(PPh3)3 (1.0 mol%), xylene 1.5 mL, 120
C, 2h.
b
Isolated yields based on carboxylic acid anhydrides.
Scheme 1. Plausible mechanism.
and are tolerant to air. The reaction conditions are mild, and many
different substituents can be used without compromising the
yields. A reaction mechanism including the oxidative coupling,
followed by reductive elimination to give the product, was pro-
posed. In view of the importance of aryl ketones in organic and
medicinal chemistry, and the easy availability and stability of po-
tassium aryltrifluoroborates, this novel method should find broad
use in organic synthesis.
4. Experiment section
4.1. General
NMR spectra were obtained on a 400 MHz spectrometer with
CDCl3 as solvent. The chemical shifts are reported in ppm relative to
CDCl3 (d¼7.26) for 1H NMR and relative to the central CDCl3 reso-
nance (d¼77.0) for 13C NMR. Coupling constants (J) are given in Hz.
Multiplicities are reported as follows: singlet (s), doublet (d),
doublet of doublets (dd), triplet (t), quartet (q), and multiplet (m).
GC-Mass spectra were recorded on a Luniere Tech. Ltd
TRACEDSQ instrument. Unless otherwise noted, all reactions were
4637
performed in air. Reactions were monitored by analytical thin layer
chromatography using 0.20 mm Anhui Liangchen silica gel plates.
Silica gel (200e300 mesh) (from Anhui Liangchen Chem. Company,
Ltd.) was used for flash chromatography. The potassium aryltri-
fluoroborates and the aromatic carboxylic acid anhydrides were
prepared according to literature procedures.15e17 RhCl (PPh3)3 was
also prepared according to a literature procedure.18 Other chem-
icals and reagents were obtained from commercial sources and
used directly.
4.2. General procedure for the preparation of 3
A reaction vessel was charged with a mixture of a benzoic an-
hydride (or an aryl carboxylic anhydride) (0.30 mmol), potassium
aryltrifluoroborate (or potassium phenyltrifluoroborate)
(0.60 mmol), K2CO3 (0.60 mmol), CuI (0.30 mmol), RhCl (PPh3)3
(0.003 mmol, 1.0 mol %) and xylene (1.5 mL). The mixture was
heated to 120
C and stirred for 2 h. After the completion of the
reaction, the mixture was quenched with 5 mL of water, and then
extracted with ethyl acetate (310 mL). The combined organic
layers were dried over magnesium sulfate. After removal of the
solvent in vacuo, the product was isolated by column chromatog-
raphy. Ethyl acetate/petroleum ether was used for elution and the
yield was calculated based on the amount of aryl benzoic anhydride
(the purified products were identified by NMR spectra).
4.2.1. Benzophenone (3a).19 White solid, mp 48e50
C. Yield: 95%.
1
H NMR (400 MHz, CDCl3) d (ppm): 7.80e7.82 (m, 4H), 7.57e7.58
(m, 2H), 7.48e7.50 (m, 4H). 13C NMR (CDCl3, 100 MHz), d (ppm):
196.7, 137.5, 132.4, 130.0, 128.2. Analytical Data. Calcd (found) for
C13H10O: C, 85.69 (85.56); H, 5.53 (5.78).
4.2.2. 4-Methylbenzophenone (3b).20 Yellow oil. Yield: 94% (or
88%). 1H NMR (CDCl3, 400 MHz), d (ppm): 7.79 (d, J¼7.6 Hz, 2H), 7.73
(d, J¼8.1 Hz, 2H), 7.58 (dd, J¼7.5, 7.4 Hz, 1H), 7.47 (dd, J¼7.7, 7.6 Hz,
2H), 7.28 (t, J¼8.0 Hz, 2H), 2.44 (s, 3H). 13C NMR(CDCl3, 100 MHz),
d (ppm): 196.5, 143.3, 138.0, 134.9, 132.2, 130.3, 130.0, 129.0, 128.2,
21.7. Analytical Data. Calcd (found) for C14H12O: C, 85.68 (85.26); H,
6.16 (6.28).
4.2.3. 3-Methylbenzophenone (3c).21 Light yellow oil. Yield: 92%. 1H
NMR (CDCl3, 400 MHz), d (ppm): 7.79 (dd, J¼8.2, 1.2 Hz, 2H), 7.57
(m, 3H), 7.44 (t, J¼7.6 Hz, 2H), 7.32e7.35 (m, 2H), 2.40 (s, 3H). 13C
NMR (CDCl3, 100 MHz), d (ppm): 196.9, 138.0, 137.6, 137.5, 133.1,
132.3, 130.4, 129.9, 128.1, 128.0, 127.3, 21.3. Analytical Data. Calcd
(found) for C14H12O: C, 85.68 (85.71); H, 6.16 (6.08).
4.2.4. 4-Methoxylbenzophenone (3d).22 Pale yellow oil. Yield: 89%
(or 81%). 1H NMR (CDCl3, 400 MHz), d (ppm): 7.86 (dd, J¼6.8, 1.9 Hz,
2H), 7.79 (dd, J¼7.0, 1.3 Hz, 2H), 7.59 (t, J¼7.6 Hz, 1H), 7.50 (t,
J¼8.1 Hz, 2H), 6.99 (dd, J¼6.8, 1.9 Hz, 2H), 3.92 (s, 3H). 13C NMR
(CDCl3, 100 MHz), d (ppm): 195.5, 163.3, 138.4, 132.6, 131.9, 130.2,
129.7, 128.2, 113.6, 55.5. Analytical Data. Calcd (found) for C14H12O2:
C, 79.22 (78.91); H, 5.70 (5.88).
4.2.5. 3-Methoxylbenzophenone (3e).23 Pale yellow solid, mp
36e39
C. Yield: 86%. 1H NMR (CDCl3, 400 MHz), d (ppm): 7.84 (d,
J¼8.5 Hz, 2H), 7.61 (t, J¼7.3 Hz, 1H), 7.51 (t, J¼7.5 Hz, 2H), 7.38e7.40
(m, 3H), 7.16 (dd, J¼7.6, 1.6 Hz, 1H), 3.89 (s, 3H). 13C NMR (CDCl3,
100 MHz), d (ppm): 196.5, 159.6, 138.9, 137.6, 132.4, 130.0, 129.2,
128.3, 122.9, 118.9, 114.4, 55.5. Analytical Data. Calcd (found) for
C14H12O2: C, 79.22 (79.11); H, 5.70 (5.65).
4.2.6. 2-Methylbenzophenone (3f).5 Light yellow solid, mp
114e116
C. Yield: 76%. 1H NMR (CDCl3, 400 MHz), d (ppm): 7.81 (d,
J¼7.7 Hz, 2H), 7.58 (t, J¼7.3 Hz, 1H), 7.45 (t, J¼7.6 Hz, 2H), 7.39 (d,
4638 X. Liu et al. / Tetrahedron 71 (2015) 4635e4639
J¼7.3 Hz, 1H), 7.33e7.25 (m, 3H), 2.34 (s, 3H). 13C NMR (CDCl3,
100 MHz), d (ppm): 198.6, 138.6, 137.7, 136.7, 133.1, 131.0, 130.2,
130.1, 128.5, 128.4, 125.2, 20.0. Analytical Data. Calcd (found) for
C14H12O: C, 85.68 (85.55); H, 6.16 (6.37).
4.2.7. 2-Methoxylbenzophenone (3g).24 Pale yellow solid, mp
37e39
C. Yield: 72%. 1H NMR (CDCl3, 400 MHz), d (ppm): 7.82 (m,
2H), 7.56e7.54 (m, 1H), 7.49e7.46 (m, 3H), 7.37e7.35 (m, 1H),
7.06e7.01 (m, 2H), 3.71 (s, 3H) 13C NMR (CDCl3, 100 MHz), d (ppm):
196.5, 157.3, 137.8, 133.0, 131.9, 129.8, 129.5, 128.8, 128.2, 120.5,
111.4, 55.6. Analytical Data. Calcd (found) for C14H12O2: C, 79.22
(79.41); H, 5.70 (5.58).
25
4.2.8. 4-Bromobenzophenone (3h). Pale pink solid, mp 81e83
C.
Yield: 93%. 1H NMR (CDCl3, 400 MHz), d (ppm): 7.77 (dd, J¼9.0,
1.0 Hz, 2H), 7.67 (dd, J¼8.5, 2.0 Hz, 2H), 7.63 (dd, J¼8.5, 2.0 Hz, 2H),
7.60e7.63 (m, 1H), 7.49 (t, J¼7.75 Hz, 2H). 13C NMR (CDCl3,
100 MHz), d (ppm): 195.6, 137.2, 136.3, 132.7, 131.6, 131.5, 129.9,
128.4, 127.5. Analytical Data. Calcd (found) for C13H9BrO: C, 59.8
(58.95); H, 3.47 (3.68).
4.2.9. 1-Naphthylphenone (3i).2e White solid, mp 75e76
C. Yield:
88%. 1H NMR (CDCl3, 400 MHz), d (ppm): 8.10 (d, J¼7.8 Hz, 1H), 7.96
(d, J¼8.1 Hz, 1H), 7.89e7.84 (m, 3H), 7.56e7.40 (m, 7H). 13C NMR
(CDCl3, 100 MHz), d (ppm): 197.9, 138.2, 136.2, 133.6, 133.1, 131.2,
130.8, 130.3, 128.4, 128.3, 127.7, 127.2, 126.4, 125.6, 124.2. Analytical
Data. Calcd (found) for C17H12O: C, 87.9 (87.21); H, 5.21 (5.18).
4.2.10. 4-tert-Butylbenzophenone (3j).26 Yellow oil. Yield: 92%. 1H
NMR (CDCl3, 500 MHz), d (ppm): 7.90 (d, J¼8.5 Hz, 2H), 7.47 (d,
J¼8.5 Hz, 2H), 2.58 (s, 3H), 1.34 (s, 9H). 13C NMR (CDCl3, 125 MHz),
d (ppm): 196.8, 142.8, 133.7, 128.2, 127.4, 25.5, 20.6. Analytical Data.
Calcd (found) for C17H18O: C, 85.67 (87.01); H, 7.61 (7.48).
4.2.11. 3-Trifluoromethylbenzophenone (3k).27 White solid, mp
112e114
C. Yield: 90%. 1H NMR (CDCl3, 400 MHz), d (ppm): 8.07 (s
1H), 7.98 (d, J¼7.7 Hz, 1H), 7.79e7.86 (m, 3H), 7.64 (dd, J¼7.3, 7.5 Hz,
2H), 7.52 (dd, J¼7.8, 7.6 Hz, 2H). 13C NMR (CDCl3, 100 MHz), d (ppm):
195.2, 138.3, 136.8, 133.1, 133.0, 131.1 (q, JC,F¼33.1 Hz), 130.0, 129.0,
128.8 (q, JC,F¼3.8 Hz),128.6, 126.7 (q, JC,F¼3.8 Hz), 123.7 (q, JC,
F¼271.3 Hz). Analytical Data. Calcd (found) for C14H9F3O: C, 67.20
(67.31); H, 3.63 (3.58).
4.2.12. 3-Cyanobenzophenone (3l).22 Pale yellow oil. Yield: 87%. 1H
NMR (CDCl3, 400 MHz), d (ppm): 7.88 (dd, J¼8.5, 1.5 Hz, 2H),
7.81e7.78 (m, 4H), 7.66e7.63 (m, 1H), 7.54e7.50 (m, 2H). 13C NMR
(CDCl3, 100 MHz), d (ppm): 195.0, 141.2, 136.3, 133.3, 132.2, 130.2,
130.1, 128.6, 118.0, 115.7. Analytical Data. Calcd (found) for C14H9NO:
C, 81.14 (81.22); H, 4.38 (4.07).
4.2.13. 1,2-Diphenyl-ethanone (3m).28 White solid, mp: 58e60
C.
Yield: 90%. 1H NMR (CDCl3, 500 MHz), d (ppm): 4.22 (s, 2H),
7.17e7.23 (m, 3H), 7.26 (t, J¼7.5 Hz, 2H), 7.38 (t, J¼7.5 Hz, 2H), 7.48
(t, J¼7.0 Hz, 1H), 7.94 (d, J¼7.5 Hz, 2H). 13C NMR (CDCl3, 100 MHz),
d (ppm): 45.7, 127.0, 128.76, 128.78, 128.81, 129.6, 133.3, 134.7, 136.8,
197.8.
4.2.14. 2-Chlorobenzophenone (3n).29 White solid, mp 42e43
C.
Yield: 71%. 1H NMR (CDCl3, 400 MHz), d (ppm): 7.82 (d, J¼7.4 Hz,
2H), 7.60 (t, J¼7.4 Hz, 1H), 7.49e7.44 (m, 4H), 7.40e7.37 (m, 2H). 13C
NMR (CDCl3, 100 MHz), d (ppm): 195.3, 138.6, 136.4, 133.7, 131.3,
131.1, 130.1, 130.2, 129.1, 128.6, 126.7. Analytical Data. Calcd (found)
for C13H9ClO: C, 72.07 (73.21); H, 4.19 (4.10).
4.2.15. 4-Chlorobenzophenone (3o).29 Pale yellow solid, mp
73e75
C. Yield: 93%. 1H NMR (CDCl3, 400 MHz), d (ppm): 7.76 (t,
J¼7.8 Hz, 4H), 7.59 (t, J¼7.4 Hz,1H), 7.50e7.44 (m, 4H). 13C NMR
(CDCl3, 100 MHz), d (ppm): 195.4, 138.8, 137.2, 135.8, 132.6, 131.4,
129.9, 128.6, 128.3. Analytical Data. Calcd (found) for C13H9ClO: C,
72.07 (71.71); H, 4.19 (4.08).
4.2.16. 4-Nitrobenzophenone (3p).22 Light yellow solid, mp
76e77
C. Yield: 87%. 1H NMR (CDCl3, 400 MHz), d (ppm): 8.35 (d,
J¼8.8 Hz, 2H), 7.95 (d, J¼8.4 Hz, 2H), 7.82e7.80 (m, 2H), 7.66e7.51
(m, 3H). 13C NMR (CDCl3, 100 MHz), d (ppm): 194.8, 149.8, 142.8,
136.2, 133.5, 130.7, 130.1, 128.7, 123.5. Analytical Data. Calcd (found)
for C13H9NO3: C, 68.72 (69.01); H, 3.99 (4.01).
4.2.17. 2-Furanyl(phenyl)methanone (3q).30 Brown oil. Yield: 92%.
1
H NMR (CDCl3, 400 MHz), d (ppm): 7.98e7.95 (m, 2H), 7.71e7.72 (t,
J¼0.8 Hz,1H), 7.59e7.62 (t, J¼7.4 Hz, 1H), 7.50 (t, J¼7.4 Hz, 2H), 7.23
(d, J¼3.6 Hz, 1H), 6.60e6.62 (m, 1H). 13C NMR (CDCl3, 100 MHz),
d (ppm): 182.6, 152.3, 147.1, 137.3, 132.6, 129.3, 128.4, 120.6, 112.2.
4.2.18. 2-Benzoylthiophene (3r).31 White solid, mp: 52e55
C.
Yield: 46%. 1H NMR (CDCl3, 400 MHz), d (ppm): 7.84e7.86 (m, 2H),
7.70e7.71 (m, 1H), 7.62e7.63 (m, 1H), 7.56e7.61 (m, 1H), 7.47e7.50
(m, 2H), 7.14e7.18 (m, 1H) ppm 13C NMR (CDCl3, 100 MHz), d (ppm):
188.2, 143.6, 138.1, 134.8, 134.2, 132.2, 129.1, 128.4, 127.9.
4.2.19. Phenyl(pyridin-4-yl)methanone (3s).32 White solid, mp:
72e73
C. Yield: 90%. 1H NMR (CDCl3, 400 MHz), d (ppm): 8.79 (d,
J¼5.7 Hz, 2H), 7.80 (d, J¼7.8 Hz, 2H), 7.62 (t, J¼7.4 Hz, 1H), 7.55 (d,
J¼5.6 Hz, 2H), 7.49 (t, J¼7.7 Hz, 2H). 13C NMR (CDCl3, 100 MHz),
d (ppm): 194.7, 150.1, 144.0, 135.6, 133.2, 129.8, 128.4, 122.5.
4.2.20. 3-Methylbenzophenone (3t).31 Yellow oil. Yield: 45%. 1H
NMR (CDCl3, 400 MHz), d (ppm): 2.42 (s, 3H), 7.33e7.41 (m, 2H),
7.48 (t, J¼7.6, 2H), 7.56e7.63 (m, 3H), 7.81e7.79 (m, 2H); 13C NMR
(CDCl3, 100 MHz), d (ppm): 21.3, 127.3, 128.0, 128.2, 130.0, 130.4,
132.3, 133.1, 137.6, 137.7, 138.1, 196.9.
Acknowledgements
This work was supported by grants from the National Science
Foundation of China (NSFC 21102102, 21372175, and 21072149).
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