Palladium-Catalyzed Suzuki Coupling of N-Acyloxazolidinones via Selective Cleavage of C–N Bonds

Article abstract of DOI:10.1002/ejoc.202000575

By implementing a palladium-catalyzed Suzuki coupling reaction of N-acyloxazolidinones with arylboronic acid, we herein report on the preparation of substituted diaryl ketones via selective cleavage of exocyclic C–N Bonds. The reaction was carried out under mild reaction conditions with excellent functional group compatibility in good yields (up to 93 %).

Full text of DOI:10.1002/ejoc.202000575

Communication
doi.org/10.1002/ejoc.202000575
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European Journal of Organic Chemistry
Palladium Catalysis
Palladium-Catalyzed Suzuki Coupling of N-Acyloxazolidinones
via Selective Cleavage of C–N Bonds
Junsheng Jian,[a] Zhanyu He,[a] Yuqi Zhang,[a] Tingting Liu,[a] Lizhen Liu,[a] Zijia Wang,*[a]
Hui Wang,[a] Sanyong Wang,*[b] and Zhuo Zeng*[a]
Abstract: By implementing a palladium-catalyzed Suzuki cou- via selective cleavage of exocyclic C–N Bonds. The reaction was
pling reaction of N-acyloxazolidinones with arylboronic acid, we carried out under mild reaction conditions with excellent func-
herein report on the preparation of substituted diaryl ketones tional group compatibility in good yields (up to 93 %).
Introduction
straightforward method for the synthesis of a series of ketones.
In 2015, Garg and co-workers[10] reported the first Ni-catalyzed
Suzuki coupling reaction of amides with organoboron com-
pounds, which proceeds by an uncommon cleavage of the
amide C–N bond (Scheme 1). These results bring to light that
classically considered inert amides can be employed as syn-
thons in reactions that unexpectedly form C–C bonds through
cleavage of the C–N bond using inexpensive metal catalysis.
Since then, Zou[11] Szostak[12] and Huang[13] respectively devel-
oped Pd-catalyzed conversion of amides to ketones by cleavage
of the C–N bond. Especially, Szostak observed that the degree
of difficulty of the C–N bond cleavage is relative to nN→π*CO
conjugation by DFT calculation. According to our experience of
The structure of Ketones units has been widely employed to
build construction of complex natural products and pharma-
ceuticals.[1] In order to streamline synthesis of aryl ketones, vari-
ous methods were developed via C–C bond formation,[2] For
example, the employment of metal-catalyzed Suzuki–Miyaura
cross-coupling of electrophilic precursors with arylboronic acids
synthesized aryl ketones. The cross-coupling process of organo-
boron compounds has been widely used by organic chemists
because of its non-toxicity, thermal stability, and moisture sta-
bility.[3] In 1997, Bumagin and co-workers[4] reported the first
“ligand-free” Pd-catalyzed reaction of an aromatic acyl chloride
with organoboron compounds to give diaryl ketones efficiently,
which occurs easily in water and acetone in the presence of a
base. Subsequently, much achievement in synthesis of ketones
from acyl chloride, acid anhydride, carboxylic acid, 2-pyridyl es-
ters, and thiol ester has been described by Gooßen,[5] Chatani,[6]
Srogl,[7] Cheng[8] and Wu[9] by Pd-catalyzed Suzuki reaction. De-
spite these significant advances, however, using amides as elec-
trophilic precursors to form acyl-palladium intermediates for
catalytic coupling reactions with organoboron compounds is
virtually unknown.
Cleavage of amide C–N bonds represents one of the most
challenging transformations in organic synthesis due to the
high C–N bond dissociation energy. Therefore, if the amide
C–N bonds can be broken to generate an acyl group into or-
ganic molecules and give a ketone, it will become a simple and
[a] J. Jian, Z. He, Y. Zhang, Dr. T. Liu, L. Liu, Dr. Z. Wang, H. Wang,
Prof. Z. Zeng
College of Chemistry, South China Normal University,
Guangzhou 510006, Guangdong, P. R. China
E-mail: wslnwzj@foxmail.com
zhuoz@scnu.edu.cn
[b] S. Wang
Guangye L&P Food Ingredient Co., Ltd.,
Guangzhou, 510308, Guangdong, P. R. China
E-mail: sanyongwang112@163.com
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under https://doi.org/10.1002/ejoc.202000575.
Scheme 1. Suzuki–Miyaura coupling of amides.
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studying on activation of C–N bonds,[14] activation of amides 3b and 3e are low because of the steric hindrance effect. The
C–N bonds depends on electron density on the nitrogen atom. reason of low yields of 3i and 3j is EWGs which make intermedi-
For example, di-Boc (tert-butyloxy carbonyl) and pyrrolidine-2,5- ate II unstable in Scheme 4. Notably, naphthalene and hetero-
dione dicarbonyl amides, the C–N bonds are relatively easily cycle are also suitable for the catalytic reaction to furnish ket-
activated. Instead, we designed the conversion of activated ones 3k–3m even though the low yields of 3l and 3m was
amides 3-benzoyloxazolidin-2-ones, monocarbonyl ester obtained due to the effect of the sulfur and oxygen atom on
amides, commercially available, cheap, and air-/moisture-stable, intermediate II in Scheme 4.
to ketones via selective exocyclic the cleavage C–N bond. This
method would provide a new approach for synthesis of a series
of diaryl ketones by Suzuki cross-coupling with acyl-transfer re-
agent 3-benzoyloxazolidin-2-ones.
Results and Discussion
We initiated our investigation using Pd-catalyzed system con-
sisting of 3-benzoyloxazolidin-2-one 1a and phenylboronic acid
2a as a substrate model in toluene at 110 °C for 12 h. Suzuki
coupling of 1a with 2a was observed in 5 % by using Pd(OAc)2
(Table 1, entry 1). Unfortunately, Pd(PPh3)2Cl2 and PdCl2 as cata-
lysts cannot give the target product even adding several li-
gands such as PCy3, Xantphos, dppp and dppf (entries2–6). It is
delighted to us that the (IPr)Pd(allyl)Cl catalyst can dramatically
improve yield to 79 % without ligands (entry 7). Follow by the
solvents, THF, dioxane, DMF and o-xylene, were checked (en-
tries 8–11). Obviously, o-xylene delivered the best result to give
the corresponding product 3a in 88 %. The amount of Pd cata-
lyst and temperature also were investigated, but both of them
provided lower yields (entries12–13).
Scheme 2. Scope of amides in the cross-coupling with potassium aryltri-
Table 1. Optimization of reaction conditions.[a]
fluoroborates.
Next, we turned our attention to the organoboron substrates
with differently substituted functional groups (Scheme 3).
Likely, o- and p-methyl-substituted phenylboronic acids also
gave ketones 3b and 3e. Organoboronic acids, including elec-
tron-rich and -poor groups, delivered the corresponding prod-
Entry
Cat. Pd
Ligand
Solvent
Yield[%][d]
1
2
3
4
5
6
7
8
Pd(OAc)2
Pd(PPh3)2Cl2
PdCl2
PdCl2
PdCl2
PPh3
none
PCy3
toluene
toluene
toluene
toluene
toluene
toluene
toluene
THF
1,4-dioxane
DMF
o-xylene
o-xylene
o-xylene
< 5
N.D.
N.D.
N.D.
N.D.
N.D.
79
20
45
N.D.
88
72
xantphos
dppp
dppf
none
none
none
none
none
none
none
PdCl2
(IPr)Pd(allyl)Cl
(IPr)Pd(allyl)Cl
(IPr)Pd(allyl)Cl
(IPr)Pd(allyl)Cl
(IPr)Pd(allyl)Cl
(IPr)Pd(allyl)Cl
(IPr)Pd(allyl)Cl
9
10
11
12[b]
13[c]
62
[a] Reaction conditions: 1a (0.2 mmol), 2a (0.4 mmol), catalyst (5 mol-%),
ligand (5 mol-%), K2CO3 (2 equiv.), solvents (2.0 mL), 110 °C, 12 h, In N2.
[b] 80 °C, boronic acids (2 equiv.). [c] Catalyst (3 mol-%). [d] Isolated yield.
With the suitable reaction condition in hand, the scope of
amides 1 was surveyed (Scheme 2). The reaction of o-, m- and
p-methyl-substituted benzoyl amides smoothly produced the
corresponding ketones 3b–3d, respectively. Several substituted
3-benzoyloxazolidin-2-ones with EDG and EWG proved to be
amenable acyl-transfer reagents to afford the relevant ketones
3e–3j with moderate to high catalytic efficiency. The yields of
Scheme 3. Scope of potassium aryltrifluoroborates in the cross-coupling with
amides.
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mercially available reagents and catalysts were purchased from
China supplier Energy Chemical with purity 98 %. Flash chromatog-
raphy was performed using 200–300 mesh silica gel. 1H and 19F
NMR data were recorded with AVANCE NEO Bruker (600 MHz) and
Varian AS (400 MHz) spectrometers in CDCl3 with tetramethylsiliane
ucts 3e–3j. Other groups, naphthyl, aldehyde and phenyl, can
be applicable to our reaction condition to give 3k–3o in 85 %,
46 % and 78 %. In case of the aldehyde group, the active alde-
hyde group can form certain undesired by-products to give rise
to the low yield of 3n.
1
as an internal standard. H NMR data are given for all compounds
The proposed mechanism for the acylation of Suzuki cou-
pling of 3-benzoyloxazolidin-2-one derivatives with organo-
boron substrates is shown in Scheme 4, based on the previous
report: insertion of Pd(0) into the C-N bond of the 3-benzoyl-
oxazolidin-2-one forms an acylpalladium(II) complex II, which
transmetalate with phenylboronic acid to give the complex III;
reductive elimination forming the ketones and regenerate the
in the ESI.
General Procedure for Amides Synthesis: An oven-dried round-
bottomed flask (50 mL) equipped with a stirring bar was charged
with CH2Cl2 (20 mL), 2-oxazolidone (870 mg, 10 mmol) and benzoic
acid (1.34 g, 11 mmol). DCC (2.27 g, 11 mmol) and DMAP(160 mg,
1.3 mmol) were added to the mixture with vigorous stirring at r.t.
for 24 h. After cooling to room temperature, the mixture was filtered
through a short pad of silica gel, then the silica gel was washed
with CH2Cl2 (3 × 20 mL) and the organic phases were combined.
After the solvent was removed, the crude product was purified by
silica gel column chromatography using petroleum ether/ethyl
acetate (3:1) as eluent afforded N-benzoylsaccharin (1.62 g, 84 %).
Pd(0)
.
General Procedure for Suzuki–Miyaura Coupling of Amides: To
a 10 mL round-bottom flask was added 3-benzoyloxazolidin-2-one
(0.20 mmol, 38.2 mg), (IPr)Pd(allyl)Cl (0.01 mmol, 5.7 mg), K2CO3
(0.40 mmol, 31.6 mg), phenylboronic acid (0.4 mmol, 48.8 mg) and
1 mL o-xylene. Then, the mixture was stirred at 100 °C for 12 h.
After cooling to room temperature, the mixture was filtered through
a short pad of silica gel, then the silica gel was washed with CH2Cl2
(3 × 10 mL) and the organic phases were combined and concen-
trated in vacuo. The residue was purified by column chromatogra-
phy on silica gel (petroleum ether/ethyl acetate = 20:1) as eluent
afforded butyl benzoate 3a (33.6 mg, 88 %).
Characterization Data of Amides
3-Benzoyloxazolidin-2-one (1a):[15] Following general procedure,
1
1a was isolated as a white solid (1.62 g, 84 %); H NMR (400 MHz,
CDCl3) δ = 7.66 (d, J = 7.2 Hz, 2H), 7.58–7.53 (t, J = 7.6 Hz, 1H),
7.45–7.40 (m, 2H), 4.48 (t, J = 7.8 Hz, 2H), 4.17 (t, J = 7.8 Hz, 2H).
3-(2-Methylbenzoyl)oxazolidin-2-one (1b):[15] Following general
1
procedure, 1b was isolated as a white solid (1.42 g, 69 %); H NMR
(400 MHz, CDCl3) δ = 7.39–7.32 (m, 1H), 7.29–7.20 (m, 3H), 4.44 (t,
J = 8.0 Hz, 2H), 4.17 (t, J = 8.0 Hz, 2H), 2.34 (s, 3H).
Scheme 4. Proposed mechanism for Pd-catalyzed acylative Suzuki coupling.
3-(3-Methylbenzoyl)oxazolidin-2-one (1c).[15] Following general
procedure, 1c was isolated as a white solid (2.10 g, 73.1 %); 1H NMR
(600 MHz, CDCl3) δ = 7.49–7.41 (m, 2H), 7.35 (d, J = 7.6 Hz, 1H),
7.33–7.27 (m, 1H), 4.44 (t, J = 7.8 Hz, 2H), 4.13 (t, J = 7.8 Hz, 2H),
2.39 (s, 3H).
Conclusions
We have reported the first Suzuki coupling of 3-benzoylox-
azolidin-2-ones with arylboronic acids by selective the cleavage
of exocyclic the amide C-N bonds. This method is achieved un-
der mild conditions with highly functional groups, is tolerant,
and can be strategically employed in synthesis of ketones in
moderate to good yields. Further key features and synthetic
transformations are underway in our laboratory. We hope that
the present result will provide useful insight into synthetic or-
ganic chemistry of Suzuki coupling reactions.
3-(4-Methylbenzoyl)oxazolidin-2-one (1d):[15] Following general
1
procedure, 1d was isolated as a white solid (1.80 g, 88 %); H NMR
(400 MHz, CDCl3) δ = 7.58 (d, J = 8.0 Hz,2H), 7.23 (d, J = 8.0 Hz, 2H),
4.48 (t, J = 7.8 Hz, 2H), 4.16 (t, J = 7.8 Hz, 2H), 2.41 (s, 3H).
3-(2-Methoxybenzoyl)oxazolidin-2-one (1e).[15] Following gen-
eral procedure, 1e was isolated as a white solid (1.50 g, 68 %); 1H
NMR (400 MHz, CDCl3) δ = 7.47–7.42 (m, 1H), 7.34 (dd, J = 7.6,
1.6 Hz, 1H), 7.03–6.98 (m, 1H), 6.92 (d, J = 8.4 Hz, 1H), 4.46 (t, J =
7.8 Hz, 2H), 4.19 (t, J = 7.8 Hz, 2H), 3.82 (s, 3H).
3-(3-Methoxybenzoyl)oxazolidin-2-one (1f):[15] Following general
procedure, 1f was isolated as a white solid (1.58 g, 71 %); H NMR
(400 MHz, CDCl3) δ = 7.37–7.32 (m, 1H), 7.23 (d, J = 7.6 Hz, 1H),
7.17 (s, 1H), 7.10–7.06 (m, 1H), 4.48 (t, J = 7.8 Hz, 2H), 4.16 (t, J =
7.8 Hz, 2H), 3.83 (s, 3H).
1
Experimental Section
List of Known Compounds/General Methods: All reactants re-
ported in the manuscript are commercially available and have been
prepared by the method reported previously. N-acylsuccinimides
were prepared by the general methods. All solvents were purchased
at the China supplier and used without any purification. All com-
3-(4-Methoxybenzoyl)oxazolidin-2-one (1g).[15] Following gen-
eral procedure, 1g was isolated as a white solid (1.42 g, 64 %); 1H
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NMR (400 MHz, CDCl3) δ = 7.73 (d, J = 7.69 Hz, 2H), 6.92 (d, J =
7.6 Hz, 2H), 4.48 (t, J = 7.8 Hz, 2H), 4.15 (t, J = 7.8 Hz, 2H), 3.90 (s,
3H).
1H), 7.50–7.46 (m, 2H), 7.39–7.36 (m, 3H), 7.14 (d, J = 6.4 Hz, 1H),
3.86 (s, 3H).
(4-Methoxyphenyl)(phenyl)methanone (3g):[14d] Following gen-
eral procedure, 3g was isolated as a white solid (36.5 mg, 86 %); 1H
NMR (400 MHz, CDCl3) δ = 7.83 (d, J = 8.8 Hz, 2H), 7.76 (d, J =
7.6 Hz, 2H), 7.57 (t, J = 7.4 Hz, 1H), 7.49–7.45 (m, 2H), 6.97 (d, J =
8.8 Hz, 2H), 3.89 (s, 3H).
3-(4-Fluorobenzoyl)oxazolidin-2-one (1h):[15] Following general
1
procedure, 1h was isolated as a white solid (1.09 g, 52 %); H NMR
(400 MHz, CDCl3) δ = 7.71 (dd, J = 8.8, 5.2 Hz, 2H), 7.14–7.10 (m,
2H), 4.51 (t, J = 7.8 Hz, 2H), 4.18 (t, J = 7.8 Hz, 2H); 19F NMR
(376 MHz, CDCl3) δ = –105.74.
3-[4-(Trifluoromethyl)benzoyl]oxazolidin-2-one (1i).[15] Follow-
ing general procedure, 1i was isolated as a white solid (1.11 g,
43 %); 1H NMR (400 MHz, CDCl3) δ = 7.72 (m, 4H), 4.52 (t, J = 7.8 Hz,
2H), 4.20 (t, J = 7.8 Hz, 2H). 19F NMR (376 MHz, cdcl3) δ = –63.14.
(4-Fluorophenyl)(phenyl)methanone (3h).[14d] Following general
procedure, 3h was isolated as a white solid (31.2 mg, 78 %); 1H NMR
(400 MHz, CDCl3) δ = 7.88–7.82 (m, 2H), 7.77 (d, J = 7.2 Hz, 2H),
7.60 (t, J = 7.6 Hz, 1H), 7.52–7.47 (m, 2H), 7.18–7.14 (m, 2H); 19F
NMR (376 MHz, CDCl3) δ = –105.95.
Methyl 4-(2-Oxooxazolidine-3-carbonyl)benzoate (1j):[15] Follow-
ing general procedure, 1j was isolated as a white solid (1.68 g,
67 %); 1H NMR (400 MHz, CDCl3) δ = 8.09 (d, J = 8.0 Hz, 2H), 7.68
(d, J = 8.0 Hz, 2H), 4.51 (t, J = 7.8 Hz, 2H), 4.18 (t, J = 7.8 Hz, 2H),
3.93 (s, 3H).
Phenyl[4-(trifluoromethyl)phenyl]methanone (3i):[14d] Following
general procedure, 3i was isolated as a white solid (32.5 mg, 65 %);
1H NMR (400 MHz, CDCl3) δ = 7.90 (d, J = 8.0 Hz, 2H), 7.81 (d, J =
7.2 Hz, 2H), 7.76 (d, J = 8.0 Hz, 2H), 7.63 (t, J = 7.4 Hz, 1H), 7.54–
7.49 (m, 2H). 19F NMR (376 MHz, CDCl3) δ = –63.03.
(2-Naphthoyl)oxazolidin-2-one (1k):[15] Following general proce-
dure, 1k was isolated as a white solid (1.82 g, 75 %); 1H NMR
(600 MHz, CDCl3) δ = 7.97 (dd, J = 14.8, 8.3 Hz, 2H), 7.94–7.87 (m,
1H), 7.60–7.45 (m, 4H), 4.06 (t, J = 8.0 Hz, 2H), 3.96 (t, J = 8.0 Hz,
2H).
Methyl 4-benzoylbenzoate (3j).[14d] Following general procedure,
3i was isolated as a white solid (29.8 mg, 62 %); H NMR (400 MHz,
CDCl3) δ = 8.15 (d, J = 8.4 Hz, 2H), 7.84 (d, J = 8.4 Hz, 2H), 7.80 (d,
J = 7.2 Hz, 2H), 7.62 (t, J = 7.4 Hz, 1H), 7.52–7.48 (m, 2H), 3.96 (s,
3H).
1
3-(Thiophene-2-carbonyl)oxazolidin-2-one (1l):[15] Following
general procedure, 1l was isolated as a white solid (1.30 g, 66 %);
1H NMR (400 MHz, CDCl3) δ = 7.95 (d, J = 4.0 Hz, 1H), 7.65 (d, J =
4.6 Hz, 1H), 7.14–1.10 (m, 1H), 4.49 (t, J = 7.8 Hz, 2H), 4.17 (t, J =
7.8 Hz, 2H).
Naphthalen-2-yl(phenyl)methanone (3k):[14d] Following general
procedure, 3k was isolated as a white solid (41.4 mg, 81 %); 1H NMR
(400 MHz, CDCl3) δ = 8.27 (s, 1H), 7.95 (b, 2H), 7.92 (d, J = 8.0 Hz,
2H), 7.87 (d, J = 6.8 Hz, 2H), 7.66–7.59 (m, 2H), 7.58–7.53 (m, 3H).
Phenyl(thiophen-2-yl)methanone (3l).[14d] Following general pro-
cedure, 3l was isolated as a white solid (27.1 mg, 72 %); 1H NMR
(400 MHz, CDCl3) δ = 7.87 (d, J = 6.8 Hz, 2H), 7.73 (dd, J = 4.8,
0.8 Hz, 1H), 7.65 (dd, J = 4.0, 1.2 Hz, 1H), 7.60 (t, J = 7.4 Hz, 1H),
7.52–7.48 (m, 2H), 7.17 (dd, J = 4.8, 3.6 Hz, 1H).
3-(Furan-2-carbonyl)oxazolidin-2-one (1m):[16] Following general
1
procedure, 1m was isolated as a white solid (0.9 g, 50 %); H NMR
(400 MHz, CDCl3) δ = 7.64 (s, 1H), 7.50 (d, J = 3.6 Hz, 1H), 6.58–6.55
(m, 1H), 4.50 (t, J = 7.8 Hz, 2H), 4.18 (t, J = 7.8 Hz, 2H).
Characterization Data of Disubstituted Ketones
Furan-2-yl(phenyl)methanone (3m):[14d] Following general proce-
dure, 3m was isolated as a white solid (21.0 mg, 61 %); 1H NMR
(400 MHz, CDCl3) δ = 7.97 (d, J = 7.2 Hz, 2H), 7.72 (d, J = 1.6 Hz,1H),
7.60 (t, J = 7.4 Hz, 1H), 7.50 (t, J = 7.4 Hz, 2H), 7.24 (d, J = 3.6 Hz,
1H), 6.60 (dd, J = 3.2, 1.6 Hz, 1H).
Benzophenone (3a):[14d] Following general procedure, 3a was iso-
lated as a white solid (33.6 mg, 88 %); 1H NMR (400 MHz, CDCl3)
δ = 7.80 (d, J = 7.2 Hz, 4H), 7.59 (t, J = 7.4 Hz, 2H), 7.48 (t, J = 7.6 Hz,
4H).
4-Benzoylbenzaldehyde (3n).[14d] Following general procedure, 3n
was isolated as a white solid (19.3 mg, 46 %); 1H NMR (400 MHz,
CDCl3) δ = 10.13 (s, 1H), 8.00 (d, J = 8.0 Hz, 2H), 7.92 (d, J = 8.0 Hz,
2H), 7.81 (d, J = 8.0 Hz, 2H), 7.63 (t, J = 7.0 Hz, 1H), 7.53–7.49 (m,
2H).
Phenyl(o-tolyl)methanone (3b):[14d] Following general procedure,
3b was isolated as a white solid (26.7 mg, 68 %); 1H NMR (400 MHz,
CDCl3) δ = 7.81 (d, J = 6.8 Hz, 2H), 7.61–7.58 (m, 1H), 7.48–7.46 (m,
2H), 7.42–7.38 (m, 1H), 7.33–7.29 (m, 2H), 7.28–7.24 (m, 1H), 2.34 (s,
3H).
Phenyl(m-tolyl)methanone (3c):[3] Following general procedure, [1,1′-Biphenyl]-4-yl(phenyl)methanone (3o):[14d] Following gen-
3c was isolated as a white solid (34.5 mg, 88 %); 1H NMR (400 MHz,
CDCl3) δ = 7.80 (d, J = 7.6 Hz, 2H), 7.63 (s, 1H), 7.58 (d, J = 7.6 Hz,
2H), 7.50–7.46 (m, 2H), 7.41–7.34 (m, 2H), 2.42 (s, 3H).
Phenyl(p-tolyl)methanone (3d):[14d] Following general procedure,
3d was isolated as a white solid (35.3 mg, 90 %); 1H NMR (400 MHz,
CDCl3) δ = 7.79 (d, J = 7.2 Hz, 2H), 7.73 (d, J = 8.0 Hz, 2H), 7.60–
7.56 (m, 1H), 7.47 (t, J = 7.6 Hz, 2H), 7.28 (d, J = 8.0 Hz, 2H), 2.44 (s,
3H).
(2-Methoxyphenyl)(phenyl)methanone (3e):[14d] Following gen-
eral procedure, 3e was isolated as a white solid (17.8 mg, 42 %); 1H
NMR (400 MHz, CDCl3) δ = 7.82 (d, J = 6.8 Hz, 2H), 7.58–7.54 (m,
1H), 7.50–7.41 (m, 3H), 7.37 (dd, J = 7.2, 1.2 Hz, 1H), 7.05 (dd, J =
7.2, 6.8 Hz, 1H), 7.00 (d, J = 8.4 Hz, 1H), 3.73 (s, 3H).
eral procedure, 3o was isolated as a white solid (40.3 mg, 78 %); 1H
NMR (400 MHz, CDCl3) δ = 7.89 (d, J = 8.0 Hz, 2H), 7.83 (d, J =
7.2 Hz, 2H), 7.70 (d, J = 8.0 Hz, 2H), 7.64 (d, J = 6.8 Hz, 2H), 7.59 (t,
J = 7.4 Hz, 1H), 7.50–7.46 (m, 4H), 7.40 (t, J = 7.2 Hz, 1H).
Acknowledgments
The authors gratefully acknowledge the support of the Science
and Technology Planning Project of Guangdong Province
(2017A010103017), National Natural Science Foundation of
China (51703069, 21272080), and Special Innovation Projects of
Common Universities in Guangdong Province (20178S0182).
(3-Methoxyphenyl)(phenyl)methanone (3f).[14d] Following gen-
eral procedure, 3f was isolated as a white solid (32.3 mg, 76 %); H
NMR (400 MHz, CDCl3) δ = 7.81 (d, J = 7.6 Hz, 2H), 7.62–7.57 (m,
Keywords: Bond cleavage · N-Acyloxazolidiones · Palladium
catalysis · Cross-coupling · Ketones
1
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Received: April 27, 2020
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Communication
doi.org/10.1002/ejoc.202000575
EurJOC
European Journal of Organic Chemistry
Palladium Catalysis
J. Jian, Z. He, Y. Zhang, T. Liu,
L. Liu, Z. Wang,* H. Wang,
S. Wang,* Z. Zeng* ............................ 1–6
Palladium-Catalyzed Suzuki Cou-
pling of N-Acyloxazolidinones via
Selective Cleavage of C–N Bonds
The preparation of substituted diaryl N-acyloxazolidinones as a new acyla-
ketones by selective cleavage of exo- tion reagent with arylboronic acids is
cyclic C–N bonds utilizing palladium- described for the first time.
catalyzed Suzuki coupling reaction of
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