Palladium-Catalyzed Carbonylative Coupling Reactions of N,N-Bis(methanesulfonyl)amides through C–N Bond Cleavage

Article abstract of DOI:10.1002/ejoc.201801124

Palladium-catalyzed carbonylative coupling reactions of various N,N-bis(methanesulfonyl)amides with arylboronic acids through C–N bond cleavage were carried out. The reactions proceeded under mild conditions in a short period of time without any additives to afford a wide range of unsymmetrical aryl ketones in excellent yields. This is the first example of a carbonylative coupling reaction using N,N-bis(methanesulfonyl)amide as a coupling substrate.

Full text of DOI:10.1002/ejoc.201801124

A Journal of
Accepted Article
Title: Palladium-Catalyzed Carbonylative Coupling Reactions of N,N-
Bis(methanesulfonyl)amides via C-N Bond Cleavage
Authors: Minkyung Lim, Hyeji Kim, Jaeyoung Ban, Junghan Son, Jae
Kyun Lee, Sun-Joon Min, Sang Uck Lee, and Hakjune Rhee
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201801124
Link to VoR: http://dx.doi.org/10.1002/ejoc.201801124
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10.1002/ejoc.201801124
European Journal of Organic Chemistry
FULL PAPER
Palladium-Catalyzed Carbonylative Coupling Reactions of N,N-
Bis(methanesulfonyl)amides via C-N Bond Cleavage
Minkyung Lim,[a]† Hyeji Kim,[a]† Jaeyoung Ban,[a] Junghan Son,[b] Jae Kyun Lee,[c] Sun-Joon Min,*[b]
Sang Uck Lee*[a,b] and Hakjune Rhee*[a,b]
reported reactions are hampered by the use of additives, high
temperature, and long reaction times. Only a few examples of
the coupling reactions with amides without using any additive
have been reported.[8i,8m,8p] Therefore, the discovery of new
reactive amides as coupling partners is challengeable.
Abstract: Palladium-catalyzed carbonylative coupling reactions of
various N,N-bis(methanesulfonyl)amides with arylboronic acids via
C-N bond cleavage were carried out. The reactions proceeded under
mild conditions in a short period of time without any additives to
afford a wide range of unsymmetrical aryl ketones in excellent yields.
This is the first example of a carbonylative coupling reaction using
N,N-bis(methanesulfonyl)amide as a coupling substrate.
Previous amide substrates
(a)
O
O
O
O
O
O
Boc
Bn
Ph
Ph
Ar
N
Ar
N
Ar
N
Ar
N
Ar
N
Boc
Boc
Ms
Ts
O
Introduction
2016, Garg[8n]
O
2016, Szostak[8i]
2015, Zou[8a]
2015, Szostak[8e]
O
2017, Szostak[8k]
Aryl ketones are important structural motifs in the synthesis of
functional organic materials, pharmaceuticals, photoactivators,
and flavor compounds.[1] Conventionally, Friedel-Crafts acylation
is used for the synthesis of aryl ketones, but this method is
limited by the stringent reaction conditions, poor regioselectivity,
and the use of corrosive reagents.[2] Transition-metal catalyzed
coupling reactions have emerged as more efficient
transformation techniques that utilize milder conditions and
provide improved regioselectivity.[3] Numerous methods involving
O
O
O
O
O
Me
Ar
N
S
Ar
N
Ar
N
Ar
N
N
N
O
O
2016
2017
Szostak[8j]
2017, Szostak[8m]
[8p]
Szostak[8h]
Zeng
2017, Szostak[8l]
[8q]
and
and
Zeng
work
This
(b)
O
O
S
O
R1
O
[Pd]
R2
N
a
variety of electrophilic coupling partners, including acyl
+
Ar
B(OH)2
R2
Ar
chlorides,[4] anhydrides,[5] esters,[6] thioesters,[7] and amides[8]
have been reported. Among these, the coupling reactions of
amides with arylboronic acids by C-N bond cleavage are
noteworthy. Amides are known to be poor electrophiles, which is
attributed to the resonance stability of the amide bond.[9] In 2015,
Garg and coworkers demonstrated amide bond activation during
the conversion of an amide to an ester in the presence of a
nickel catalyst.[10] Inspired by this finding, Zou,[8a,8b] Szostak,[8e-8m]
Garg,[8n] and Zeng[8p,8q] reported metal-catalyzed coupling
reactions employing various amides. A wide range of amide
substrates such as N-tosyl-amides,[8a] N-Boc-carbamates,[8n] N-
acyl-saccharins,[8h,8p] N,N-di-Boc amides,[8i] N-mesyl-amides,[8k]
and N-acyl-succinimides[8j,8q] have been successfully employed
as coupling partners (Scheme 1a). However, most of the
S
O
O
R1
=
R1 Methyl p-tolyl
,
=
R2
heterocyclic
Aryl, alkyl,
Scheme 1. Amides used for carbonylative coupling reactions.
In our interest in finding new amide substrates for these
carbonylative coupling reactions, we envisioned that N,N-
bis(sulfonyl)amide (Scheme 1b) would be a suitable substrate
for C-N bond cleavage because amide C-N bond would be
destabilized by its high electron-withdrawing property.
Furthermore, steric repulsion between N,N-bis(sulfonyl)amide
and amide carbonyl group leads to amide bond distortion, which
could promote C-N bond cleavage upon metal insertion. We
have previously demonstrated that N,N-bis(sulfonyl)amine
derivatives such as N,N-ditosylallylamine[11] and N,N-
ditosylbenzylamines[12] are used as reactive electrophiles for Pd-
catalyzed Tsuji−Trost allylic alkylations. Thus, it is worthwhile to
explore N,N-bis(sulfonyl)amide as a potential substrate for use
in a coupling reaction. Herein, we report an additive-free
palladium-catalyzed coupling reaction by utilizing various N,N-
bis(methanesulfonyl)amides as carbonyl donors via C-N bond
cleavage. This is the first example of a coupling reaction using
N,N-bis(methanesulfonyl)amide as a coupling partner.
[a]
[b]
Dr. M. Lim, H. Kim, J. Ban, Prof. Dr. S. U. Lee, Prof. Dr. H. Rhee.
Department of Bionanotechnology, Hanyang University, Sangnok-gu
Hanyang Daehak-ro 55, Ansan, Gyeonggi-do, 15588, Republic of
Korea, hrhee@hanyang.ac.kr, sulee@hanyang.ac.kr
J. Son, Prof. Dr. S. -J. Min, Prof. Dr. S. U. Lee, Prof. Dr. H. Rhee.
Department of Applied Chemistry, Hanyang University, Sangnok-gu
Hanyang Daehak-ro 55, Ansan, Gyeonggi-do, 15588, Republic of
Korea, sjmin@hanyang.ac.kr
[c]
†
Dr. J. K. Lee, Center for Neuro-Medicine, Korea Institute of Science
and Technology (KIST), Seongbuk-gu Hwarangro 14-gil 5, Seoul
136-791, Republic of Korea
These authors contributed equally.
Supporting information for this article is given via a link at the end of
the document.
Results and Discussion
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10.1002/ejoc.201801124
European Journal of Organic Chemistry
FULL PAPER
that of N,N-bis(p-toluenesulfonyl)benzamides (1a) (τ + χN =
82.7°) and the former showed higher reactivity in the
coupling reactions. However, because the reaction takes
place in solution, utilization of the solid-state data (X-ray
crystallography data) might be insufficient for modeling the
reactivity of distorted amides. To confirm the reactivity of
N,N-bis(sulfonyl)benzamides in solution, we calculated the
stability of an oxidative addition intermediate, namely, acyl-
Pd(II) complex in the coupling reaction (see below
Initially, we investigated the possibility of the use of N,N-
bis(sulfonyl)amides as substrates for carbonylative coupling
reactions. Thus, we first attempted to synthesize N,N-
bis(sulfonyl)amides according to literature procedures.[13]
Although most N,N-bis(sulfonyl)amides are unknown, we
could successfully access to N,N-bis(p-toluenesulfonyl)-
amides and N,N-bis(methanesulfonyl)amides following a
modified procedure. The coupling reactions of N,N-
bis(sulfonyl)benzamides
1 and 2 with phenylboronic acid 3a
intermediate
5 in Scheme 5). Density functional theory
were performed under a typical Suzuki reaction condition.
As shown in Scheme 2, the reactions of both substrates
(DFT) calculations indicated that 2a has a lower free energy
(∆G) of intermediate than 1a (66.64 kcal mol-1 vs. 83.52
kcal mol-1), which is in good agreement with the
experimental results (for more details, see SI). Therefore,
on the basis of the Winkler−Dunitz distortion parameters
and the energy stabilization of acyl-palladium intermediate,
N,N-bis(methanesulfonyl)benzamide was selected as the
coupling substrate.
1a/1b and 2a/2b proceeded to give the corresponding
ketones 4a and 4b as we expected. Interestingly, we
observed that the yields of 4a and 4b from 2a and 2b were
significantly higher than those from 1a and 1b. Presumably,
N,N-bis(methanesulfonyl)benzamides (2a and 2b) are more
reactive than N,N-bis(p-toluenesulfonyl)benzamides
and 1b) under the reaction condition.
(1a
Table 1. Optimization of the reaction conditions.[a]
O
O
mol%
5
Cl2
Pd(PPh3)2
K3PO
O
O
R2
equiv)
4 (2.5
N
Ms
+
Base, Catalyst
solvent
B(OH)2
PhB(OH)2
3a 2.5
toluene, 50 o 4 h
C,
N
R2
+
R1
1a
R1
Ms
,
equiv)
(
Cl
Cl
:
:
=
=
R1
H R2=Ts
,
R1 Cl, R2=Ts
:
:
=
=
4a
4b
R
R
32%
H,
Cl, 42%
(Ts)
(Ts)
1b
2b
3a
4b
:
:
=
=
2a
2b
R1
H
,
R2=Ms
:
:
=
=
4a
4b
R
R
53%
H,
Cl, 91%
(Ms)
(Ms)
R1 Cl, R2=Ms
Yield
(%)[b]
Entry
Catalyst (mol%)
Base
Solvent
Time
Scheme 2. Initial study of palladium-catalyzed carbonylative coupling
reactions employing N,N-bis(sulfonyl)benzamides.
Pd(OAc)2 (5)
Pd/C (5)
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
Et3N
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
4 h
4 h
39
4
1
2
PdCl2 (5)
4 h
43
10
20
48
39
88
91
94
99
3
Pd2(dba)3 (5)
4 h
4
Pd(PPh3)4 (5)
4 h
5
[Pd(allyl)Cl]2 (5)
Pd(CH3CN)4(BF4)2 (5)
PdCl2·(CH3CN)2 (5)
Pd(PPh3)2Cl2 (5)
Pd(PPh3)2Cl2 (5)
Pd(PPh3)2Cl2 (5)
4 h
6
Figure 1. X-ray crystal structures of N,N-bis(p-toluenesulfonyl)-
4 h
7
benzamide (CCDC 1822720, 1a
)
and N,N-bis(methanesulfonyl)-
benzamide (CCDC 1822719, 2a) with 50% ellipsoidal probability.
4 h
8
Next, crystallographic and computational studies of N,N-
4 h
9
bis(p-tolunesulfonyl)benzamides
1 and N,N-bis(methane-
4 h
10
11
sulfonyl)benzamides were performed to determine an
2
optimal substrate for the coupling reaction. In general, the
reactivity of an amide is usually evaluated by the sum of the
distortion parameters (τ+χN), where the distortion stimulates
C-N bond breaking by reducing the resonance effect of the
amide. The ground-state distortion of amides is
characterized by the twist angle (τ) and pyramidalization at
the nitrogen (χN) (i.e., the Winkler− Dunitz distortion
parameter).[8e,14] In order to apply this parameter to our
synthesized amides, structures of 1a and 2a were
determined by X-ray diffraction (Figure 1). The X-ray
structures confirmed that 1a (τ = 81.0°, χN = 1.7°) and 2a (τ
= 63.2°, χN = 27.1°) contain a highly distorted amide bond.
The amide bond distortion of N,N-bis(methanesulfonyl)-
benzamides (2a) (τ + χN = 90.3°) was slightly greater than
K2CO3
10 min
1,4-
Dioxane
Pd(PPh3)2Cl2 (5)
K2CO3
4 h
52
12
Pd(PPh3)2Cl2 (5)
Pd(PPh3)2Cl2 (5)
Pd(PPh3)2Cl2 (5)
Pd(PPh3)2Cl2 (1)
K2CO3
K2CO3
K2CO3
K2CO3
THF
DMF
4 h
4 h
19
trace
52
13
14
15
16
CHCl3
Toluene
4 h
20 min
99[c]
[a] Reaction conditions: 2b (1.0 mmol), 3a (2.5 mmol), base (2.5 mmol),
solvent 8.0 mL, 50 oC. [b] Isolated yield. [c] 3a (1.5 mmol), K2CO3 (3.0 mmol),
65 oC.
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10.1002/ejoc.201801124
European Journal of Organic Chemistry
FULL PAPER
reactions of N,N-bis(methanesulfonyl)benzamides with
electron-withdrawing groups (Scheme 3, 4g
halogen substituents (4b 4c) provided high yields in short
reaction times (92−99%). Benzamides with electron-
donating groups (4d 4e, and 4f) and heteroaromatics (4i
4j) produced the coupled products in 62−92% yields. In
addition, alkyl ketones 4k 4n could be effectively
synthesized via this coupling process from the
corresponding aliphatic N,N-bis(methanesulfonyl)amide
, 4h) and
,
Having identified
cleavage, we optimized the carbonylative coupling reaction
using 4-chloro-N,N-bis(methanesulfonyl)benzamide 2b
a suitable substrate for C-N bond
,
,
(
)
and phenylboronic acid under various reaction conditions.
Key results were summarized in Table 1 (more details, see
Table S2 in SI). Catalysts such as Pd(PPh3)2Cl2, Pd(OAc)2,
Pd/C, Pd(PPh3)4, and PdCl2 were tested in the reaction, and
the Pd(II) catalysts were found to be more effective than the
Pd(0) catalysts (Table 1, entries 1−9). Notably,
Pd(PPh3)2Cl2 produced the best yield of 91% (Table 1, entry
9). Using K2CO3 as a base, the product was obtained in 10
min with 99% yield (Table 1, entry 11). Toluene was more
effective for the reaction than polar solvents such as
tetrahydrofuran (THF), 1,4-dioxane, or dimethylformamide
(DMF). Finally, by varying the amounts of catalyst and
reaction temperature, the best condition was chosen as
shown in entry 16 in Table 1.
(
−
)
2
although the yields were decreased in some cases due to
the instability of substrates.
Scheme 4. Scope of arylboronic acids in the carbonylative coupling
reaction.[a]
K2CO3
O
O
mol%
1
Cl2
Pd(PPh3)2
Ms
N
+
Ar
ArB(OH)2
toluene, 65 o
C
Ms
4
2a
3
O
O
O
O
Scheme 3. Scope of N,N-bis(methanesulfonyl)amides in the
carbonylative coupling reaction.[a]
Cl
F
4a
40 min, 98%
O
4b
4c
4
,
,
4h,
O
75%
82%
4d
4h
,
2
74%
h,
h,
,
K2CO3
O
O
O
O
mol%
1
Cl2
Pd(PPh3)2
B(OH)2
Ms
R
R
N
+
toluene, 65 o
C
Ms
O2N
F3C
H3CO
3a
2
4
h,
4g
3
47%[b]
h,
4e
2
99%
4f
,
,
50 min, 98%
O
24
trace[b]
,
,
h,
R=
O
heterocyclic
Aryl, alkyl,
O
O
O
O
O
O
Cl
F
4o, 4 46%[b]
h,
,
4p
4q
30 min, 82%
,
40 min, 96%
80%[b]
4a
,
40 min, 98%
O
4b
4c
30
,
20
min,
O
99%
min,
97%
4d
2
,
,
h,
[a] Reaction conditions: N,N-bis(methanesulfonyl)benzamide 2a (1.0
O
O
mmol), arylboronic acid
3 (1.5 mmol), K2CO3 (3.0 mmol), Pd(PPh3)2Cl2 1
mol%, toluene 8.0 mL, 65 oC. [b] Reflux.
O2N
F3C
H3CO
30 min, 92%[b]
O
,
20 min, 98%
O
h,
O
4h
The scope with regard to arylboronic acid 3 was also examined
(Scheme 4). The coupling reactions of phenylboronic acids with
halogen substituents (Scheme 4, 4b, 4c) and electron-donating
groups (4d−4f) yielded satisfactory results (74−99%). When
naphthylboronic acid and biphenylboronic acid were employed in
this protocol, the corresponding aryl ketones 4p and 4q were
obtained in 96% and 82% yields, respectively. However,
substrates with electron-withdrawing groups such as 4g and 4o
gave relatively moderate yields even under reflux conditions (46%
and 47%).
2
,
92%
4f
4j
4e
30 min, 62%[b]
O
4g
,
,
S
O
91%[b]
30 min, 72%[b]
76%[b]
h,
4l
6
,
4i
4k
4
,
1
,
,
43%[b]
h,
O
h,
O
12 48%[b]
12 37%[b]
4n
,
h,
4m
,
h,
[a] Reaction conditions: N,N-bis(methanesulfonyl)amidederivatives
2
At last, the mechanism of the carbonylative coupling
reaction by N,N-bis(methanesulfonyl)amide was proposed
in Scheme 5.[8q] Oxidative addition occurred at the amide
C–N bond of the N,N-bis(methanesulfonyl)amide to afford
(1.0 mmol), phenylboronic acid 3a (1.5 mmol), K2CO3 (3.0 mmol),
Pd(PPh3)2Cl2 1 mol%, toluene 8.0 mL, 65 C. [b] Phenylboronic acid 3a
(3.0 mmol).
o
The scope of the coupling reactions with various N,N-
bis(methanesulfonyl)amides (2) was investigated under the
acyl-Pd(II) complex
Pd(II) complex
5
; following transmetallation, aryl-acyl
6
was formed; reductive elimination
established reaction conditions employing Pd(PPh3)2Cl2 (1
mol% Pd content), K2CO3 (3.0 equiv), and phenylboronic
acid (1.5 equiv), at 65 °C in toluene (Table 1, entry 16); the
results are shown in Scheme 3. The reaction time was
determined as the time at which the starting material
disappeared or no longer diminished. The coupling
occurred to produce the desired aryl ketones and
regenerate the Pd(0) species.
Conclusions
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10.1002/ejoc.201801124
European Journal of Organic Chemistry
FULL PAPER
In conclusion, we describe the synthesis of aryl ketones using
palladium-catalyzed carbonylative coupling reactions of various
N,N-bis(methanesulfonyl)amides with arylboronic acids via C-N
bond cleavage. Considering the Winkler−Dunitz distortion
parameters and the energy stabilization of acyl-palladium
intermediate by the analysis of X-ray structure and DFT
with double-focusing mass analyzers at the Daegu center of
Korea Basic Science Institute. X-ray crystallography
measurements were taken on
a Rigaku R-AXIS RAPID
diffractometer using graphite monochromated Mo-Ka radiation.
Synthesis of N,N-Bis(p-toluenesulfonyl)benzamide (1a):
Silver carbonate (1.38 g, 5.0 mmol) was added a solution of pre-
synthesized bis(p-toluenesulfonyl)amine[15] (1.63 g, 5.0 mmol) in
anhydrous acetonitrile (20 mL). Freshly distilled benzoyl chloride
calculation, we selected N,N-bis(methanesulfonyl)amide
a
suitable substrate for this coupling reaction. The carbonylative
coupling reactions proceeded under mild conditions in a short
period of time without any additives to provide a wide range of
unsymmetrical aryl ketones in good to excellent yields.
Therefore, N,N-bis(methanesulfonyl)amides are effective
substrates for the carbonlyative coupling reaction and they will
be further applied to other coupling reactions as highly reactive
electrophiles.
o
(1.16 mL, 10.0 mmol) was added slowly to the solution at 0 C.
The flask was wrapped with aluminum foil and the mixture was
stirred at room temperature under argon. After the solution was
stirred for 4 h, the solvent was removed under vacuum. The
reaction mixture was filtered through a celite pad and washed
with CH2Cl2. The filtrate was washed with saturated Na2CO3
solution, and the organic layer was dried over MgSO4, and
concentrated under vacuum. Precipitation with ethyl acetate and
hexane afforded the product. White solid, 1.59 g (74 %);
Ph3P
Ph3P
Cl
Cl
+
K
2CO3
Pd
o
1
m.p.176.1-177.1 C; Rf = 0.25 (EtOAc:Hexane = 1:5); H NMR
(400 MHz, CDCl3): δ = 7.84-7.81 (m, 6H), 7.64 (t, J = 7.5 Hz,
1H), 7.41 (t, J = 7.8 Hz, 2H), 7.29 (d, J = 8.4 Hz, 4H), 2.46 (s,
6H); 13C NMR (100 MHz, CDCl3): δ = 166.9, 145.6, 135.7, 134.9,
133.3, 131.5, 129.4, 129.3, 128.7, 21.7; IR (neat): 3069, 2988,
2923, 1730, 1593, 1359, 1224, 1163, 981, 812 cm-1; HRMS
(FAB-double focusing): m/z [M+H]+ for C21H19NO5S2, calculated:
430.0783, found: 430.0784.
ArB(OH)2
Ar-Ar
O
Ms
O
R
N
n
(PPh3) Pd(0)
Ms
R
Ar
O
S
=
Ms
Product
O
oxidative
addition
reductive
elimination
Synthesis of 4-Chloro-N,N-bis(p-toluenesulfonyl)benzamide
(1b)[13c]: 4-Clorobenzaldehyde (1.69 g, 12.0 mmol) and pre-
synthesized bis(p-toulenesulfonyl)amine[15] (1.95 g, 6.0 mmol)
were added to flask with a magnetic stirring bar and EtOAc (30
mL). To this mixture n-Bu4NI (0.66 g, 1.8 mmol) and tert-butyl
hydroperoxide (5.5 M in decane, 5.45 mL) were added at room
temperature. After stirring at 70 °C for 2 h, the organic solvent
was removed under vacuum and the residue was purified by
flash silica gel column chromatography to afford the desired
product. White solid, 1.11g (42 %); m.p. 183.5-184.9 oC; Rf =
0.37 (EtOAc:Hexane = 1:5); 1H NMR (400 MHz, CDCl3): δ =
7.81-7.77 (m, 6H), 7.39 (d, J = 8.6 Hz, 2H), 7.30 (d, J = 8.2 Hz,
4H), 2.47 (s, 6H); 13C NMR (100 MHz, CDCl3): δ = 166.0, 145.8,
141.8, 135.6, 132.8, 131.9, 129.5, 129.4, 129.2, 21.8.
R
O
m
(PPh3) Pd(II)
Ms
R
O
N
Ms
m
Pd(II)(PPh3)
5
Ar
6
ArB(OH)2
K
2CO3
KN Ms
Ms
Scheme 5. Presumed mechanism of palladium-catalyzed carbonylative
coupling reaction.
Synthesis of N,N-Bis(methanesulfonyl)amides for 2a-2j:
Silver carbonate (1.38 g, 5.0 mmol) was added a solution of pre-
synthesized bis(methanesulfonyl)amine[16] (0.87 g, 5.0 mmol) in
anhydrous acetonitrile (20 mL). Freshly distilled acyl chloride
Experimental Section
General: All chemicals were purchased from commercial
sources (Sigma Aldrich, TCI and Alfa Aesar) used without any
further purification, unless specifically mentioned. Analytical thin
layer chromatography (TLC) was conducted on E. Merck 60
aF254 aluminum-backed silica gel plates (0.2 mm) with a
fluorescent indicator. Flash column chromatography was
performed using silica gel (230-400 mesh). 1H and 13C NMR
were recorded on a Bruker 400 MHz instrument using CDCl3 or
DMSO-d6 containing tetramethylsilane (TMS) as an internal
standard. Infrared spectra were recorded on a Bruker Alpha FT-
IR spectrometer. Melting points were determined with a Sanyo
Gallenkamp melting point apparatus. HRMS data were obtained
on a High Resolution Mass Spectrometer (JMS-700) equipped
o
(10.0 mmol) was added slowly to the solution at 0 C. The flask
was wrapped with aluminum foil and the mixture was stirred at
room under argon. After the solution was stirred several hours,
the solvent was removed under vacuum (for more details, see
Table S1 in SI). The reaction mixture was filtered through a
celite pad and washed with CH2Cl2. The filtrate was washed with
saturated Na2CO3 solution, and the organic layer was dried over
MgSO4, and concentrated under vacuum. Precipitation with ethyl
acetate and hexane afforded the product.
N,N-Bis(methanesulfonyl)benzamide (2a)[13a]
1.15 g (83 %); m.p. 135.0 C; Rf = 0.18 (EtOAc:Hexane = 1:5);
: White solid,
o
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10.1002/ejoc.201801124
European Journal of Organic Chemistry
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1H NMR (400 MHz, CDCl3): δ = 7.96 (d, J = 7.2 Hz, 2H), 7.69 (t,
J = 7.5 Hz, 1H), 7.54 (t, J = 7.8 Hz, 2H), 3.54 (s, 6H); 13C NMR
(100 MHz, CDCl3): δ = 166.4, 135.2, 133.3, 130.3, 129.2, 43.7.
C10H10F3NO5S2, calculated: 344.9952, found: 344.9949.
4-Nitro-N,N-bis(methanesulfonyl)benzamide (2h): White solid,
o
0.90 g (56 %); m.p. 166.7-167.5 C; Rf = 0.15 (EtOAc:Hexane =
4-Chloro-N,N-bis(methanesulfonyl)benzamide (2b)[13c]: White
1:5); H NMR (400 MHz, CDCl3): δ = 8.39 (d, J = 8.9 Hz, 2H),
1
solid, 1.32
g
(85 %); m.p. 175.2-176.8 oC; Rf
=
0.23
8.09 (d, J = 8.9 Hz, 2H), 3.58 (s, 6H); 13C NMR (100 MHz,
CDCl3): δ = 165.9, 151.3, 138.8, 130.8, 124.4, 44.1; IR (neat):
3121, 3058, 3022, 1709, 1531, 1368, 1348, 1319, 1236, 1161,
958 cm-1; HRMS (EI-double focusing): m/z [M]+ for C9H10N2O7S2,
calculated: 321.9929, found: 321.9931.
(EtOAc:Hexane = 1:5); 1H NMR (400 MHz, CDCl3): δ = 7.90 (d, J
= 8.7 Hz, 2H), 7.53 (d, J = 8.7 Hz, 2H), 3.55 (s, 6H); 13C NMR
(100 MHz, CDCl3): δ = 165.7, 142.2, 131.9, 131.7, 129.7, 43.8.
4-Fluoro-N,N-bis(methanesulfonyl)benzamide (2c): White
solid, 1.23g (83 %); m.p. 140.0-141.0 oC; Rf
=
0.18
N,N-Bis(methanesulfonyl)furan-2-carboxamide (2i): White
(EtOAc:Hexane = 1:5); 1H NMR (400 MHz, CDCl3): δ = 8.01 (dd,
J = 8.9, 5.2 Hz, 2H), 7.23 (t, J = 8.5 Hz, 2H), 3.55 (s, 6H); 13C
NMR (100 MHz, CDCl3): δ = 167.0 (d, J = 257.9 Hz), 165.2,
133.3 (d, J = 9.8 Hz), 129.6 (d, J = 2.9 Hz), 116.7 (d, J = 22.4
Hz), 43.7; IR (neat): 3043, 3024, 2940, 1723, 1599, 1368, 1324,
1241, 1163, 958, 763 cm-1; HRMS (EI-double focusing): m/z [M]+
for C9H10FNO5S2, calculated: 294.9984, found: 294.9987.
solid, 0.60
g
(45 %); m.p. 165.5-166.3 oC; Rf
=
0.10
1
(EtOAc:Hexane = 1:5); H NMR (400 MHz, CDCl3): δ = 7.72 (s,
1H), 7.53 (d, J = 3.7 Hz, 1H), 6.68 (dd, J = 3.7, 1.6 Hz, 1H), 3.63
(s, 6H); 13C NMR (100 MHz, CDCl3): δ = 154.7, 148.5, 147.0,
123.7, 114.1, 44.3; IR (neat): 3148, 3025, 2946, 1698, 1563,
1451, 1362, 1346, 1161, 920, 779 cm-1; HRMS (EI-double
focusing): m/z [M]+ for C7H9NO6S2, calculated: 266.9871, found:
266.9870.
4-Methyl-N,N-bis(methanesulfonyl)benzamide (2d): White
solid, 1.09
g
(75 %); m.p. 151-152.4 oC; Rf
=
0.25
N,N-Bis(methanesulfonyl)thiophene-2-carboxamide
(2j):
(EtOAc:Hexane = 1:5); 1H NMR (400 MHz, CDCl3): δ = 7.87 (d, J
= 8.3 Hz, 2H), 7.34 (d, J = 8.0 Hz, 2H), 3.54 (s, 6H), 2.45 (s,
White solid, 0.67 g (47 %); m.p. 166.0-167.0 oC; Rf = 0.13
(EtOAc:Hexane = 1:5); 1H NMR (400 MHz, CDCl3): δ = 7.96 (dd,
3H) ; 13C NMR (100 MHz, CDCl3): δ = 166.0, 146.9, 130.7, 130.6, J = 3.9, 1.2 Hz, 1H), 7.87 (dd, J = 4.9, 1.2 Hz, 1H), 7.24 (dd, J =
130.0, 43.7, 21.9; IR (neat): 3040, 3022, 2932, 1719, 1605, 1365, 4.9, 4.0 Hz, 1H), 3.57 (s, 6H); 13C NMR (100 MHz, CDCl3): δ =
1348, 1322, 1158, 918, 753 cm-1; HRMS (EI-double focusing):
m/z [M]+ for C10H13NO5S2, calculated: 291.0235, found:
291.0233.
158.6, 138.1, 137.7, 137.5, 129.3, 43.6; IR (neat): 3044, 3023,
2940, 1682, 1408, 1349, 1319, 1250, 1161, 1055, 944, 738 cm-1;
HRMS (EI-double focusing): m/z [M]+ for C7H9NO5S3, calculated:
282.9643, found: 282.9645.
4-tert-Butyl-N,N-bis(methanesulfonyl)benzamide (2e): White
solid, 1.33
g
(80 %); m.p. 119-119.7oC; Rf
=
0.13
Synthesis of N,N-Bis(methanesulfonyl)amides for 2k-2n:
The same equivalents of KOH and pre-synthesized
(EtOAc:Hexane = 1:5); 1H NMR (400 MHz, CDCl3): δ = 7.92 (d, J
= 8.6 Hz, 2H), 7.55 (d, J = 8.6 Hz, 2H), 3.55 (s, 6H), 1.35 (s, 9H); bis(methanesulfonyl)amine17 was dissolved in methanol and
13C NMR (100 MHz, CDCl3): δ = 165.8, 159.7, 130.6, 130.2,
126.3, 43.6, 35.3, 30.8; IR (neat): 3042, 2965, 2872, 1718, 1603,
1355, 1249, 1160, 953, 922, 843 cm-1; HRMS (EI-double
stirred at room temperature. After 3 hours, a white solid was
obtained by filtration and dried in vacuum oven at 60 oC. Freshly
distilled acyl chloride (70.0 mmol) was added to a solution of
focusing): m/z [M]+ for C13H19NO5S2, calculated: 333.0705, found: thoroughly dried potassium bis(methanesulfonyl)amide (1.06 g,
333.0705.
5.0 mmol) and benzene (1.0 mL). And the reaction mixture was
heated over several hours under argon (for more details, see
Table S1 in SI). After the reaction was complete, the solvent was
removed under vacuum and add 10 mL of CH2Cl2. The insoluble
salt was removed by filtration, and the CH2Cl2 of filtrate was
4-Methoxy-N,N-bis(methanesulfonyl)benzamide (2f): White
solid, 1.03
(EtOAc:Hexane = 1:5); 1H NMR (400 MHz, CDCl3): δ = 7.96 (d, J
g = 0.15
(67 %); m.p. 138-139.2 oC; Rf
= 8.9 Hz, 2H), 7.01 (d, J = 8.9 Hz, 2H), 3.90 (s, 3H), 3.53 (s, 6H); removed. The solution of chloroform and hexane (1:10, v/v) was
13C NMR (100 MHz, CDCl3): δ = 165.6, 164.8, 133.4, 125.3,
added in the mixture and then filtered to remove the insoluble
114.7, 55.7, 43.6; IR (neat): 3025, 2941, 2848, 1713, 1603, 1369, white solid. The solvent of colorless solution was removed to
1252, 1162, 1014, 920, 838 cm-1; HRMS (EI-double focusing):
m/z [M]+ for C10H13NO6S2, calculated: 307.0184, found:
307.0182.
afford the pure product.
N,N-Bis(methanesulfonyl)acetamide (2k)[13a]:White solid, 0.96
g (89 %); m.p. 108.0-109.0 oC; 1H NMR (400 MHz, CDCl3): δ
3.51 (s, 6H), 2.57 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 169.7,
44.5, 28.2.
4-Trifluoromethyl-N,N-bis(methanesulfonyl)benzamide (2g):
White solid, 1.07 g (62 %); m.p. 140.8-141.7 oC; Rf = 0.15
(EtOAc:Hexane = 1:5); 1H NMR (400 MHz, CDCl3): δ = 8.05 (d, J
= 8.2 Hz, 2H), 7.80 (d, J = 8.3 Hz, 2H), 3.56 (s, 6H); 13C NMR
(100 MHz, CDCl3): δ = 166.1, 136.7, 136.1 (q, J = 32.9 Hz),
130.3, 126.3 (q, J = 3.7 Hz), 123.1 (q, J = 271.4 Hz), 43.9; IR
(neat): 3358, 3028, 2920, 2850, 1732, 1371, 1321, 1162, 1131,
842 cm-1; HRMS (EI-double focusing): m/z [M]+ for
N,N-Bis(methanesulfonyl)propanamide (2l)[13a]: White solid,
1.07 g (93 %); m.p. 82.4-83.4 oC; H NMR (400 MHz, CDCl3): δ
1
= 3.49 (s, 6H), 2.87 (q, J = 7.3 Hz, 2H), 1.24 (t, J = 7.3 Hz, 3H);
13C NMR (100 MHz, CDCl3): δ = 173.7, 44.5, 35.1, 8.8.
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10.1002/ejoc.201801124
European Journal of Organic Chemistry
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2-Methyl-N,N-bis(methanesulfonyl)propanamide
(2m)[13a]
:
128.1, 125.2, 35.0, 31.1.
White solid, 0.95 g (78 %); m.p. 79.2-80.1 oC; 1H NMR (400 MHz,
CDCl3): δ = 3.50 (s, 6H), 3.04 (sept, J = 6.9 Hz, 1H), 1.29 (d, J =
6.9 Hz, 6H); 13C NMR (100 MHz, CDCl3): δ = 177.3, 44.5, 40.7,
18.8.
(4-Methoxyphenyl)(phenyl)methanone (4f)[18]
: White solid,
o
132 mg (62 %); m.p. 62.9-63.9 C; Rf = 0.15 (EtOAc:Hexane =
1
1:50); H NMR (400 MHz, CDCl3): δ = 7.83 (d, J = 8.9 Hz, 2H),
7.77-7.74 (m, 2H), 7.56 (t, J = 7.4 Hz, 1H), 7.49-7.45 (m, 2H),
6.98-6.94 (m, 2H), 3.88 (s, 3H); 13C NMR (100 MHz, CDCl3): δ =
195.5, 163.1, 138.2, 132.5, 131.8, 130.1, 129.7, 128.1, 113.5,
55.4.
N,N-Bis(methanesulfonyl)butanamide (2n)[13b]: White solid,
o
1
0.69 g (57 %); m.p. 65-66 C; H NMR (400 MHz, CDCl3): δ =
3.50 (s, 6H), 2.82 (t, J = 7.2 Hz, 2H), 1.76 (sext, J = 7.2 Hz, 2H),
1.00 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ = 172.8,
44.5, 43.2, 18.2, 13.1.
Phenyl[4-(trifluoromethyl)phenyl)]methanone (4g)[19]: White
solid, 245 mg (98 %); m.p.112.0-113.2 oC; Rf
= 0.25
Coupling Reaction of N,N-Bis(methanesulfonyl)amides with
Arylboronic Acids: N,N-Bis(methanesulfonyl)amide (1.0 mmol),
arylboronic acid (183 mg, 1.5 mmol), K2CO3 (415 mg, 3.0 mmol)
and Pd(PPh3)2Cl2 (7.20 mg, 0.01 mmol) were added to a dried
flask under an argon atmosphere, and anhydrous toluene (8.0
mL) was added with vigorous stirring at 65 °C. The reaction time
was determined by TLC monitoring. After completion of the
reaction, the reaction mixture was cooled to room temperature.
The mixture was extracted with ethyl acetate and brine solution.
The organic layer was dried over MgSO4, and concentrated at
(EtOAc:Hexane = 1:50); 1H NMR (400 MHz, CDCl3): δ = 7.89 (d,
J = 8.0 Hz, 2H), 7.82-7.79 (m, 2H), 7.75 (d, J = 8.1, 2H), 7.64 (t,
J = 7.4 Hz, 1H), 7.51 (t, J = 7.6 Hz, 2H); 13C NMR (100 MHz,
CDCl3): δ = 195.5, 140.7, 136.7, 133.7 (q, J = 32.5 Hz), 133.1,
130.10, 130.07, 128.5, 125.3 (q, J = 3.7 Hz), 123.6 (q, J = 271.0
Hz).
(4-Nitrophenyl)(phenyl)methanone (4h)[20]: White solid, 209
mg (92 %); m.p. 135.0-136.1 oC; Rf = 0.43 (EtOAc:Hexane =
1
1:5); H NMR (400 MHz, CDCl3): δ = 8.33 (d, J = 8.8 Hz, 2H),
reduced
pressure.
Flash
column
chromatography
7.93 (d, J = 8.8 Hz, 2H), 7.79 (d, J = 7.1 Hz, 2H), 7.65 (t, J = 7.4
Hz, 1H), 7.52 (t, J = 7.7 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ
= 194.72, 149.71, 142.78, 136.17, 133.41, 130.63, 130.03,
128.61, 123.46.
(EtOAc:Hexane) afforded the desired product.
Diphenylmethanone (4a)[8p]: White solid, 179 mg (98 %); m.p.
48.7-49.5 C; Rf = 0.20 (EtOAc:Hexane = 1:50); 1H NMR (400
o
MHz, CDCl3): δ = 7.85-7.82 (m, 4H), 7.64-7.59 (m, 2H), 7.53-
7.49 (m, 4H); 13C NMR (100 MHz, CDCl3): δ = 196.8, 137.6,
132.5, 130.1, 128.3.
(2-Furanyl)(phenyl)methanone (4i)[8p]: White solid, 157 mg
o
1
(91 %); m.p. 42.2-43.5 C; Rf = 0.34 (EtOAc:Hexane = 1:5); H
NMR (400 MHz, CDCl3): δ = 7.98-7.96 (m, 2H), 7.71 (dd, J = 1.6,
0.6 Hz, 1H), 7.60 (tt, J = 7.4, 1.5 Hz, 1H), 7.50 (t, J = 7.5 Hz, 2H),
7.24 (dd, J = 3.5, 0.6 Hz, 1H), 6.60 (dd, J = 3.6, 1.7 Hz, 1H); 13C
NMR (100 MHz, CDCl3): δ = 182.7, 152.2, 147.2, 137.2, 132.7,
129.3, 128.5, 120.8, 112.3.
(4-Chlorophenyl)(phenyl)methanone (4b)[8p]: White solid, 214
mg (99 %); m.p. 76.1-77.0 oC; Rf = 0.20 (EtOAc:Hexane = 1:50);
1H NMR (400 MHz, CDCl3): δ = 7.79-7.74 (m, 4H), 7.63-7.58 (m,
1H), 7.51-7.45 (m, 4H); 13C NMR (100 MHz, CDCl3): δ = 195.5,
138.9, 137.2, 135.8, 132.6, 131.4, 129.9, 128.6, 128.4.
(2-Thienyl)(phenyl)methanone (4j)[8p]: White solid, 136 mg
o
1
(72 %); m.p. 58.0-59.2 C; Rf = 0.45 (EtOAc:Hexane = 1:5); H
NMR (400 MHz, CDCl3): δ = 7.89-7.86 (m, 2H), 7.73 (dd, J = 5.0,
1.1 Hz, 1H), 7.65 (dd, J = 3.8, 1.1 Hz, 1H), 7.62-7.58 (m, 1H),
7.52-7.48 (m, 2H), 7.17 (dd, J = 4.9, 3.8 Hz, 1H); 13C NMR (100
MHz, CDCl3): δ = 188.2, 143.6, 138.1, 134.8, 134.2, 132.3,
129.2, 128.4, 127.9.
(4-Fluorophenyl)(phenyl)methanone (4c)[8p]: White solid, 194
mg (97 %); m.p.49.0-50.2 oC; Rf = 0.23 (EtOAc:Hexane = 1:50);
1H NMR (400 MHz, CDCl3): δ = 7.88-7.83 (m, 2H), 7.78-7.76 (m,
2H), 7.62-7.58 (m, 1H), 7.51-7.47 (m, 2H), 7.19-7.14 (m, 2H);
13C NMR (100 MHz, CDCl3): δ = 195.3, 165.4 (d, J = 252.5 Hz),
137.5, 133.8 (d, J = 3.0 Hz), 132.7 (d, J = 9.0 Hz), 132.5, 129.9,
128.3, 115.4 (d, J = 21.7 Hz).
1-Phenylethanone (4k)[8p]: Colorless oil; 91.3 mg (76 %); Rf =
0.53 (EtOAc:Hexane = 1:5); 1H NMR (400 MHz, CDCl3): δ =
7.93-7.91 (m, 2H), 7.54-7.49 (m, 1H), 7.43-7.39 (m, 2H), 2.55 (s,
3H); 13C NMR (100 MHz, CDCl3): δ = 197.8, 136.8, 132.8, 128.3,
128.0, 26.3.
(4-Methylphenyl)(phenyl)methanone (4d)[8p]: White solid, 157
mg (80 %); m.p. 62.1-62.9 oC; Rf = 0.20 (EtOAc:Hexane = 1:50);
1H NMR (400 MHz, CDCl3): δ = 7.78(d, J = 7.1 Hz, 2H), 7.73 (d,
J = 8.1 Hz, 2H), 7.57 (t, J = 7.4 Hz, 1H), 7.47 (t, J = 7.5 Hz, 2H),
7.28 (d, J = 8.0 Hz, 2H), 2.44 (s, 3H); 13C NMR (100 MHz,
CDCl3): δ = 196.5, 143.2, 137.9, 134.8, 132.1, 130.3, 129.9,
128.9, 128.2, 21.6.
1-Phenyl-1-propanone (4l)[21]: Colorless oil; 57.7 mg (43 %); Rf
1
= 0.25 (EtOAc: Hexane=1:50); H NMR (400 MHz, CDCl3): δ =
7.98-7.95 (m, 2H), 7.57-7.53 (m, 1H), 7.47-7.44 (m, 2H), 3.01 (q,
J = 7.2 Hz, 2H), 1.23 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): δ = 200.8, 136.9, 132.8, 128.5, 127.9, 31.7, 8.2.
(4-(1,1-Dimethylethyl)phenyl)(phenyl)methanone
(4e)[17]
:
Colorless oil, 219 mg (92 %); Rf = 0.15 (EtOAc:Hexane = 1:50);
1H NMR (400 MHz, CDCl3): δ = 7.82-7.76 (m, 4H), 7.58 (t, J =
7.4 Hz, 1H), 7.51-7.46 (m, 4H), 1.37 (s, 9H); 13C NMR (100 MHz,
CDCl3): δ = 196.4, 156.1, 137.8, 134.7, 132.1, 130.1, 129.9,
2-Methyl-1-phenylpropanone (4m)[22]: Colorless oil; 71.1 mg
(48 %); Rf = 0.55 (EtOAc: Hexane=1:5); 1H NMR (400 MHz,
CDCl3): δ = 7.97-7.95 (m, 2H), 7.57-7.53 (m, 1H), 7.49-7.45 (m,
2H), 3.56 (sept, J = 6.8 Hz, 1H), 1.22 (d, J = 6.8Hz, 6H); 13C
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201801124
European Journal of Organic Chemistry
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35.4, 19.2.
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1-Phenyl-1-butanone (4n)[23]: Colorless oil; 54.8 mg (37 %); Rf
= 0.40 (EtOAc:Hexane=1:20); 1H NMR (400 MHz, CDCl3): δ =
7.98-7.95 (m, 2H), 7.55 (t, J = 7.3 Hz, 1H), 7.46 (t, J = 7.5 Hz,
2H), 2.95 (t, J = 7.3 Hz, 2H), 1.78 (sext, J = 7.4 Hz, 2H), 1.00(t, J
= 7.4 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ = 200.4, 137.1,
132.8, 128.5, 128.0, 40.5, 17.7, 13.9.
1-(4-Benzoylphenyl)ethanone (4o)[24]: White solid, 103 mg
o
1
(46 %); m.p. 82.6-83.2 C; Rf = 0.33 (EtOAc:Hexane = 1:5); H
NMR (400 MHz, CDCl3): δ = 8.06 (d, J = 8.1 Hz, 2H), 7.87 (d, J
= 8.0 Hz, 2H), 7.81 (d, J = 8.2 Hz, 2H), 7.63 (t, J = 7.4 Hz, 1H),
7.51 (t, J = 7.7 Hz, 2H), 2.68 (s, 3H); 13C NMR (100 MHz, CDCl3):
δ = 197.5, 196.0, 141.3, 139.5, 136.9, 133.0, 130.1, 130.0, 128.5,
128.1, 26.9.
(2-Naphthalenyl)(phenyl)methanone (4p)[25]: White solid, 223
o
mg (96 %); m.p. 82.4-83.4 C; Rf = 0.63 (EtOAc:Hexane = 1:5);
1H NMR (400 MHz, CDCl3): δ = 8.28 (s, 1H), 7.95-7.86 (m, 6H),
7.65-7.50 (m, 5H); 13C NMR (100 MHz, CDCl3): δ = 196.7, 137.8,
135.2, 134.8, 132.3, 132.2, 131.8, 130.0, 129.4, 128.29, 128.29,
128.25, 127.8, 126.7, 125.7.
(4-Phenylphenyl)(phenyl)methanone (4q)[26]: White solid, 212
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1
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This research was supported by the Basic Science Research
Program administered through the National Research
Foundation of Korea (NRF), funded by the Ministry of Education
(2015R1D1A1A09058536) and by the Korean Ministry of
Education through the BK21-Plus Project of the Hanyang
University Graduate Program.
Keywords: N,N-Bis(methanesulfonyl)amides • Carbonylative
coupling reactions • C-N bond cleavage • Distorted amide •
Suzuki cross coupling
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10.1002/ejoc.201801124
European Journal of Organic Chemistry
FULL PAPER
Entry for the Table of Contents
FULL PAPER
Key Topic*
O
O
Minkyung Lim, Hyeji Kim, Jaeyoung
Ban, Junghan Son, Jae Kyun Lee, Sun-
Joon Min,* Sang Uck Lee* and Hakjune
Rhee*
O
2Cl2 1 mol%, K2CO
Toluene
S
Pd(PPh3)
3
R
N
S
+
Ar
B(OH)2
O
R
Ar
O
O
65 o 20 min-12 h
C,
24
to
examples up
99%
R=
heteroaromatic
Aryl, alkyl,
yield
Page No. – Page No.
N,N
-Bis(methanesulfonyl)amide
Palladium-catalyzed carbonylative coupling reaction of various N,N-
bis(methanesulfonyl)amides as a new coupling partner with arylboronic acids was
achieved without using additives.
Palladium-Catalyzed Carbonylative
Coupling Reactions of N,N-
Bis(methanesulfonyl)amides via C-N
Bond Cleavage
*N,N-Bis(methanesulfonyl)amide, Carbonylative Coupling Reaction.
This article is protected by copyright. All rights reserved.