Sulfonylation of Benzylic C?H Bonds through the Reaction of Aryl(o-tolyl)methanones with Sulfonyl Hydrazides or Sulfonyl Chlorides

Article abstract of DOI:10.1002/asia.201800591

A sulfonylation of benzylic C?H bonds of aryl(o-tolyl)methanones with arylsulfonyl hydrazides or arylsulfonyl chlorides has been developed. Arylsulfonyl hydrazides and arylsulfonyl chlorides were employed as sulfonylating reagents respectively to complete this transformation. During the reaction, enols were generated in situ from aryl(o-tolyl)methanones under UV irradiation, and subsequently reacted with sulfonyl radicals to provide a range of aryl(2-(arylsulfonylmethyl)aryl)methanones.

Full text of DOI:10.1002/asia.201800591

CHEMISTRY
AN ASIAN JOURNAL
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Accepted Article
Title: Sulfonylation of Benzylic C-H Bond through a Reaction of Aryl(o-
tolyl)methanones with Sulfonyl Hydrazides or Sulfonyl Chlorides
Authors: Xinxing Gong, Jiahao Chen, Xiaofang Li, Wenlin Xie, and Jie
Wu
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Chemistry - An Asian Journal
10.1002/asia.201800591
FULL PAPER
Sulfonylation of Benzylic C-H Bond through a Reaction of Aryl(o-
tolyl)methanones with Sulfonyl Hydrazides or Sulfonyl Chlorides
[
a]
[a]
[b]
[b]
[a,c]
Xinxing Gong, Jiahao Chen, Xiaofang Li, Wenlin Xie,* and Jie Wu*
Dedication ((optional))
Abstract:
A
benzylic C-H bond sulfonylation of aryl(o-
used in photochemistry as photosensers for their ability in
6
e,11
tolyl)methanones with arylsulfonyl hydrazides or arylsulfonyl
chlorides is reported. Both arylsulfonyl hydrazides and arylsulfonyl
chlorides are employed as sulfonylation reagents to complete this
transformation under different conditions. During the reaction
process, enols are generated in situ from aryl(o-tolyl)methanones
under ultraviolet irradiation, which react with sulfonyl radicals
providing a range of aryl(2-(arylsulfonylmethyl)aryl)methanones.
absorbing photon under illumination in certain region.
Another straightforward protocol was employing those small
1
2
molecules as photocatalysts as well as reactants. Previous
reports revealed that the intramolecular single electron transfer
(SET) or hydrogen atom transfer (HAT) process would take
place when phenylketones were used under ultraviolet
irradiation. For instance, carboxylation of benzylic C-H bond was
realized from the reaction of o-alkylphenylketones and carbon
1
2f
dioxide (Scheme 1, eq 1). The photoinduced enols were the
key intermediate in this transformation. The enols generated
from ketones could be trapped by dienophiles via Diels–Alder
reaction, and the enantioselective reaction could be achieved in
Introduction
Sulfones and related compounds, which are widely found in a
broad scope of bioactive natural products, agrochemical
compounds, and pharmaceuticals, are of great significance in
12e
the presence of chiral amine catalyst (Scheme 1, eq 2).
Recently, a photoinduced trifluoromethylation via phenylenol
was also disclosed. The mechanistic studies indicated that enols
were the key intermediates, and the transformation did not go
1
organic chemistry and drug discovery. Additionally, sulfonyl unit
2
is usually used as a versatile motif in organic synthesis. Thus,
12a
through a radical pathway (Scheme 1, eq 3). In the past few
many efforts have been given for the construction of sulfone
compounds. Traditionally, sulfone derivatives were synthesized
years, we have focused on the insertion of sulfur dioxide through
13
radical process.
The combination of aryldiazonium
3
from nucleophilic substitution of carbon electrophiles with thiols
2 2
tetrafluoroborates and sulfur dioxide surrogate of DABCO·(SO )
4
or disulfides and the subsequent oxidation. However, its
14
could provide arylsulfonyl radical efficiently. We envisioned
that sulfonylation of benzylic C-H bond might be feasible from
aryldiazonium tetrafluoroborates and sulfur dioxide. Thus, we
application was restricted due to the unpleasant smell of thiols
and incompatibility of sensitive functional groups under oxidative
conditions. Recently, sulfonylation reactions were conveniently
achieved from a range of sulfonyl precursors, such as sulfonyl
initiated
a program for the method development with the
sulfonylation of benzylic C-H bond via a radical process.
5
6
7
hydrazides,
sulfonyl chlorides,
sulfinic acids,
sodium
8
9
sulfonates, and sulfur dioxide surrogates. Sulfonyl radicals
could be generated from these precursors in the presence of
metal catalysis or under metal-free conditions. This strategy is
proven to be an efficient method for the generation of diverse
sulfones or sulfonyl compounds.
previous reports
O
O
R
H
UV light (365 nm)
DMSO, rt, 2 h
R
+
+
CO2
(1)
(2)
COOH
Photochemistry has been utilized as a powerful tool to realize
C-H bond functionalization with good chemoselectivity and
O
HO Ar
O
O
1
0
regioselectivity for decades. Aldehydes and ketones are widely
catalyst
Ar
R2
N
R2
N
hν
R1
O
R1
O
[
[
a]
b]
X. Gong, J. Chen, Prof. Dr. J. Wu
Room A7018, Department of Chemistry
Fudan University
O
O
2
005 Songhu Road, Shanghai 200438, China
UV light (365 nm)
DMSO, rt, 1 h
R
H
R
(3)
E-mail: jie_wu@fudan.edu.cn
+
Togni-CF3
CF3
Dr. X. Li, Prof. Dr. W. Xie
School of Chemistry and Chemical Engineering
Hunan University of Science and Technology
Xiangtan 411201, China
Scheme 1. Examples for the benzylic C-H bond functionalization
E-mail: xwl2000zsu@163.com
[
c]
Prof. Dr. J. Wu
Results and Discussion
State Key Laboratory of Organometallic Chemistry
Shanghai Institute of Organic Chemistry, Chinese Academy of
Sciences
At the beginning, reaction of phenyl(o-tolyl)methanone 1a with
3
45 Linglin Road, Shanghai 200032, China
phenyldiazonium tetrafluoroborate and sulfur dioxide surrogate
of DABCO·(SO
2 2
) was performed under different conditions
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
including palladium catalysis and copper catalysis.
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Chemistry - An Asian Journal
10.1002/asia.201800591
FULL PAPER
Unfortunately, no positive results were obtained. We therefore
shifted our focus to arylsulfonyl hydrazides or arylsulfonyl
chlorides, since arylsulfonyl radcials could be generated from
arylsulfonyl hydrazides or arylsulfonyl chlorides as well. We
commenced on our studies from the reaction of phenyl(o-
tolyl)methanone 1a and 4-methylbenzenesulfonohydrazide 2a in
-ꢀ
KIꢀ
KIꢀ
KIꢀ
KIꢀ
KIꢀ
KIꢀ
KIꢀ
KIꢀ
1,4-dioxaneꢀ
1,4-dioxaneꢀ
1,4-dioxaneꢀ
1,4-dioxaneꢀ
1,4-dioxaneꢀ
1,4-dioxaneꢀ
1,4-dioxaneꢀ
1,4-dioxaneꢀ
ndꢀ
traceꢀ
traceꢀ
traceꢀ
ndꢀ
1
1
mCPBAꢀ
Ph(COO)2ꢀ
12
1
3
2 2 8
K S O ꢀ
14
1
,4-dioxane under ultraviolet irradiation (Table 1). Initially, a
DTBPꢀ
TBHPꢀ
TBHPꢀ
TBHPꢀ
1
5
combination of iodide and TBHP mediated system was
employed to convert sulfonohydrazide into sulfonyl radical.
Several iodides and iodine were examined, and the desired
sulfonylated product 3a could be obtained in 28% yield in the
presence of NaI (Table 1, entry 1). A trace amount of product
was observed when TBAI or iodine was used in the reaction
[b]
50ꢀ
1
6
[
c]
60ꢀ
17
[d]
ndꢀ
1
8
[
a] a
(
Table 1, entries 2 and 3). The yield increased to 45% when
Reaction conditions: phenyl(o-tolyl)methanone 1a (0.2 mmol), 4-
potassium iodide was employed as a replacement (Table 1,
entry 4). It was quite interesting that the corresponding product
could be obtained in 20% yield with TBHP alone (Table 1, entry
methylbenzenesulfonohydrazide 2a (0.4 mmol), additive (10 mol %),
oxidant (0.4 mmol), solvent (4.0 mL), N
2
, UV, 8h, isolated yield based on
[
b]
[c]
phenyl(o-tolyl)methanone 1a.
In the presence of KI (0.5 equiv). In the
[
d]
5
), probably due to the promotion of transformation from
presence of KI (0.5 equiv) and TBHP (3.0 equiv). In the dark.
sulfonylhydrazide by the free tert-butoxy radical. Other solvents,
such as 1,2-dichloroethane (DCE), DMA, MeCN, THF, and
DMSO were screened subsequently. However, no better results
were obtained (Table 1, entries 6-10). No reaction occurred
without the addition of TBHP. (Table 1, entry 11) Further
investigation revealed that TBHP was the best choice for this
transformation, and reaction using other oxidants displayed
inferior results (Table 1, entries 12-15). It was found that the
amount of KI and TBHP had influence on the final outcome
With the optimized reaction conditions in hand, we then
explored the substrate scope of this transformation (Scheme 2).
Other arylsulfonylhydrazides were firstly examined in the
reaction of phenyl(o-tolyl)methanone 1a. It was found that this
sulfonylative process had good tolerance of different
substitutions on the aromatic ring. Similar results were obtained
when substrates with methoxy, tert-butyl, methyl, chloro,
trifluoromethyl, and trifluoromethoxy groups were employed
under the conditions. Further investigation of reaction scope was
explored by using different aryl(o-tolyl)methanones with 4-
methylbenzenesulfonohydrazide 2a. All reactions worked well to
provide the corresponding products 3i-3o in moderate yields.
Functional groups such as cyano group were compatible in the
transformation. Good regioselectivity was observed when (2,4-
dimethylphenyl)(phenyl)methanone was used as the substrate in
the reaction of 4-methylbenzenesulfonohydrazide 2a, leading to
compound 3p in 60% yield. Other substrates such as alkyl(o-
tolyl)ketones and alkylsulfonyl hydrazides were also examined.
However, only a trace amount of product was obtained when
alkyl(o-tolyl)ketones or alkylsulfonyl hydrazides were employed
under the standard conditions.
(
Table 1, entries 16 and 17). The desired product 3a would be
afforded in 60% yield when 0.5 equivalent of KI and 3.0
equivalent of TBHP were utilized. No reaction occurred in the
dark.
Table 1. Initial studies for the reaction of phenyl(o-tolyl)methanone 1a and 4-
[
a]
methylbenzenesulfonohydrazide 2a.
O
O
O
O
oxidant, additive
UV, solvent
Ph
Ph
Ts
+
S
p-Tol
NHNH2
1
a
2a
3a
Entry
Oxidant
Additive
Solvent
Yield (%)
TBHPꢀ
NaIꢀ
1,4-dioxaneꢀ
28ꢀ
1
2
3
4
5
6
7
8
9
TBHPꢀ
TBHPꢀ
TBHPꢀ
TBHPꢀ
TBHPꢀ
TBHPꢀ
TBHPꢀ
TBHPꢀ
TBHPꢀ
I
2
ꢀ
1,4-dioxaneꢀ
1,4-dioxaneꢀ
1,4-dioxaneꢀ
1,4-dioxaneꢀ
DCEꢀ
traceꢀ
traceꢀꢀ
45ꢀ
TBAIꢀ
KIꢀ
-ꢀ
20ꢀ
KIꢀ
KIꢀ
KIꢀ
KIꢀ
KIꢀ
traceꢀ
ndꢀ
DMAꢀ
THFꢀ
30ꢀ
MeCNꢀ
32ꢀ
DMSOꢀ
traceꢀ
1
0
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Chemistry - An Asian Journal
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FULL PAPER
tolyl)methanone 1a with 4-methylbenzenesulfonohydrazide 2a or
4
-methylbenzenesulfonyl chloride 4a under the standard
conditions, only a trace amount of desired product 3a was
produced when 3.0 equiv of TEMPO was added as a radical
scavenger (Scheme 4, eq 1). Additionally, compound 5 with a
vinyl group which could further capture the benzyl radical
generated in situ was utilized to react with 4-
methylbenzenesulfonohydrazide 2a. However, we did not
observe the formation of the corresponding sulfonylative product
(
Scheme 4, eq 2). Additionally, a trace amount of product 3a
was obtained when 1,2-diphenylethene was added into the
reaction system. The corresponding product 6 with the capture
of sulfonyl radical was formed in 23% yield (Scheme 4, eq 3).
Furthermore, ketones with ortho-hydroxy group or ortho-amino
group
were
employed
in
the
reaction
of
4-
methylbenzenesulfonohydrazide 2a. However, it failed to afford
Scheme 2. Scope exploration for the reaction of aryl(o-tolyl)methanones 1
with arylsulfonylhydrazides 2.
the desired products (Scheme 4, eq 4).
O
O
O
2a
O
S
p-Tol
or
NHNH
2
standard conditions
TEMPO (3.0 equiv)
Ph
Ph
Ts
Moreover, in addition to sulfonohydrazides, arylsulfonyl
chlorides were also used in the sulfonylation of benzylic C-H
bond. The result is shown in Scheme 3. It is known that
arylsulfonyl radicals could be generated from the homolysis of
arylsulfonyl chlorides via a SET process with excited ketones
+
(1)
O
O
S
4a
p-Tol
Cl
trace
1a
O
O
O
O
standard conditions
6
e
+
S
(2)
(3)
under ultraviolet irradiation in 1,4-dioxane. Thus, the reaction
was conducted by using phenyl(o-tolyl)methanone 1a and 4-
methylbenzenesulfonyl chloride 4a under ultraviolet irradiation. A
series of additives and solvents were examined (data not shown
in Scheme 3), and the results revealed that the desired product
p-Tol
NHNH
2
Ts
5
2a
nd
O
standard
conditions
3
a: trace
O
O
Ph
S
+
+
+
p-Tol
NHNH
2
Ph
Ph
Ts
3
a could be obtained in 55% yield in the presence of cessium
Ph
Ph
2
a
carbonate in 1,4-dioxane. This reaction condition was then
extended to other aryl(o-tolyl)methanones with arylsulfonyl
chlorides. As expected, the benzylic C-H bond sulfonylation
proceeded well, providing the corresponding products 3 in
similar yields.
1a
6
: 23%
O
O
O
O
Ph
standard conditions
S
Ph
Ts
+
p-Tol
NHNH2
(4)
XH
X
2
a
X = O, N
O
O
R2
O
O Cs CO3 (2.0 equiv)
R2
Scheme 4. Control experiments
2
R1
+
S
R1
H
Ar
Cl
SO2Ar
UV, N2
5,12
Based on the above results and previous reports,
a
1
4
1,4-dioxane
3
possible mechanism involving radical pathway was proposed, as
shown in Scheme 5. Initially, arylsulfonylhydrazide would be
converted into arylsulfonyl radical induced by KI and
O
O
O
Ph
Ts
Ph
Ph
SO C H p-Cl
5
c,5d,5h,5i
SO C H p-OMe
TBHP.
Alternatively, homolysis of arylsulfonyl chloride
2
6
4
2 6 4
would occur in the presence of excited ketone under ultraviolet
irradiation, leading to arylsulfonyl radical. In the meantime,
excited stage of ketone A could be generated in situ from aryl(o-
tolyl)methanone 1. After intramolecular 1,5-hydrogen transfer via
3
a, 55%
3c, 60%
3f, 55%
O
O
O
C H p-OMe
C H p-F
Ph
Ts
6
4
6 4
Ts
Ts
triple-state oxygen atom and
a fast intersystem crossing
1
2a
3
j, 57%
3m, 53%
3p, 56%
(ISC), enol B would be generated. Subsequently, arylsulfonyl
radical would be trapped by enol B, giving rise to radical C. The
corresponding sulfonated product 3 would be produced by
further aromatization and oxidation.
Scheme 3. Scope exploration for the reaction of aryl(o-tolyl)methanones 1
with arylsulfonyl chlorides 4.
To gain more insights into the mechanism, some control
experiments were carried out. For the reaction of phenyl(o-
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FULL PAPER
1
O
OH
R2
O
S
OH
R2
SO Ar
Phenyl(2-(tosylmethyl)phenyl)methanone (3a).
H NMR (400
MHz, CDCl ): δ 7.78 – 7.29 (m, 11H), 7.13 (s, 2H), 4.84 (s, 2H), 2.30
(s, 3H). C NMR (100 MHz, CDCl ): δ 197.3, 144.6, 139.1, 137.2,
135.6, 133. 6, 132.9, 131.0, 130.7, 130.5, 129.7, 128.3, 128.0, 127.8,
3
R2 UV
Ar
O
C
13
R1
R1
R
1
3
2
1
B
+
+
5
8.0, 21.6. HRMS (ESI) calcd for C21
H
19
O
3
S : 351.1049 (M+H ),
hν
R2
ISC
found: 351.1049.
aromatization
R2
*
1,5-H
1
OH
Phenyl(2-((phenylsulfonyl)methyl)phenyl)methanone (3b).
NMR (400 MHz, CDCl ): δ 7.73 – 7.64 (m, 3H), 7.57 (dd, J = 10.5,
4.3 Hz, 1H), 7.53 – 7.35 (m, 9H), 4.85 (s, 2H). C NMR (100 MHz,
CDCl ): δ 197.6, 139.5, 138.8, 137.6, 133.9, 133.2, 131.2, 130.8,
30.7, 129.3, 129.2, 128.6, 128.5, 127.7, 58.3. HRMS (ESI) calcd for
H
transfer
O
OH
R1
R1
R2
3
A
R1
13
SO Ar
2
3
KI, tBuOOH
-N2
O
S
O
O
1
S
+
+
oxidation
- H+
Ar
NHNH2
20 17 3
C H O S : 337.0893 (M+H ), found: 337.0885.
Ar
O
2
hν - Cl
O
(
2-(((4-
Methoxyphenyl)sulfonyl)methyl)phenyl)(phenyl)methanone (3c).
NMR (400 MHz, CDCl ): δ 7.63 (d, J = 7.8 Hz, 2H), 7.58 – 7.29 (m,
1
R2
3
H
O
O
R1
4
S
SO Ar
2
3
Ar
Cl
1
3
9
H), 6.77 (d, J = 8.7 Hz, 2H), 4.84 (s, 2H), 3.75 (s, 3H). C NMR
(
1
C
100 MHz, CDCl ): δ 197.5, 163.9, 139.2, 137.4, 133.8, 133.2, 131.2,
3
Scheme 5.
A plausible mechanism for the sulfonylation of aryl(o-
30.7, 130.1, 128.3, 128.0, 114.4, 58.3, 55.8. HRMS (ESI) calcd for
tolyl)methanones with sulfonyl hydrazides or sulfonyl chlorides
+
+
21
19 4
H O S : 367.0999 (M+H ), found: 367.0985.
(
2-(((4-(tert-
Butyl)phenyl)sulfonyl)methyl)phenyl)(phenyl)methanone (3d).
NMR (400 MHz, CDCl ): δ 7.75 (d, J = 7.1 Hz, 2H), 7.63 (d, J = 8.5
Hz, 2H), 7.57 (t, J = 7.4 Hz, 1H), 7.44 (dd, J = 8.0, 6.5 Hz, 6H), 7.39
1
Conclusions
H
3
In conclusion, we have disclosed
a benzylic C-H bond
1
3
(
dd, J = 4.5, 1.4 Hz, 2H), 4.84 (s, 2H), 1.28 (s, 9H). C NMR (100
MHz, CDCl ): δ 197.6, 157.6, 139.4, 137.6, 135.9, 133.6, 132.9,
31.0, 130.9, 130.5, 128.2, 128.1, 127.9, 127.6, 126.1, 58.1, 31.0.
HRMS (ESI) calcd for
393.1508.
sulfonylation of aryl(o-tolyl)methanones with arylsulfonyl
hydrazides or arylsulfonyl chlorides. Both arylsulfonyl hydrazides
and arylsulfonyl chlorides are employed as sulfonylation
reagents to complete this transformation under different
conditions. During the reaction process, enols are generated in
situ from aryl(o-tolyl)methanones under ultraviolet irradiation,
which react with arylsulfonyl radicals providing a range of aryl(2-
3
1
+
+
24 25 3
C H O S : 393.1519 (M+H ), found:
1
Phenyl(2-((o-tolylsulfonyl)methyl)phenyl)methanone (3e).
NMR (400 MHz, CDCl ): δ 7.70 – 7.63 (m, 3H), 7.55 (t, J = 7.4 Hz,
1H), 7.51 – 7.46 (m, 2H), 7.42 – 7.26 (m, 5H), 7.16 (t, J = 7.6 Hz,
H
3
(
arylsulfonylmethyl)aryl)methanones. This method provides an
1
3
1
(
1
5
H), 7.07 (d, J = 7.6 Hz, 1H), 4.85 (s, 2H), 2.51 (s, 3H). C NMR
100 MHz, CDCl ): δ 197.2, 139.3, 138.6, 137.1, 136.5, 133.8, 133.7,
33.0, 132.6, 130.9, 130.5, 130.5, 130.4, 128.1, 127.8, 127.4, 126.3,
alternative strategy to fulfill the sulfonylation of benzylic C-H
bond.
3
+
+
19 3
7.1, 20.0. HRMS (ESI) calcd for C21H O S : 351.1049 (M+H ),
found: 351.1058.
Experimental Section
(
21-(((4-Chlorophenyl)sulfonyl)methyl)phenyl)(phenyl)methanone
(3f). H NMR (400 MHz, CDCl ): δ 7.63 – 7.55 (m, 5H), 7.52 (d, J =
3.1 Hz, 2H), 7.40 (ddd, J = 11.2, 9.6, 5.9 Hz, 4H), 7.29 (d, J = 8.6 Hz,
General procedure for the reaction of aryl(o-tolyl)methanones 1 with
arylsulfonylhydrazides 2: Aryl(o-tolyl)methanone 1 (0.20 mmol) in
3
1
3
1
,4-dioxane (2.0 mL) was added to
a
mixture of arylsulfonyl
atmosphere. Then
2H), 4.86 (s, 2H). C NMR (100 MHz, CDCl
3
): δ 197.1, 140.5, 138.9,
hydrazide 2 (0.60 mmol) and KI (0.10 mmol) at N
2
137.0, 136.9, 133.5, 133.2, 131.1, 130.8, 130.4, 129.8, 129.3, 128.2,
+
TBHP (0.60 mmol) in 1,4-dioxane (2.0 mL) was added to the
reaction system. The mixture was stirred under ultraviolet radiation
at room temperature. After 8 hours, the solvent was evaporated
under reduced pressure. The residue was purified directly by flash
128.0, 127.4, 57.9. HRMS (ESI) calcd for C20
(M+H ), found: 371.0505.
H
16ClO
3
S : 371.0503
+
Phenyl(2-(((4-
1
column
chromatography
(n-hexane/EA=4:1)
to
give
the
(
trifluoromethyl)phenyl)sulfonyl)methyl)phenyl)methanone (3g).
H
corresponding product 3.
NMR (400 MHz, CDCl
3
): δ 7.81 (d, J = 8.2 Hz, 2H), 7.66 – 7.61 (m,
1
3
4
H), 7.58 – 7.52 (m, 3H), 7.44 – 7.39 (m, 4H), 4.91 (s, 2H). C NMR
2
General procedure for the reaction of aryl(o-tolyl)methanones 1 with
arylsulfonyl chlorides 4: Aryl(o-tolyl)methanone 1 (0.20 mmol) in 1,4-
dioxane (4.0 mL) was added to a mixture of arylsulfonyl chloride 4
3
(100 MHz, CDCl ): δ 197.2, 142.1, 138.8, 137.2, 133.4 (d, JCF= 37.2
Hz), , 131.2, 131.0, 130.3, 129.0, 128.2, 127.0, 126.1, 126.1, 57.9.
+
+
HRMS (ESI) calcd for
405.0760.
C
21
H
16
F
3
O
3
S : 405.0767 (M+H ), found:
(
2 3 2
0.40 mmol) and Cs CO (0.40 mmol) at N atmosphere. The mixture
was stirred under ultraviolet radiation at room temperature. After 8
hours, the solvent was evaporated under reduced pressure. The
residue was purified directly by flash column chromatography (n-
hexane/EA=4:1) to give the corresponding product 3.
Phenyl(2-(((4-
1
(
trifluoromethoxy)phenyl)sulfonyl)methyl)phenyl)methanone (3h).
H
3
NMR (400 MHz, CDCl ): δ 7.76 (d, J = 8.8 Hz, 2H), 7.70 (d, J = 7.2
Hz, 2H), 7.62 (t, J = 7.4 Hz, 1H), 7.56 – 7.52 (m, 2H), 7.46 (dd, J =
1
3
1
4.8, 7.0 Hz, 4H), 7.22 (d, J = 8.3 Hz, 2H), 4.91 (s, 2H). C NMR
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1
+
(
100 MHz, CDCl
3
): δ 197.5, 153.2, 138.1 (d, JCF = 255.0 Hz), 137.5,
118.27, 116.23, 58.17, 21.90. HRMS (ESI) calcd for C22
376.1002 (M+H ), found: 376.1007.
H
18NO
3
S :
+
1
33.7, 133.3, 131.0, 130.8, 130.7, 130.6, 128.4, 127.4, 120.8 (d,
3
1
J
CF= 10.4 Hz), 120.3 (d,
J
CF= 258.0 Hz), 58.3. HRMS (ESI) calcd
S : 421.0716 (M+H ), found: 421.0708.
+
+
1
for C21
H
16
F
3
O
4
(
4-Methyl-2-(tosylmethyl)phenyl)(p-tolyl)methanone
(3p).
H
3
NMR (400 MHz, CDCl ): δ 7.64 (d, J = 7.1 Hz, 2H), 7.57 (d, J = 8.3
1
p-Tolyl(2-(tosylmethyl)phenyl)methanone (3i). H NMR (400 MHz,
CDCl
Hz, 2H), 7.42 (t, J = 7.7 Hz, 2H), 7.34 (s, 1H), 7.30 – 7.25 (m, 1H),
7.18 (dd, J = 16.8, 7.9 Hz, 3H), 4.87 (s, 2H), 2.43 (s, 3H), 2.31 (s,
3
): δ 7.50 (ddd, J = 9.5, 6.0, 4.9 Hz, 6H), 7.39 – 7.33 (m, 2H),
1
3
7
(
1
1
.20 (d, J = 8.1 Hz, 2H), 7.11 (d, J = 8.1 Hz, 2H), 4.81 (s, 2H), 2.42
3
3H). C NMR (100 MHz, CDCl ): δ 197.56, 144.74, 141.86, 137.82,
1
3
s, 3H), 2.28 (s, 3H). C NMR (100 MHz, CDCl
3
): δ 197.1, 144.8,
44.1, 139.6, 135.8, 134.8, 131.0, 130.9, 129.9, 129.8, 129.1, 129.0,
28.6, 128.5, 127.9, 58.2+, 21.8, 21.7. HRMS (ESI) calcd for
136.42, 135.91, 134.69, 134.60, 130.74, 129.88, 129.82, 128.62,
128.53, 128.24, 128.05, 58.16, 21.75, 21.65. HRMS (ESI) calcd for
+
+
22 21 3
C H O S : 365.1206 (M+H ), found: 365.1206.
+
22 21 3
C H O S : 365.1206 (M+H ), found: 365.1206.
1
(
4-Fluoro-2-(tosylmethyl)phenyl)(phenyl)methanone (3q).
NMR (400 MHz, CDCl ): δ 7.63 – 7.53 (m, 4H), 7.45 – 7.34 (m, 3H),
7.27 – 7.23 (m, 1H), 7.16 (d, J = 8.0 Hz, 2H), 7.07 (td, J = 8.4, 2.5
H
1
(
4-Methoxyphenyl)(2-(tosylmethyl)phenyl)methanone (3j).
NMR (400 MHz, CDCl ): δ 7.64 (d, J = 8.9 Hz, 2H), 7.53 – 7.44 (m,
H), 7.36 (ddd, J = 18.9, 10.2, 4.8 Hz, 2H), 7.12 (d, J = 8.0 Hz, 2H),
.88 (d, J = 8.9 Hz, 2H), 4.80 (s, 2H), 3.88 (s, 3H), 2.30 (s, 3H).
): δ 196.01, 163.77, 144.76, 139.84, 135.79,
33.63, 133.24, 133.14, 130.20, 129.88, 129.82, 128.58, 128.47,
H
3
3
1
3
4
6
Hz, 1H), 4.85 (s, 2H), 2.32 (s, 3H). C NMR (100 MHz, CDCl
3
): δ
1
3
1
3
C
196.3, 163.4 (d, JCF = 253.7 Hz), 144.7, 137.3, 135.4 (d, JCF = 14.9
Hz), 133.1, 133.0, 131.1 (d, JCF = 8.7 Hz), 130.4, 129.8, 128.3,
3
NMR (100 MHz, CDCl
3
2
2
1
1
C
128.15, 120.7 (d, JCF = 22.7 Hz), 114.8 (d, JCF = 21.2 Hz), 57.7,
+ +
27.74, 113.57, 58.25, 55.80, 21.83. HRMS (ESI) calcd for
21.6. HRMS (ESI) calcd for C21
369.0959.
3
H18FO S : 369.0955 (M+H ), found:
+
+
22
21 4
H O S : 381.1155 (M+H ), found: 381.1155.
1
13a
1
(
4-(tert-Butyl)phenyl)(2-(tosylmethyl)phenyl)methanone (3k).
NMR (400 MHz, CDCl ): δ 7.60 (d, J = 8.4 Hz, 2H), 7.53 (d, J = 8.2
Hz, 2H), 7.48 (s, 2H), 7.44 (d, J = 8.4 Hz, 2H), 7.37 (d, J = 2.5 Hz,
H
(2-Tosylethene-1,1-diyl)dibenzene (6).
CDCl ) δ 7.47 (d, J = 8.2 Hz, 2H), 7.36 (m, 2H), 7.30 (t, J = 7.4 Hz,
4H), 7.20 (d, J = 7.4 Hz, 2H), 7.15 (d, J = 8.2 Hz, 2H), 7.10 (d, J =
H NMR (400 MHz,
3
3
1
3
2
H), 7.14 (d, J = 8.1 Hz, 2H), 4.86 (s, 2H), 2.31 (s, 3H), 1.37 (s, 9H).
3
7.1 Hz, 2H), 6.99 (s, 1H), 2.38 (s, 3H). C NMR (100 MHz, CDCl ):
1
3
C NMR (100 MHz, CDCl
3
): δ 197.2, 156.9, 144.8, 139.5, 135.8,
δ 154.9, 144.0, 139.4, 138.8, 135.8, 130.5, 123.0, 129.6, 129.2,
1
1
4
34.8, 133.8, 131.0, 130.8, 129.9, 129.8, 128.6, 128.5, 128.0, 125.3,
128.8, 128.4, 128.0, 21.8.
+
25.2, 58.2, 35.4, 31.3, 21.8. HRMS (ESI) calcd for C25
H
27
O
3
S :
+
07.1675 (M+H ), found: 407.1668.
1
(
4-Chlorophenyl)(o-tolyl)methanone (3l).
H NMR (400 MHz,
CDCl
3
): δ 7.58 (d, J = 8.5 Hz, 2H), 7.50 – 7.31 (m, 7H), 7.27 (d, J =
13
Acknowledgements
7
.6 Hz, 1H), 7.10 (d, J = 8.1 Hz, 2H), 4.77 (s, 2H), 2.27 (s, 3H). C
3
NMR (100 MHz, CDCl ): δ 196.3, 145.0, 139.7, 139.0, 135.8, 132.3,
1
2
3
32.2, 130.0, 129.9, 128.7, 128.6, 128.6, 128.5, 127.9, 58.1, 21.9,
Financial support from National Natural Science Foundation of
+
+
1.8. HRMS (ESI) calcd for C21
85.0667.
H
18ClO
3
S : 385.0660 (M+H ), found:
China
(
Nos. 21672037 and 21532001
)
is gratefully
acknowledged. We thank Prof. Tianning Diao (Department of
Chemistry, The New York University) for English review.
1
(
4-Fluorophenyl)(2-(tosylmethyl)phenyl)methanone
NMR (400 MHz, CDCl ): δ 7.77 – 7.67 (m, 2H), 7.53 (d, J = 8.2 Hz,
H), 7.49 – 7.31 (m, 4H), 7.15 (d, J = 8.1 Hz, 2H), 7.09 (t, J = 8.6 Hz,
(3m).
H
3
Keywords: arylsulfonyl hydrazide • arylsulfonyl chloride • aryl(o-
tolyl)methanone • benzylic C-H bond sulfonylation • ultraviolet
irradiation
2
2
1
1
=
1
3
3
H), 4.81 (s, 2H), 2.32 (s, 3H). C NMR (100 MHz, CDCl ): δ 196.0,
1
65.9 (d, JCF = 254.0 Hz), 144.9, 139.3, 135.9, 133.9, 133.6, 133.5,
3
33.4, 131.2, 130.6, 130.0, 130.0, 128.6, 128.5, 127.8, 115.6 (d, JCF
3
8.0 Hz), 115.4 (d,
JCF = 7.2 Hz). 58.2, 21.8, 21.8. HRMS (ESI)
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+
3
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(
2-1(Tosylmethyl)phenyl)(4-(trifluoromethyl)phenyl)methanone
3n). H NMR (400 MHz, CDCl ): δ 7.82 (d, J = 8.1 Hz, 2H), 7.69 (d,
J = 8.3 Hz, 2H), 7.58 – 7.47 (m, 3H), 7.41 (dd, J = 13.9, 7.2 Hz, 2H),
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(
3
7
1
3
1
(
3
s, 3H). C NMR (100 MHz, CDCl ): δ 196.6, 145.0, 137.3 (d, JCF =
2
1
C
88.2 Hz), 135.8, 134.4, 134.1, 131.7, 131.0, 130.0, 129.9, 128.6,
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+
+
22
H
18
F
3
O
3
S : 419.0923 (M+H ), found: 419.0911.
1
4
-(2-(Tosylmethyl)benzoyl)benzonitrile (3o). H NMR (400 MHz,
CDCl
3
): δ 7.86 (d, J = 8.2 Hz, 2H), 7.75 (d, J = 8.2 Hz, 2H), 7.59 –
7
7
.50 (m, 3H), 7.41 (dd, J = 17.5, 7.6 Hz, 2H), 7.32 (d, J = 7.4 Hz, 1H),
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.23 (d, J = 8.0 Hz, 2H), 4.83 (s, 2H), 2.38 (s, 3H). C NMR (100
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32.14, 131.85, 131.10, 130.07, 129.98, 128.51, 128.39, 127.91,
MHz, CDCl
1
3
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Chemistry - An Asian Journal
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Chemistry - An Asian Journal
10.1002/asia.201800591
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Xinxing Gong, Jiahao Chen, Xiaofang Li,
Wenlin Xie,* and Jie Wu*
O
O
R2
O
O
X
hν
R2
R1
+
R1
S
H
Ar
SO Ar
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2
X = NHNH or Cl
2
Sulfonylation of Benzylic C-H Bond
through a Reaction of Aryl(o-
Sulfonyla)onꢀofꢀbenzylicꢀC-Hꢀbond
tolyl)methanones with Sulfonyl
Hydrazides or Sulfonyl Chlorides
SulfonylationꢀofꢀbenzylicꢀC-Hꢀbondꢀthroughꢀaꢀreactionꢀofꢀaryl(o-tolyl)methanonesꢀwithꢀ
sulfonylꢀ hydrazidesꢀ orꢀ sulfonylꢀ chloridesꢀ isꢀ reported.ꢀ Duringꢀ theꢀ reactionꢀ process,ꢀ
enolsꢀareꢀgeneratedꢀinꢀsituꢀfromꢀaryl(o-tolyl)methanonesꢀunderꢀultravioletꢀirradiation,ꢀ
whichꢀ reactꢀ withꢀ sulfonylꢀ radicalsꢀ providingꢀ aꢀ rangeꢀ ofꢀ aryl(2-
(
arylsulfonylmethyl)aryl)methanones.
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