Visible-light promoted aerobic difunctionalization of alkenes with sulfonyl hydrazides for the synthesis of β-keto/hydroxyl sulfones

Article abstract of DOI:10.1039/c9ob00278b

A practical method has been developed for the conversion of alkenes to β-keto/hydroxyl sulfones by their reaction with sulfonyl hydrazides under metal-free conditions. This reaction proceeds through the oxidative addition of alkenes by sulfonyl radicals that are generated by visible-light induced oxidation of sulfonyl hydrazides. Notaly the reaction uses O₂ as the terminal oxidant, instead of metal catalysts or oxidants like TBHP, leading to H₂O and N₂ as the clean by-products. The key features of this reaction include readily available reagents, mild reaction conditions and broad substrate scope.

Full text of DOI:10.1039/c9ob00278b

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Takeharu Haino et al.
Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
benzene
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DOI: 10.1039/C9OB00278B
ARTICLE
Visible-light promoted aerobic difunctionalization of alkenes with
sulfonyl hydrazides for the synthesis of β-keto/hydroxyl sulfones
Jie Wu, a Yulan Zhang, a Xinchi Gong, a Yunge Meng, a and Chunyin Zhu*a,b
Received 00th January 20xx,
Accepted 00th January 20xx
A practical method has been developed for the conversion of alkenes to β-keto/hydroxyl sulfones by their reaction with
sulfonyl hydrazides under metal-free conditions. This reaction proceeds through the oxidative addition of alkenes by sulfonyl
radicals that are generated by visible-light induced oxidation of sulfonyl hydrazides. Notaly the reaction uses O2 as the
terminal oxidant, instead of metal catalysts or oxidants like TBHP, leading to H2O and N2 as the clean by-products.The key
features of this reaction include readily available reagents, mild reaction conditions and broad substrate scope.
DOI: 10.1039/x0xx00000x
of styrenes with sulfonylhydrazides for the synthesis of β-
ketosulfones (Eq. 3, Scheme 1).10
Introduction
Cu(OAc)2, 70 oC, O2
eq. 1
Alkenes have been exploited as starting materials for chemical
production in industry due to their diverse and abundant
availability from petrochemical sources.1 Among the numerous
utilizations of alkenes, difunctionalization of alkenes has
evolved to be one of the most powerful and straightforward
tools to integrate small molecules into intricate molecular
architectures via one-step introduction of two functional
groups that possess significantly synthetic utility in chemical
synthesis.2 In this regard, the oxysulfonylation of alkenes has
emerged as an ideal strategy for the synthesis of β -keto
sulfones, which are valuable skeletons found in many organic
compounds due to their biological properties3 and widespread
synthetic applications4. As a consequence, extensive research
efforts have been devoted to this transformation by the study
of sulphur sources, oxidants and catalysts. For example, Wei
Wang et al. Ref. 5a
O
O
O
O
R
S
CF3COOH, 70 oC, O2
S
Ar
eq. 2
eq. 3
R
NHNH2
Ar
Liu et al. Ref. 9
O
TBAB, TBHP, 60 oC, O2
Zhang & Sun Ref. 10
Our previous work:
methylene blue (2 mol%)
DABCO (1 equiv.) MeCN
O
Ar
R2
+
NHNH2
eq. 4
R1
R1
Ar
air, 7w blue LEDs, rt
R2
This work:
OH
O
O
O
R'
R
R
MB+, DABCO, visible-light
rt, air (open vial)
NHNH2
O
O
R'
Ar
S
S
Ar
R' = H
S
O
O
Ar
R
R'  H
Scheme 1. Syntheses of β-ketosulfones by difunctionalization of alkenes with
sulfonyl hydrazides.
Recently, visible light photoredox catalysis (VLPC)11 has
received increasing attention from the synthetic community
due to the mild conditions and high efficiency, and this strategy
has also been introduced to the oxidative difunctionalization of
alkenes12. In this context, major advance has been made in the
synthesis of β-ketosulfones by using visible light photoredox
catalysis. For example, Yang and co-workers developed a
visible-light-promoted oxysulfonylation reaction of alkenes with
sulfinic acids by using tert-butyl hydroperoxide (TBHP) as
oxidant for the synthesis of β -keto sulfones.13 Niu and co-
workers reported a Ir(ppy)2(dtbbpy)PF6-catalyzed visible-light-
induced oxidative difunctionalization of alkenes with sulfonyl
chlorides using air under mild conditions without any other
additives.14 Lipshutz and co-workers accomplished the aqueous
sulfonylation of various alkenes and enol acetates using
arenesulfonyl chlorides in the presence of a novel amphoteric
PQS-attached photocatalyst.15 As a continuation of our interest
in the utilization of hydrazine derivatives under photocatalytic
conditions16, we reported a metal-free protocol for the
conversion of alkenes to ketones through oxidative radical
and
Wang
reported
copper-catalyzed
aerobic
difunctionalization of alkenes with sulfonylhydrazides for the
synthesis ofβ-ketosulfones (Eq. 1, Scheme 1). Yadav et al.
5
accomplished K2S2O8-mediated aqueous oxysulfonylation of
simple alkenes with sodium arenesulfinates in the presence of
O2.6 Later, they also reported AgNO3-catalyzed oxysulfonylation
of alkenes with thiophenols as the sulphur source in the
presence of O2 (air) and K2S2O8 as oxidants.7 The same group
also achieved the transformation with sodium arenesulfinates
by using the AgNO3/K2S2O8 combination.8 Liu and co-workers
disclosed CF3COOH-promoted oxysulfonylation of alkenes with
sulfonyl hydrazides in the presence of O2 under elevated
temperature (Eq. 2, Scheme 1).9 Zhang and Sun reported tetra-
n-butylammonium bromide-mediated aerobic oxysulfonylation
a. School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang
212013, PR China. E-mail: zhucycn@gmail.com
b. State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University,
Xiamen 361005, P.R. China.
† Footnotes relating to the title and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
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ARTICLE
Journal Name
addition with arylhydrazines (Eq. 4, Scheme 1)16b. Now, by DABCO or replacing it with other bases, the reactions lead to
View Article Online
DOI: 10.1039/C9OB00278B
replacing arylhydrazines with sulfonyl hydrazides, we inferior results (entries 6−12). This phenomenon can be
discovered a visible-light promoted aerobic difunctionalization explained by the fact that base can significantly lower the redox
of alkenes for the synthesis of β-keto/hydroxyl sulfones potential of toluene sulfonyl hydrazide from +1.24 V vs SCE to
(Scheme 1). Herein we would like to report the details of this +0.53 V vs SCE by deprotonation17, making it easier to be
transformation.
oxidized by the excited MB+. The screening of solvents revealed
that EtOH is superior to other solvents, such as MeOH, CH2Cl2,
THF, DMSO, DMF and MeCN (Table 1 entries 13-18). Finally, a
reaction was performed under the irradiation of green LEDs,
and it gave a yield of 76% that is close to the one under standard
conditions.
Results and discussion
Table 1. Effect of Reaction Parameters on the difunctionalization of alkenes with
a
sulfonyl hydrazides
With the optimized conditions in hand, we proceeded to
evaluate the scope and generality of this difunctionalization of
alkenes. Initial studies began by holding the hydrazine reagent
constant (i.e., 4-methylbenzenesulfonohydrazide 2a) when
reacting alkenes with various substitution groups/patterns. The
reaction tolerated a range of functional groups including
electron-withdrawing groups (F, Cl and Br) and -donating
groups (Me and OMe). Some of these functional groups are
useful for further synthetic diversification. Notably,
O
O
O
O
MB+ (2 mol%)
Tol
S
S
DABCO (1 equiv.) EtOH
NHNH2
+
O
air, 7w blue LEDs, rt
3aa
2a
1a
entry variation from the standard conditions yield/%b
1
2
3
4
5
6
7
8
None
No MB+
78
<10
trace
40
33
29
56
43
31
46
42
30
69
62
31
37
30
67
76
No visible light, no MB+
Eosin Y, instead of MB+
Rhodamine B, instead of MB+
No DABCO
divinylbenzene
substrates
could
react
with
4-
methylbenzenesulfonohydrazide at one side selectively in good
yields (3ja and 3ka). For internal olefins, the reaction of (E)-
prop-1-en-1-ylbenzene with 4-methylbenzenesulfonohydrazide
was tried, however, it gave a disordered mixture.
DBU, instead of DABCO
Et3N,instead of DABCO
Pyridine, instead of DABCO
Piperidine, instead of DABCO
Cs2CO3,instead of DABCO
K2CO3,instead of DABCO
MeOH, instead of EtOH
CH2Cl2,instead of EtOH
THF, instead of EtOH
DMSO, instead of EtOH
DMF, instead of EtOH
MeCN, instead of EtOH
Green LEDs instead of blue LEDs
9
Table 2. Reaction of 4-methylbenzenesulfonohydrazide 2a with different alkenes
10
11
12
13
14
15
16
17
18
19c
1a
MB+ (2 mol%)
O
O
S
O
S
DABCO (1 equiv.) EtOH
NHNH2
Tol
+
R1
R1
Tol
O
O
air, 7w blue LEDs, rt
3
1
2a
O
O
O
O
S
O
O
O
O
S
S
Tol
Tol
S
Tol
Tol
O
O
O
O
Br
Cl
3aa, 78%
3ba, 89%
Br
3ca, 67%
3da, 83%
O
O
S
O
O
S
O
O
O
O
S
Tol
Tol
S
Tol
Tol
O
O
O
O
F
aStandard conditions: 1.5 mmol of 1a, 0.5 mmol of 2a, 0.01 mmol of methylene
blue, 0.5 mmol of DABCO, air (open flask), and EtOH (1.5 mL) at room temperature
under the irradiation of 7 W blue LEDs; MB+ = methylene blue, DABCO = 1,4-
Diazabicyclo[2.2.2]octane. bisolated yield. cThe reaction was irradiated by 7 W
green LEDs
O
3ea, 72%
3fa, 68%
3ga, 65%
3ha, 77%
O
O
S
O
O
S
O
O
Tol
O
O
Tol
S
Tol
O
O
O
3ja, 73%
3ia, 82%
3ka, 64%
At the outset, the reactivity towards this difunctionalization
of alkenes was evaluated by studying the reaction of styrene 1a
and 4-methylbenzenesulfonohydrazide 2a (Table 1). To our
delight, the reaction was found to work smoothly in the
presence of methylene blue (MB+, 2 mol %), DABCO (1 equiv.)
and air (open flask) in EtOH at room temperature under the
irradiation of 7 W blue LEDs, leading to the production of β-keto
sulfones 3aa in a good yield (78%) (entry 1). Without
photocatalyst, the reaction became sluggish, resulting in a yield
less than 10% (entry 2). The reaction performed in dark
environment was totally shut down, indicating light is
indispensable for this reaction (entries 3). Compared to
methylene blue, other commercially available organic
photocatalysts including rhodamine B and eosin Y, are less
effective (entries 4−5), probably due to the lower oxidation
potential of eosin Y [E1/2(PC*/PC−) = +0.83 V vs SCE for eosin Y;
E1/2(PC*/PC−) = +1.14 V vs SCE for MB+] 11l. Moreover, without
a1.5 mmol of 1a, 0.5 mmol of 2a, 0.01 mmol of methylene blue, 0.5 mmol of DABCO,
air (open flask), and EtOH (1.5 mL) at room temperature under the irradiation of 7
W blue LEDs
Table 3. Reaction of 4-methylbenzenesulfonohydrazide 2a with 1,1-disubstituted
alkenesa
2 | J. Name., 2012, 00, 1-3
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Journal Name
ARTICLE
O
MB+ (2 mol%)
O
S
R2
O
O
O
O
Tol
HO
View Article Online
DOI: 10.1039/SCO9OB00278B
Tol
NHNH2
S
S
DABCO (1 equiv.) EtOH
control reaction
+
R1
R
NHNH2
+
R2 R1
O
O
2a
air, 7w blue LEDs, rt
CH3
1
3
3aa
2a
1a
CH3
OH
O
S
O
S
CH3
OH
O
Ph
O
S
Tol
Cl
Tol
S
Tol
Tol
Variation from the standard conditions
TEMPO
yield
0
Ph
Ph
O
OH
O
O
OH
O
Addition of
(2.0 equiv.)
eq. 1
eq. 2
Br
3oa, 75%
3na, 76%
N
Under 2 (instead of air) atmosphere
<10%
3ma, 81%
3la, 72%
Scheme 2. Control reactions
CH3
O
S
CH3
O
S
CH3
OH
O
Tol
Tol
S
Tol
OH
O
OH
O
O
O
N
3pa, 70%
3qa, 77%
3ra, 63%
400
200
a1.5 mmol of 1a, 0.5 mmol of 2a, 0.01 mmol of methylene blue, 0.5 mmol of DABCO,
air (open flask), and EtOH (1.5 mL) at room temperature under the irradiation of 7
W blue LEDs
When α-methyl styrene was subjected to the reaction, β-
hydroxyl sulfone was generated in good yield (Table 3, 3la).
Other α-methyl styrenes bearing diverse substituents including
Cl, Br and OMe, also underwent this reaction smoothly, leading
to the corresponding β-hydroxyl sulfones in good yields (3ma,
3na and 3qa). Replacing benzene ring with other aromatic rings
such as naphthalene and pyridine, the reaction worked as well
(3pa and 3ra). Notably, this reaction is also applicable to
ethene-1,1-diyldibenzene, permitting the synthesis of a tertiary
alcohol bearing two phenyl groups (3oa).
0
720
Wavelength
760
Scheme 3. Luminescence quenching of methylene blue with excitation at 664 nm
by 2a.
This difunctionalization of alkenes with a focused substrate
scope of hydrazine derivatives was also explored. As shown in
Table 4, arylsulfonohydrazide with different groups on the
benzene ring reacted smoothly with styrene under the standard
conditions, leading to various β-keto sulfones in good yields
(3ab-3ae). In addition, thiophene-2-sulfonohydrazide also
worked for the transformation to generate the desired product
3af in 73% yield.
Table 4. Reaction of styrene 1a with substituted sulfonohydrazide 2a
MB+ (2 mol%)
O
O
O
S
DABCO (1 equiv.) EtOH
NHNH2
S
+
R
Ph
R
Ph
O
O
O
2
air, 7w blue LEDs, rt
Scheme 4. The Stern- Volmer plot.
1a
3
O
O
S
O
S
O
O
To provide some insights into the mechanism of this reaction,
control experiment in the presence of radical trapper TEMPO
(2.0 equiv.) was carried out. The reaction was found to be
inhibited, as no desired 3aa was isolated and the starting
styrene 1a was recovered (eq. 1, Scheme 2). This observation
supports the idea that the reaction probably proceeds through
a radical pathway. A reaction in N2 atmosphere was performed,
and only trace amount of product was isolated (eq.2, Scheme
2), indicating O2 is necessary for this reaction. Also the
luminescence of methylene blue with excitation at 664 nm
could be readily quenched by 2a following Stern−Volmer
kinetics (Scheme 3-4), and styrene 1a cannot serve as the
emission quenchers.
F
S
Cl
Ph
Ph
Ph
O
O
O
3ab, 75%
3ac 69%
3ad, 75%
O
O
S
O
O
S
S
NO2
Ph
Ph
O
O
3ae, 76%
3af, 73%
a1.5 mmol of 1a, 0.5 mmol of 2a, 0.01 mmol of methylene blue, 0.5 mmol of DABCO,
air (open flask), and EtOH (1.5 mL) at room temperature under the irradiation of 7
W blue LEDs
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J. Name., 2013, 00, 1-3 | 3
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ARTICLE
Journal Name
Ts
NH2
Ts
NH2
-H+
-H+
NH
available reagents and broad substrates scope, this reaction will
[O]
-e
Ts
NH2 [O]
-e
Ts
Ts
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N
H
N
H
4
N
N
6
find practical application for the transforDmOaIt: i1o0n.10o3f9a/Clk9eOnBe0s0.278B
5
2a
[O], -e
-H+
N
Experimental
General information
N
MB+
+e
H+
O2
O2
OOH
blue LEDs
7
-N2
[O] =
Column chromatography was generally performed on silica gel
(200-300 mesh) and reactions were monitored by thin layer
chromatography (TLC) using UV light to visualize the course of
Ts
8
*MB+
MB•
path a
Ph
1a
1
the reactions. The H (400 MHz) and 13C NMR (100 MHz) data
O
O
OH
O
O
-H2O
-O2
O
O
were recorded on Bruker AVANCE Ⅱ 400MHz spectrometer
using CDCl3 as solvent. The chemical shifts (δ) are reported in
ppm and coupling constants (J) in Hz. 1H NMR spectra was
recorded with tetramethylsilane (δ=0.00 ppm) as internal
reference; 13C NMR spectra was recorded with CDCl3 (δ=77.00
ppm) as internal reference. All starting materials commercially
available were used directly.
O2
Ts
Ts
HOO
Ts
3aa
Ts
Ph
Ph
Ph
Ph
9
10
11
path b
OOH
OH
O
O
Ts
Ts
Ph
Ph
3aa
12
Typical procedure for the synthesis of products 3
Scheme 5. Plausible mechanistic pathways for the reaction
To a solution of sulfonhydrazide 2 (0.5 mmol) and alkene 1 (1.5
mmol) in EtOH (1.5 mL) was added Methylene Blue (0.01 mmol)
and DABCO (1 mmol). The reaction mixture was stirred at 25℃
under air atmosphere (open vial) and irradiated by blue LED (7
W). After the completion of the reaction which was indicated by
TLC (usually 24 hours), removal of solvent followed by column
chromatography afforded desired products.
On the basis of these experimental observations and our
previous studies on the reaction of hydrazine derivatives16, a
plausible mechanism is proposed for this reaction (Scheme 5).
First, methylene blue is irradiated to the excited state *MB+
using blue LEDs, and this excited state is then reductively
quenched by 2a along with the generation of ionic radical 4 and
methylene blue radical (MB•). After deprotonation, ionic radical
4 is transformed to radical 5, which can also quench the excited
state *MB+ and lose a proton to give intermediate 6. Another
single-electron oxidation by *MB+, followed by deprotonation,
results in the formation of Ts• 8. During the course MB• is
oxidized back to MB+ by molecular oxygen with itself being
reduced to hydroperoxyl radical (HOO•). Furthermore,
intermediate 10, which is generated from the addition of Ts• to
styrene 1a followed by incorporation of dioxygen, could react
with hydroperoxyl radical to form 11. Then 11 decomposes to
afford the desired product 3aa, with concomitant formation of
molecular oxygen and water through Russell fragmentation18.
Another possible pathway from intermediate 9 to 3aa is the
combination of 9 with HOO• to form intermediate 12, followed
by its decomposition to final product 3aa (path b).
Characterization of products 3
1-phenyl-2-tosylethan-1-one (3aa) 19. Petroleum ether/ethyl
1
acetate =10:1, white solid, 78% yield (106 mg). H NMR (400
MHz, CDCl3) δ 7.97 (d, J = 7.7 Hz, 2H), 7.78 (d, J = 8.1 Hz, 2H),
7.64 (t, J = 7.3 Hz, 1H), 7.50 (t, J = 7.6 Hz, 2H), 7.35 (d, J = 8.0 Hz,
2H), 4.74 (s, 2H), 2.46 (s, 3H). 13C NMR (101 MHz, CDCl3) δ
188.15, 145.36, 135.82, 134.31, 129.84, 129.34, 128.84, 128.62,
63.61, 21.70.
1-(4-bromophenyl)-2-tosylethan-1-one (3ba) 19. Petroleum
1
ether/ethyl acetate =10:1, white solid, 89% yield (155 mg). H
NMR (400 MHz, CDCl3) δ 8.02 (t, J = 1.8 Hz, 1H), 7.91 (ddd, J =
7.8, 1.6, 1.0 Hz, 1H), 7.80 – 7.71 (m, 3H), 7.38 (dd, J = 15.3, 7.8
Hz, 3H), 4.70 (s, 2H), 2.47 (s, 3H). 13C NMR (101 MHz, CDCl3) δ
186.69, 144.92, 137.41, 132.04, 130.34, 128.55, 127.98, 123.18,
63.98.
19
1-(3-bromophenyl)-2-tosylethan-1-one (3ca)
.
Petroleum
1
ether/ethyl acetate =10:1, white solid, 67% yield (118 mg). H
NMR (400 MHz, CDCl3) δ 8.02 (t, J = 1.6 Hz, 1H), 7.91 (d, J = 7.8
Hz, 1H), 7.76 (t, J = 6.9 Hz, 3H), 7.38 (dd, J = 15.3, 7.8 Hz, 3H),
4.70 (s, 2H), 2.47 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 186.98,
145.64, 137.41, 137.12, 135.54, 132.09, 130.40, 129.95, 128.60,
Conclusions
In conclusion, we have developed a metal-free protocol for
the conversion of alkenes to β-keto/hydroxyl sulfones through
difunctionalization of alkenes with sulfonyl hydrazides. This
reaction avoids the need for the use of metal catalysts or
oxidants like TBHP. Instead, by using O2 as the terminal oxidant,
this visible-light induced reaction leads to H2O and N2 as the
clean by-products. Preliminary mechanistic studies suggested
the reaction goes through VLPC-promoted oxidation of sulfonyl
hydrazides to sulfonyl radical followed by its addition to
alkenes. Taken together with its operational simplicity, readily
128.03, 123.18, 63.68, 21.75.
1-(4-chlorophenyl)-2-tosylethan-1-one (3da)
19
.
Petroleum
1
ether/ethyl acetate =10:1, white solid, 83% yield (130 mg). H
NMR (400 MHz, CDCl3) δ 7.91 (d, J = 6.8 Hz, 2H), 7.76 (d, J = 8.3
Hz, 2H), 7.47 (d, J = 8.6 Hz, 2H), 7.36 (d, J = 8.3 Hz, 2H), 4.70 (s,
2H), 2.46 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 186.90, 145.56,
141.08, 135.62, 134.11, 130.79, 129.91, 129.21, 128.58, 63.74,
21.72.
4 | J. Name., 2012, 00, 1-3
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Journal Name
1-(4-fluorophenyl)-2-tosylethan-1-one (3ea)
ether/ethyl acetate =10:1, white solid, 72% yield (106 mg). H Found: C, 67.86; H, 5.24.
NMR (400 MHz, CDCl3) δ 8.15 – 7.94 (m, 2H), 7.77 (d, J = 8.2 Hz, 2-phenyl-1-tosylpropan-2-ol (3la) 20. Petroleum ether/ethyl
2H), 7.36 (d, J = 8.0 Hz, 2H), 7.26 – 7.08 (m, 2H), 4.71 (s, 2H), acetate =10:1, white solid, 72% yield (103mg). H NMR (400
2.47 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 186.58, 167.76, 165.20, MHz, CDCl3) δ 7.50 (d, J = 8.3 Hz, 2H), 7.33 – 7.29 (m, 2H), 7.24
145.52, 135.66, 132.51 – 132.12 (m), 129.90, 128.56, 116.21, – 7.14 (m, 5H), 4.66 (s, 1H), 3.67 (dd, J = 45.6, 14.6 Hz, 2H), 2.40
ARTICLE
19
.
Petroleum 323.1 (M + Na+). Anal. calcd for C17H16O3S: C, 67.98; H, 5.37.
View Article Online
1
DOI: 10.1039/C9OB00278B
1
115.99, 63.75, 21.71.
(s, 3H), 1.72 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 144.53, 137.39,
1-(p-tolyl)-2-tosylethan-1-one (3fa) 19. Petroleum ether/ethyl 133.62, 129.71, 128.25, 127.56, 127.13, 124.65, 73.17, 66.69,
acetate =20:1, white solid, 68% yield (98 mg). 1H NMR (400 MHz, 30.76, 21.57.
CDCl3) δ 7.87 (d, J = 8.3 Hz, 2H), 7.78 (d, J = 8.3 Hz, 2H), 7.35 (d, 2-(4-bromophenyl)-1-tosylpropan-2-ol (3ma) 20. Petroleum
1
J = 8.0 Hz, 2H), 7.29 (d, J = 8.0 Hz, 2H), 4.71 (s, 2H), 2.46 (s, 3H), ether/ethyl acetate =10:1, white solid, 81% yield (183mg). H
2.44 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 187.67, 145.57, 145.30, NMR (400 MHz, CDCl3) δ 7.45 (dd, J = 13.3, 5.4 Hz, 2H), 7.29 –
135.82, 133.39, 129.82, 129.54 (d, J = 3.7 Hz), 128.61, 63.58, 7.23 (m, 2H), 7.19 (d, J = 8.1 Hz, 2H), 7.15 – 7.08 (m, 2H), 4.72
21.76 (d, J = 7.4 Hz).
(s, 1H), 3.66 (dd, J = 53.1, 14.7 Hz, 2H), 2.45 (d, J = 7.6 Hz, 3H),
1-(m-tolyl)-2-tosylethan-1-one (3ga) 19. Petroleum ether/ethyl 1.64 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 144.81, 143.28, 136.84,
acetate =20:1, white solid, 65% yield (93mg). 1H NMR (400 MHz, 131.17, 129.75, 127.51, 126.61, 121.32, 72.80, 66.25, 31.02,
CDCl3) δ 7.79 (s, 1H), 7.77 (s, 2H), 7.75 (s, 1H), 7.73 (s, 1H), 7.44 21.62.
(d, J = 7.6 Hz, 1H), 7.37 (dd, J = 15.3, 7.8 Hz, 3H), 4.72 (s, 2H), 2-(3-chlorophenyl)-1-tosylpropan-2-ol (3na)
2.46 (s, 3H), 2.42 (s, 3H).13C NMR (101 MHz, CDCl3) δ 188.30, ether/ethyl acetate =10:1, white solid, 76% yield (161mg). H
20
.
Petroleum
1
145.33, 138.74, 135.83, 135.15, 129.76 (d, J = 10.2 Hz), 128.67 NMR (400 MHz, CDCl3) δ 8.02 (t, J = 1.6 Hz, 1H), 7.91 (d, J = 7.8
(d, J = 5.5 Hz), 126.66, 63.58, 21.68, 21.31.
Hz, 1H), 7.76 (t, J = 6.9 Hz, 3H), 7.38 (dd, J = 15.3, 7.8 Hz, 3H),
1-(4-methoxyphenyl)-2-tosylethan-1-one (3ha) 19. Petroleum 4.70 (s, 2H), 2.47 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 186.98,
1
ether/ethyl acetate =5:1, white solid, 77% yield (117mg). H 145.64, 137.41, 137.12, 135.54, 132.09, 130.40, 129.95, 128.60,
NMR (400 MHz, CDCl3) δ 7.95 (d, J = 8.9 Hz, 2H), 7.76 (d, J = 8.2 128.03, 123.18, 63.68, 21.75.
Hz, 2H), 7.34 (d, J = 8.1 Hz, 2H), 6.95 (d, J = 8.9 Hz, 2H), 4.68 (s, 1,1-diphenyl-2-tosylethan-1-ol (3oa) 20. Petroleum ether/ethyl
1
2H), 3.96 (s, 3H), 2.45 (s, 3H). 13C NMR (101 MHz, CDCl3) δ acetate =10:1, white solid, 75% yield (132mg). H NMR (400
186.36, 164.55, 145.26, 135.85, 131.93, 129.81, 128.92, 128.57, MHz, CDCl3) δ 7.44 (d, J = 8.3 Hz, 2H), 7.41 – 7.34 (m, 4H), 7.26
114.07, 63.55, 55.64, 21.71.
– 7.19 (m, 6H), 7.15 (d, J = 8.1 Hz, 2H), 5.41 (s, 1H), 4.21 (s, 2H),
1-(3,4-dimethoxyphenyl)-2-tosylethan-1-one (3ia). Petroleum 2.41 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 144.51, 143.73, 137.42,
1
ether/ethyl acetate =5:1, white solid, 82% yield (136mg). H 129.70, 128.28, 127.57 (d, J = 18.7 Hz), 125.87, 65.51, 21.61.
NMR (400 MHz, CDCl3) δ 7.77 (d, J = 8.2 Hz, 2H), 7.62 (d, J = 10.3 2-(naphthalen-2-yl)-1-tosylpropan-2-ol (3pa) 20. Petroleum
Hz, 1H), 7.48 (s, 1H), 7.34 (d, J = 8.1 Hz, 2H), 6.91 (d, J = 8.5 Hz, ether/ethyl acetate =10:1, white solid, 70% yield (119mg). H
1
1H), 4.70 (s, 2H), 3.96 (s, 3H), 3.91 (s, 3H), 2.45 (s, 3H).13C NMR NMR (400 MHz, CDCl3) δ 8.04 – 7.93 (m, 1H), 7.87 (d, J = 7.3 Hz,
(101 MHz, CDCl3) δ 186.41, 154.48, 149.23, 145.27, 135.85, 1H), 7.67 (dd, J = 8.7, 4.1 Hz, 2H), 7.49 – 7.40 (m, 1H), 7.39 – 7.32
129.81, 129.04, 128.57, 125.15, 110.67, 110.13, 63.48, 56.12 (d, (m, 2H), 7.16 (d, J = 8.2 Hz, 2H), 6.78 (d, J = 8.1 Hz, 2H), 4.87 (s,
J = 19.0 Hz), 21.71. MS (ESI, m/z) 335.1 (M + H+), 357.1 (M + Na+). 1H), 4.13 (dd, J = 220.5, 15.0 Hz, 2H), 2.21 (s, 3H), 2.00 (s, 3H).
Anal. calcd for C17H18O5S: C, 61.06; H, 5.43. Found: C, 60.84; H, 13C NMR (101 MHz, CDCl3) δ 143.70, 139.04, 134.54, 129.37,
5.56.
129.20, 128.82, 126.94, 125.72, 125.09, 124.77, 124.55, 124.38,
2-tosyl-1-(3-vinylphenyl) ethan-1-one (3ja). Petroleum 73.52, 65.00, 30.14, 21.35.
1
ether/ethyl acetate =20:1, white solid, 73% yield (109mg). H 2-(4-methoxyphenyl)-1-tosylpropan-2-ol (3qa) 20. Petroleum
1
NMR (400 MHz, CDCl3) δ 7.93 (s, 1H), 7.85 (d, J = 7.8 Hz, 1H), ether/ethyl acetate =5:1, white solid, 77% yield (123mg). H
7.78 (d, J = 8.3 Hz, 2H), 7.67 (d, J = 7.7 Hz, 1H), 7.46 (t, J = 7.8 Hz, NMR (400 MHz, CDCl3) δ 7.49 (d, J = 7.1 Hz, 2H), 7.19 (dd, J =
1H), 7.35 (d, J = 8.1 Hz, 2H), 6.75 (dd, J = 17.6, 10.9 Hz, 1H), 5.84 8.6, 3.3 Hz, 4H), 6.71 (d, J = 8.8 Hz, 2H), 4.61 (s, 1H), 3.77 (s, 3H),
(d, J = 17.6 Hz, 1H), 5.38 (d, J = 10.9 Hz, 1H), 4.75 (s, 2H), 2.46 (s, 3.64 (dd, J = 49.7, 14.6 Hz, 2H), 2.40 (s, 3H), 1.69 (s, 3H). 13C NMR
3H). 13C NMR (101 MHz, CDCl3) δ 188.12, 145.42, 138.36, (101 MHz, CDCl3) δ 158.70, 144.41, 136.64, 129.65, 127.57,
137.42, 136.08, 135.54, 131.74, 129.85, 129.04, 128.63, 126.96, 125.87, 113.50, 72.89, 66.85, 55.24, 30.70, 21.57.
21
115.88, 63.69, 21.70. MS (ESI, m/z) 301.1 (M + H+), 323.1 (M + 2-(pyridin-3-yl)-1-tosylpropan-2-ol (3ra)
.
Petroleum
Na+). Anal. calcd for C17H16O3S: C, 67.98; H, 5.37. Found: C, ether/ethyl acetate =10:1, white solid, 63% yield (92mg). H
1
67.74; H, 5.26.
NMR (400 MHz, CDCl3) δ 8.18 (d, J = 4.7 Hz, 1H), 7.66 (q, J = 8.4
2-tosyl-1-(4-vinylphenyl) ethan-1-one (3ka). Petroleum Hz, 2H), 7.49 (d, J = 8.3 Hz, 2H), 7.17 (d, J = 8.1 Hz, 2H), 7.07 (ddd,
1
ether/ethyl acetate =40:1, white solid, 64% yield (96mg). H J = 6.6, 4.8, 1.7 Hz, 1H), 3.90 (dd, J = 152.0, 14.5 Hz, 2H), 2.38 (s,
NMR (400 MHz, CDCl3) δ 7.93 (d, J = 8.4 Hz, 2H), 7.78 (d, J = 8.3 3H), 1.62 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 162.51, 147.95,
Hz, 2H), 7.51 (d, J = 8.3 Hz, 2H), 7.35 (d, J = 8.0 Hz, 2H), 6.78 (dd, 144.23, 137.45, 136.93, 129.55, 127.70, 122.13, 119.34, 74.04,
J = 17.6, 10.9 Hz, 1H), 5.69 (dd, J = 189.7, 19.5 Hz, 2H), 4.72 (s, 65.17, 30.11, 21.56.
2H), 2.46 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 187.46, 145.38, 1-phenyl-2-(phenylsulfonyl) ethan-1-one (3ab) 22. Petroleum
1
143.33 (s), 135.77, 135.68, 134.89, 129.83 (d, J = 1.9 Hz), 128.61, ether/ethyl acetate =10:1, white solid, 75% yield (98mg). H
126.53, 117.76, 63.68, 21.71. MS (ESI, m/z) 301.1 (M + H+), NMR (400 MHz, CDCl3) δ 4.74 (s, 2H), 7.48(tt, J = 7.8, 1.6 Hz, 2H),
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Chem. Sci., 2017, 8, 2610. (g) Y.-Y. Liu, X.-H. Yang, R.-J.
7.55 (tt, J = 7.8, 1.6 Hz, 2H), 7.62 (tt, J = 7.4, 1.2 Hz, 1H), 7.66 (tt,
J =7.6, 1.2 Hz, 1H), 7.90 (m, 2H), 7.94 (m, 2H). 13C NMR (101
MHz, CDCl3) δ 188.1, 138.8, 135.8, 134.5, 134.4, 129.4, 129.3,
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Song, S. Luo and J.-H. Li, Nat. Commun. 8, 14720; (h) J.
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129.0, 128.7, 63.6.
2-((4-fluorophenyl) sulfonyl)-1-phenylethan-1-one (3ac)
3
4
22
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Petroleum ether/ethyl acetate =10:1, white solid, 75% yield
(104mg). 1H NMR (400 MHz, CDCl3) δ 4.75 (s, 2H),7.20-7.26 (m,
2H), 7.50 (t, J = 7.8 Hz, 2H), 7.64 (t, J = 7.4 Hz, 1H), 7.90-7.95 (m,
4H). 13C NMR (100 MHz, CDCl3) δ 188.1, 166.3 (d, 1JCF = 245.4
Hz), 135.7, 134.8 (d, 4JCF = 3.1 Hz), 134.7, 131.8 (d, 3JCF = 9.7
5
Hz), 129.4, 129.1, 116.7 (d, 2JCF = 22.6 Hz), 63.6.
2-((4-chlorophenyl) sulfonyl)-1-phenylethan-1-one (3ad)
22
.
Petroleum ether/ethyl acetate =10:1, white solid, 69% yield
(101mg). 1H NMR (400 MHz, CDCl3) δ 4.75 (s, 2H),7.48-7.53 (m,
4H), 7.64 (t, J = 7.4 Hz, 1H), 7.83 (d, J = 8.8 Hz, 2H), 7.93 (d, J =
8.4 Hz, 2H). 13C NMR (100 MHz, CDCl3) δ 188.0, 141.3, 137.2,
6
7
8
9
135.7, 134.7, 130.3, 129.7, 129.4, 129.1, 63.5.
2-((4-nitrophenyl) sulfonyl)-1-phenylethan-1-one (3ae)
22
.
Petroleum ether/ethyl acetate =10:1, white solid, 77% yield
(117mg). 1H NMR (400 MHz, CDCl3) δ 8.45 – 8.35 (m, 1H), 8.14
(ddt, J = 11.3, 9.3, 2.4 Hz, 1H), 7.94 (dt, J = 7.1, 1.4 Hz, 1H), 7.72
– 7.63 (m, 0H), 7.52 (t, J = 7.8 Hz, 1H), 4.82 (s, 1H). 13C NMR (101
MHz, CDCl3) δ 187.60, 144.03, 135.33, 134.86, 130.34, 129.19,
10 (a) X. Wan, K. Sun and G. Zhang, Sci. China Chem., 2017,
60, 353; Related works on sulfonyl hydrazides: (b) S. Cai,
Y. Xu, D. Chen, L. Li, Q. Chen, M. Huang and W. Weng,
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Weng, L. Li, R. Zhang and M. Huang, Org. Biomol.
Chem. 2016, 14, 4205.
129.09, 124.31, 63.00.
1-phenyl-2-(thiophen-2-ylsulfonyl) ethan-1-one (3af)
23
.
Petroleum ether/ethyl acetate =5:1, white solid, 73%
yield(102mg). 1H NMR (400 MHz, CDCl3): δ = 7.95 (d, J = 7.4 Hz,
2 H), 7.74 (dd, J = 4.9, 1.3 Hz, 1 H), 7.69 (dd, J = 3.8, 1.2 Hz, 1 H),
7.63 (t, J = 7.4 Hz, 1 H), 7.49 (t, J = 7.4 Hz, 2 H), 7.13 (dd, J = 4.9,
3.9 Hz, 1 H), 4.83 (s, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ
187.8, 139.4, 135.7, 135.5, 135.0, 134.5, 129.2, 128.9, 127.9,
64.4.
11 For selected reviews on photoredox catalysis: (a) J.
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Conflicts of interest
There are no conflicts to declare.
Acknowledgements
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56, 3732. (b) Yin, G.; Mu, X.; Liu, G. Acc. Chem. Res. 2016,
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We acknowledge the Qing Lan Project of Jiangsu Province and
Jiangsu University Foundation (No. 13JDG059) for financial
support.
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