Copper-Mediated 1,2-Difunctionalization of Styrenes with Sodium Arylsulfinates and tert-Butyl Nitrite: Facile Access to α-Sulfonylethanone Oximes

Article abstract of DOI:10.1002/adsc.201600109

A new copper-mediated synthesis of α-sulfonylethanone oximes from styrenes, sodium arylsulfinates and tert-butyl nitrite (t-BuONO; TBN) is presented. This intermolecular three-component method enables the one-step formation of C N and C S bonds under mild conditions, and represents a new, straightforward approach to α-sulfonylethanone oximes. (Figure presented.) .

Full text of DOI:10.1002/adsc.201600109

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DOI: 10.1002/adsc.201600109
Copper-Mediated 1,2-Difunctionalization of Styrenes with
Sodium Arylsulfinates and tert-Butyl Nitrite: Facile Access to
a-Sulfonylethanone Oximes
Ji Yang,a Yan-Yun Liu,a Ren-Jie Song,a Zhi-Hong Peng,a,* and Jin-Heng Lia,b,*
a
State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan
University, Changsha 410082, Peopleꢀs Republic of China
State Key Laboratory of Applied Organic Chemistry Lanzhou University, Lanzhou 730000, Peopleꢀs Republic of China
b
Fax : (+86)-731-8871-3642; phone: (+86)-731-8871-3642; e-mail: pzh7251@yahoo.com or jhli@hnu.edu.cn
Received: January 24, 2016; Revised: April 18, 2016; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201600109.
Abstract: A new copper-mediated synthesis of a-
sulfonylethanone oximes from styrenes, sodium ar-
ylsulfinates and tert-butyl nitrite (t-BuONO; TBN)
is presented. This intermolecular three-component
products, pharmaceuticals, and materials, and are also
valuable intermediates in synthesis.[7] Traditionally,
approaches for the synthesis of a-sulfonylethanone
oximes often require multiple synthetic steps that
have low total yields and limited functional group
choice. In 2012, He and co-workers reported the two-
component cascade oxidation–addition reactions of
olefins with N-hydroxysulfonamides for the synthesis
of a-sulfonylethanone oximes in which the addition of
NO free radicals proceeded through the oxidation of
hydroxylamine to form the corresponding oximes.[4h]
Inspired by these results, we envisioned that, by using
an oxidative–radical strategy, the three-component in-
termolecular process might be used for introducing
the sulfonyl group into the alkenes. Herein, we report
À
method enables the one-step formation of C N and
À
C S bonds under mild conditions, and represents
a new, straightforward approach to a-sulfonyletha-
none oximes.
Keywords: tert-butyl nitrite; copper; sodium arylsul-
finates; styrenes; a-sulfonylethanone oximes
The difunctionalization of alkenes that simultaneously a new, three-component intermolecular method to
adds two functional groups across a C=C double bond produce a-sulfonylethanone oximes by copper-cata-
is one of the most important and straightforward
methods for rapidly increasing molecular complexity,
and it continues to inspire considerable efforts to de-
velop new transformations.[1,2] In this field, attractive
transformations include the difunctionalization reac-
tions of alkenes with sulfonylation reagents and other
functional reagents,[3] which provide an efficient tool
for assembling useful sulfonyl-functionalized mole-
cules.[4] However, transformations of alkenes using
the three-component intermolecular strategy for the
incorporation of sulfonyl groups turned out to be
challenging. Indeed, the success of such three-compo-
nent intermolecular difunctionalization transforma-
tions is rare and restricted to oxysulfonylation[5] and
halosulfonylation (Scheme 1a).[6] Thus, the develop-
ment of new, mild three-component intermolecular
methods for incorporating a sulfonyl group into
simple alkenes, which extends beyond oxysulfonyla-
tion and halosulfonylation, is highly interesting.
The a-sulfonylethanone oximes are a class of im-
portant compounds that are found in some natural corporation of the sulfonyl group.
Scheme 1. Difunctionalization reaction of alkenes via the in-
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lyzed difunctionalization of styrenes with sodium aryl- identical yield to that obtained with 10 mol% of
sulfinates and t-BuONO (Scheme 1b). This method CuBr, but a lower amount of CuBr (5 mol%) sharply
À
allows the construction of a C S bond and a C=N decreased the yield to 38%. A screen of various sol-
double bond through cascade radical addition across vents, such as toluene, MeCN, ClCH2CH2Cl, CH2Cl2,
the C=C double bond in styrenes. This is accom- DMF and DMSO, revealed toluene as the best choice
plished by using sodium arylsulfinates, nitrosation and (entry 1 versus entries 9–13). The reaction at a loading
hydroamination and represents a mild and practical of 3 equiv. H2O in anhydrous toluene also afforded
access to a-sulfonylethanone oximes.
product 3aa in good yield (entry 14). Among the reac-
As shown in Table 1, we optimized reaction condi- tion temperatures examined, the reaction at 608C
tions for the three-component reaction of 1-methyl-4- turned out to be preferred in terms of the yield (en-
vinylbenzene (1a) with sodium benzenesulfinate (2a) tries 1, 15 and 16).
and t-BuONO. To our delight, treatment of styrene 1a
With the optimal reaction conditions in hand, a vari-
with sodium arylsulfinate 2a, t-BuONO and CuBr in ety of sodium arylsulfinates 2, was first investigated in
toluene afforded the desired 2-(phenylsulfonyl)-1-(p- the presence of styrene 1a, t-BuONO and CuBr
tolyl)ethan-1-one oxime (3aa) in 71% yield (entry 1). (Table 2). Gratifyingly, sodium arylsulfinates 2, bear-
A series of other Cu catalysts, including CuI, CuOTf, ing either electron-donating (Me and MeO) or elec-
CuBr2 and Cu(OAc)2, was subsequently tested; each tron-withdrawing (Cl, Br and NO2) groups at the 2 or
of these catalysts was less effective than CuBr (en- 4 positions of the aromatic ring were compatible with
tries 2–5). However, only a trace amount of product the optimized conditions (products 3ab–ag). While 4-
3aa was observed by GC-MS analysis in the absence Me- or 4-MeO-substituted sodium arylsulfinates 2b
of a copper catalyst (entry 6). The results show that and c afforded products 3ab and 3ac in 57% and 48%
the amount of CuBr affected the reaction (entries 7 yields, respectively, 4-NO2-substituted sodium arylsul-
and 8): a higher amount of CuBr (20 mol%) gave an finate was converted into product 3af in 61% yield.
Table 1. Optimization of the reaction conditions.[a]
Table 2. Difunctionalization tandem reaction of 1-methyl-4-
vinylbenzene (1a) with sodium arylsulfinates (2) and t-
BuONO[a]
Entry Cu (mol%)
Solvent
T [oC] Yield [%][b]
1
2
3
4
5
6
7
8
CuBr (10)
CuI (10)
CuOTf (10)
CuBr2 (10)
Cu(OAc)2 (10) toluene
–
CuBr (20)
CuBr (5)
CuBr (10)
CuBr (10)
CuBr (10)
CuBr (10)
CuBr (10)
CuBr (10)
CuBr (10)
CuBr (10)
toluene
toluene
toluene
toluene
60
60
60
60
60
60
60
60
60
71
63
52
28
56
trace
68
38
63
46
36
15
25
70
44
55
toluene
toluene
toluene
MeCN
ClCH2CH2Cl 60
CH2Cl2
DMF
DMSO
toluene
toluene
toluene
9
10
11
12
13
14[c]
15
16
60
60
60
60
40
80
[a]
Reaction conditions: 1a (0.2 mmol), 2a (2 equiv.), t-
BuONO (2 equiv.), [Cu] and solvent (2 mL) for 12 h. All
solvents contain about 0.3% to 0.5% w/w water.
Isolated yields.
[a]
Reaction conditions: 1a (0.2 mmol),
2 (2 equiv.), t-
[b]
[c]
BuONO (2 equiv.), CuBr (10 mol%) and toluene (2 mL)
at 608C for 12 h.
H2O (3 equiv.) in anhydrous toluene.
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Interestingly, the halogen groups Cl and Br were well- pleased to find that styrene 1b was able to furnish the
tolerated and, thus, provide additional opportunities desired product, 1-phenyl-2-(phenylsulfonyl)ethan-1-
for modification of the products (products 3ad, 3ae one oxime (3ba), in 68% yield. Styrenes 1 with a sub-
and 3ag). These results show that the substitution po- stituent, such as MeO, CH2Cl, Cl, Br, CN and NO2,
sition has a fundamental influence on reactivity. In on the aromatic ring were compatible with the opti-
the case of the bromo-substituted substrates 2e and mized reaction conditions, providing the correspond-
2g, the reactivity decreased from para to ortho substi- ing products 3ca–ka in moderate to good yields. Nota-
tution (products 3ae and 3ag).
bly, the steric hindrance effects of substituents impact-
A wide range of terminal styrenes 1b–l and internal ed on the reactivity. For example, the MeO-substitut-
alkenes 1m–n were subjected to the optimized condi- ed styrenes 1c, 1i and 1k smoothly underwent the di-
tions to produce products 3ba–na (Table 3). We were functionalization reaction (products 3ca, 3ia and 3ka,
respectively), but the reactivity, as measured by yield,
decreased from para to meta to ortho substitution.
Gratifyingly, the 2-vinylnaphthalene 1l was a suitable
Table 3. Variation of the styrenes.[a]
substrate for the reaction (product 3la). It was noted
that the internal alkenes 1-methoxy-4-(prop-1-en-1-
yl)benzene (1m) and (3-chloroprop-1-en-1-yl)benzene
(1n) successfully reacted with sodium arylsulfinate 2a
and t-BuONO in 62% and 51% yields, respectively
(products 3ma and 3na). Unfortunately, the aliphatic
alkene 1o failed to react under the optimized reaction
conditions.
To understand the mechanism of the three-compo-
nent intermolecular reaction, control experiments
were performed (Scheme 2). This reaction was sub-
stantially inhibited by radical scavengers, including
2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) or 2,4-
di-tert-butyl-4-methylphenol (BHT) [Eq. (1)], suggest-
ing that the reaction involves a radical pathway. An
18O-labelling experiment was also performed by using
H218O; the18O-labelled product 3aa-18O was observed,
which indicates that the hydroxy groupꢀs oxygen atom
is from H2O [Eq. (2)].
[a]
Reaction conditions:
1 (0.2 mmol), 2a (2 equiv.), t-
BuONO (2 equiv.), CuBr (10 mol%) and toluene (2 mL)
at 608C for 12 h.
Scheme 2. Control experiments.
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Therefore, we propose a possible mechanism, which Typical Procedure for the Synthesis of Sodium
is outlined in Scheme 3, for this tandem protocol.[8–10] Arylsulfinates (3)
Initially, t-BuONO readily decomposes into HNO2
4-Methylbenzenesulfinic acid sodium salt 2b was prepared
by heating 5.0 g of sodium sulfite, 3.80 g of 4-methylbenz-
AHCTUNGTREGeNNNU nesulfonyl chloride, and 3.36 g of sodium bicarbonate in
and t-BuOH in the presence of H2O, and HNO2 is
quickly converted into NO2, NO and H2O.[9,10] Sodium
benzenesulfinate releases the oxygen-centered radical
A, which is in resonance with the sulfonyl radical B,
with the aid of CuBr.[8] Addition of sulfonyl radical B
across styrene 1b forms intermediate C, which then
reacts with t-BuONO[9,10] to afford intermediate D. Fi-
nally, intermediate D is converted to the desired
oxime, 3ba, via a tautomerization process.[9i]
20 mL of water at 808C for 8 h. After cooling to room tem-
perature, water was removed under vacuum. Recrystalliza-
tion of the residue in ethanol produced a white solid; yield:
1.78 g (55%).
Similarly, other sodium arylsulfinates 2c–2g were prepared
from their corresponding sulfonyl chlorides.
Typical Procedure for Copper-Mediated Synthesis of
Oximes from Styrenes
A mixture of styrene 1 (0.2 mmol), sodium arylsulfinate 2
(0.4 mmol), t-BuONO (0.4 mmol), and CuBr (10 mol%) was
stirred in toluene (2 mL) at 608C (oil-bath temperature) for
the indicated time (about 12 h) until the complete consump-
tion of the starting material as monitored by TLC. After the
reaction was finished, the reaction mixture was cooled to
room temperature, and washed with brine. The aqueous
phase was re-extracted with EtOAc (3ꢂ10 mL) and the re-
sulting residue was purified by silica gel column chromatog-
raphy (hexane/ethyl acetate) to isolate the desired products
3.
Analytical Data for 3aa–3ag and 3ba–3na
2-(Phenylsulfonyl)-1-(p-tolyl)ethan-1-one
oxime
(3aa):
yield: 41.0 mg (71%); white solid; mp 153.9–154.38C (uncor-
rected); H NMR (400 MHz, acetone-d6): d=10.78 (s, 1H),
Scheme 3. Possible mechanisms.
1
7.82 (d, J=7.6 Hz, 2H), 7.70–7.66 (m, 1H), 7.61 (d, J=
8.4 Hz, 2H), 7.57–7.53 (m, 2H), 7.16 (d, J=8.0 Hz, 2H),
4.87 (s, 2H), 2.33 (s, 3H); 13C NMR (100 MHz, acetone-d6):
d=146.4, 140.5, 139.0, 133.6, 132.0, 128.8, 128.3, 126.5, 51.7,
20.4; LR-MS (EI, 70 eV): m/z (%)=273 (48), 208 (100), 209
(87), 193 (43); HR-MS (ESI): m/z=290.0833, calcd. for
In summary, we have developed a new, copper-
mediated difunctionalization reaction of styrenes with
sodium arylsulfinates and t-BuONO for the selective
synthesis of diverse a-sulfonylethanone oximes. This
method proceeds through a sequence of radical addi- C15H16NO3S (M+H)+: 290.0845.
3aa-18O: yield: 37.8 mg (65%); HR-MS (ESI): m/z=
tion, nitrosation and hydroamination and is a simple
and highly generalizable route for the production of
a-sulfonylethanone oximes with excellent functional
group tolerance. Further studies on the development
of conceptually novel, three-component intermolecu-
lar reactions are currently underway in our laborato-
ry.
292.0873, calcd. for C15H16N18O16O2S (M+H)+: 292.0888.
1-(p-Tolyl)-2-tosylethan-1-one oxime (3ab): yield: 34.5 mg
(57%); white solid; mp 160.9–161.38C (uncorrected);
1H NMR (400 MHz, CDCl3): d=8.54 (s, 1H), 7.70 (d, J=
8.0 Hz, 2H), 7.49 (d, J=8.0 Hz, 2H), 7.22 (d, J=7.6 Hz,
2H), 7.16 (d, J=8.0 Hz, 2H), 4.70 (s, 2H), 2.37(s, 6H);
13C NMR (100 MHz, CDCl3): d=147.8, 144.8, 140.1, 136.5,
130.8, 129.4, 129.3, 128.4, 126.5, 52.7, 21.6, 21.3; LR-MS (EI,
70 eV): m/z (%)=288 (1), 119 (100), 91 (37), 108 (23); HR-
MS (ESI): m/z=304.0990, calcd. for C16H18NO3S (M+H)+:
304.1002.
2-[(4-Methoxyphenyl)sulfonyl]-1-(p-tolyl)ethan-1-one
oxime (3ac): yield: 30.6 mg (48%); white solid; mp 143.9–
144.78C (uncorrected); 1H NMR (400 MHz, CDCl3): d=
7.91 (s, 1H), 7.74 (d, J=8.4 Hz, 2H), 7.52 (d, J=8.0 Hz,
2H), 7.17 (d, J=7.6 Hz, 2H), 6.90 (d, J=8.8 Hz, 2H), 4.70
(s, 2H), 3.84 (s, 3H), 2.37 (s, 3H); 13C NMR (100 MHz,
CDCl3): d=163.8, 148.3, 140.1, 131.0, 130.8, 130.7, 129.3,
126.5, 113.9, 55.6, 52.7, 21.3; LR-MS (EI, 70 eV): m/z (%)=
223.9 (100), 303 (95), 238 (93), 207 (90); HR-MS (ESI): m/
z=320.0940, calcd. for C16H18NO4S (M+H)+: 320.0951.
Experimental Section
General Considerations
1
The H and 13C NMR spectra were recorded in CDCl3 or
acetone-d6 solvents on an NMR spectrometer using TMS as
the internal standard. LR-MS was performed on a GC-MS
instrument, and HR-MS was measured on an electrospray
ionization (ESI) apparatus using time-of-flight (TOF) mass
spectrometry. Melting points are uncorrected.
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1
2-[(4-Chlorophenyl)sulfonyl]-1-(p-tolyl)ethan-1-one
oxime (3ad): yield: 40.7 mg (63%); white solid; mp 165.9–
167.38C (uncorrected); 1H NMR (400 MHz, CDCl3): d=
8.46 (s, 1H), 7.73 (d, J=7.6 Hz, 2H), 7.47 (d, J=8.0 Hz,
2H), 7.39 (d, J=8.4 Hz, 2H), 7.17 (d, J=8.0 Hz, 2H), 4.72
(s, 2H), 2.37 (s, 3H); 13C NMR (100 MHz, CDCl3): d=
147.6, 140.6, 140.4, 137.7, 130.5, 130.0, 129.4, 129.0, 126.5,
52.7, 21.3; LR-MS (EI, 70 eV): m/z (%)=307 (1), 119 (100),
91 (24), 117 (13); HR-MS (ESI): m/z=324.0447, calcd. for
C15H1535ClNO3S (M+H)+: 324.0456.
156.9–158.18C (uncorrected); H NMR (400 MHz, acetone-
d6): d=10.99 (s, 1H), 7.83 (d, J=8.0 Hz, 2H), 7.73 (d, J=
8.4 Hz, 2H), 7.70–7.76 (m, 1H), 7.57–7.53 (m, 2H), 7.43 (d,
J=8.0 Hz, 2H), 4.90 (s, 2H), 4.73 (s, 2H); 13C NMR
(100 MHz, acetone-d6): d=146.1, 140.4, 138.9, 134.8, 133.7,
128.9, 128.6, 128.3, 126.9, 51.7, 45.5; LR-MS (EI, 70 eV): m/
z (%)=223 (100), 286 (86), 194 (75), 77 (70); HR-MS
(ESI): m/z=324.0468, calcd. for C15H1535ClNO3S (M+H)+
324.0456.
1-(4-Chlorophenyl)-2-(phenylsulfonyl)ethan-1-one oxime
(3ea): yield: 34.6 mg (56%); white solid; mp 166.9–167.88C
(uncorrected); H NMR (400 MHz, CDCl3): d=8.18 (s, 1H),
2-[(4-Bromophenyl)sulfonyl]-1-(p-tolyl)ethan-1-one
1
oxime (3ae): yield: 52.7 mg (72%); white solid; mp 174.9–
175.38C (uncorrected); 1H NMR (400 MHz, CDCl3): d=
8.22 (s, 1H), 7.66 (d, J=8.0 Hz, 2H), 7.56 (d, J=8.0 Hz,
2H), 7.48 (d, J=7.6 Hz, 2H), 7.18 (d, J=8.0 Hz, 2H), 4.72
(s, 2H), 2.38 (s, 3H); 13C NMR (100 MHz, CDCl3): d=
147.6, 140.4, 138.2, 132.0, 130.4, 130.1, 129.4, 129.2, 126.5,
52.6, 21.3; LR-MS (EI, 70 eV): m/z (%)=318 (71), 254 (12),
207 (77), 253 (59); HR-MS (ESI): m/z=367.9943, calcd. for
C15H1579BrNO3S (M+H)+: 367.9951.
7.84 (d, J=7.6 Hz, 2H), 7.61–7.57 (m, 3H), 7.50–7.46 (m,
2H), 7.33 (d, J=8.0 Hz, 2H), 4.71 (m, 2H); 13C NMR
(100 MHz, CDCl3): d=146.9, 139.3, 136.1, 134.0, 132.0,
128.9, 128.8, 128.4, 127.9, 52.5; LR-MS (EI, 70 eV): m/z
(%)=293 (1), 139 (100), 141 (13), 77 (39); HR-MS (ESI):
m/z=310.0375, calcd. for C14H1335ClNO3S (M+H)+:
310.0299.
1-(4-Bromophenyl)-2-(phenylsulfonyl)ethan-1-one oxime
(3fa): yield: 36.6 mg (52%); white solid; mp 188.9–189.68C
(uncorrected); 1H NMR (400 MHz, CDCl3): d=11.07 (s,
1H), 7.84–7.82 (m, 2H), 7.72–7.66 (m, 3H), 7.59–7.53 (m,
4H), 4.90 (s, 2H); 13C NMR (100 MHz, CDCl3): d=145.7,
140.3, 134.1, 133.8, 131.3, 128.9, 128.5, 128.3, 122.9, 51.5;
LR-MS (EI, 70 eV): m/z (%)=338 (37), 193 (100), 117 (61),
273 (51); HR-MS (ESI): m/z=353.9786, calcd. for
C14H1379BrNO3S (M+H)+: 353.9794.
2-[(4-Nitrophenyl)sulfonyl]-1-(p-tolyl)ethan-1-one oxime
(3af): yield: 40.7 mg (61%); white solid; mp 181.9–183.38C
1
(uncorrected); H NMR (400 MHz, CDCl3): d=8.27 (d, J=
8.4 Hz, 2H), 8.01 (d, J=8.4 Hz, 2H), 7.51 (d, J=8.0 Hz,
2H), 7.19 (d, J=8.0 Hz, 2H), 4.78 (s, 2H), 2.38 (s, 3H);
13C NMR (100 MHz, CDCl3): d=150.9, 147.4, 144.6, 140.8,
130.2, 130.1, 129.5, 126.5, 123.8, 52.6, 21.3; LR-MS (EI,
70 eV): m/z (%)=352 (41), 206 (100), 286 (57), 289 (55);
HR-MS (ESI): m/z=335.0688, calcd. for C15H15N2O5S (M+
H)+: 335.0696.
4-[1-(Hydroxyimino)-2-(phenylsulfonyl)ethyl]benzonitrile
(3ga): yield: 40.2 mg (67%); white solid; mp 173.9–174.78C
(uncorrected); H NMR (400 MHz, acetone-d6): d=11.41 (s,
1
2-[(2-Bromophenyl)sulfonyl]-1-(p-tolyl)ethan-1-one
oxime (3ag): yield: 40.3 mg (55%); white solid; mp 179.9–
180.78C (uncorrected); 1H NMR (400 MHz, CDCl3): d=
8.00 (s, 1H), 7.96–7.93 (m, 1H), 7.71–7.69 (m, 1H), 7.48 (d,
J=8.0 Hz, 2H), 7.40–7.34 (m, 2H), 7.12 (d, J=8.0 Hz,2H),
5.03 (s, 2H), 2.24 (s, 3H); 13C NMR (100 MHz, CDCl3): d=
147.7, 140.0, 139.4, 135.2, 134.5, 132.2, 130.9, 129.2, 127.7,
126.6, 121.3, 50.4, 21.3; LR-MS (EI, 70 eV): m/z (%)=317
(100), 301 (99), 260 (27), 318 (25); HR-MS (ESI): m/z=
367.9956, calcd. for C15H1579BrNO3S (M+H)+: 367.9951.
1-Phenyl-2-(phenylsulfonyl)ethan-1-one oxime (3ba):
yield: 37.4 mg (68%); white solid; mp 165.9–166.68C (uncor-
rected); 1H NMR (400 MHz, acetone-d6): d=10.9 (s, 1H),
7.83 (m, J=8.0 Hz, 2H), 7.72–7.71 (m, 2H), 7.70–7.66 (m,
1H), 7.57–7.53 (m, 2H), 7.36–7.32 (m, 3H), 4.90 (s, 2H);
13C NMR (100 MHz, acetone-d6): d=146.5, 140.5, 134.8,
133.7, 129.1, 128.9, 128.2 (2C), 126.6, 51.7; LR-MS (EI,
70 eV): m/z (%)=259 (66), 194 (100), 195 (79), 91 (57);
HR-MS (ESI): m/z=276.0680, calcd. for C22H19N2O4 (M+
H)+: 276.0689.
1-(4-Methoxyphenyl)-2-(phenylsulfonyl)ethan-1-one
oxime (3ca): yield: 42.1 mg (69%); white solid; mp 167.9–
168.58C (uncorrected); 1H NMR (400 MHz, CDCl3): d=
7.84 (d, J=7.6 Hz, 2H), 7.61–7.57 (m, 3H), 7.48–7.44 (m,
2H), 6.88 (d, J=9.2 Hz, 2H), 4.72 (s, 2H), 2.84 (s, 3H);
13C NMR (100 MHz, CDCl3): d=161.0, 147.4, 139.4, 133.8,
128.8, 128.5, 128.1, 126.0, 114.0, 55.3, 52.5; LR-MS (EI,
70 eV): m/z (%)=289 (4), 135 (100), 77 (23), 133 (22); HR-
MS (ESI): m/z=306.0787, calcd. for C15H16NO4S (M+H)+:
306.0795.
1H), 7.92 (d, J=8.4 Hz, 2H), 7.85 (d, J=7.2 Hz, 2H), 7.76
(d, J=8.4 Hz, 2H), 7.73–6.69 (m, 1H), 7.60–7.56 (m, 2H),
4.96 (s, 2H); 13C NMR (100 MHz, acetone-d6): d=145.5,
140.1, 139.0, 133.9, 132.0, 129.0, 128.2, 127.3, 118.2, 112.4,
51.3; LR-MS (EI, 70 eV): m/z (%)=284 (1), 130 (100), 77
(70), 221 (48); HR-MS (ESI): m/z=301.0633, calcd. for
C15H13N2O3S (M+H)+: 301.0641.
1-(4-Nitrophenyl)-2-(phenylsulfonyl)ethan-1-one
oxime
(3ha): yield: 46.1 mg (72%); white solid; mp 155.9–157.38C
1
(uncorrected); H NMR (400 MHz, acetone-d6): d=11.52 (s,
1H), 8.23 (d, J=8.8 Hz, 2H), 8.00 (d, J=8.8 Hz, 2H), 7.85
(d, J=7.6 Hz, 2H), 7.73–7.70 (m, 1H), 7.60–7.56 (m, 2H),
5.00 (s, 2H); 13C NMR (100 MHz, acetone-d6): d=148.1,
145.4, 140.9, 140.1, 133.9, 129.0, 128.3, 127.7, 123.3, 51.4;
LR-MS (EI, 70 eV): m/z (%)=304 (81), 240 (100), 193 (73),
77 (55); HR-MS (ESI): m/z=321.0541, calcd. for
C14H13N2O5S (M+H)+: 321.0540.
1-(3-Methoxyphenyl)-2-(phenylsulfonyl)ethan-1-one
oxime (3ia): yield: 33.6 mg (55%); white solid; mp 157.9–
158.68C (uncorrected); 1H NMR (400 MHz, CDCl3): d=
8.58 (s, 1H), 7.84 (d, J=7.6 Hz, 2H), 7.58–7.55 (m, 1H),
7.46–7.42 (m, 2H), 7.28–7.24 (m, 1H), 7.17 (d, J=7.2 Hz,
2H), 6.94–6.92 (m, 1H), 4.73(s, 2H), 3.80(s, 3H); 13C NMR
(100 MHz, CDCl3): d=159.6, 147.6, 139.4, 134.9, 133.8,
129.6, 128.8, 128.4, 119.2, 115.9, 111.8, 55.3, 52.8; LR-MS
(EI, 70 eV): m/z (%)=289 (29), 135 (100), 77 (36), 107 (25);
HR-MS (ESI): m/z=306.0782, calcd. for C15H16NO4S (M+
H)+: 306.0795.
1-(3-Chlorophenyl)-2-(phenylsulfonyl)ethan-1-one oxime
(3ja): yield: 38.9 mg (63%); white solid; mp 161.9–163.48C
1-[4-(Chloromethyl)phenyl]-2-(phenylsulfonyl)ethan-1-
one oxime (3da): yield: 42.6 mg (66%); white solid; mp
1
(uncorrected); H NMR (400 MHz, CDCl3): d=8.72 (s, 1H),
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7.84 (m, J=7.6 Hz, 2H), 7.61–7.57 (m, 1H), 7.56 (s, 1H), References
7.52–7.48 (m, 1H), 7.45 (d, J=7.6 Hz, 2H), 7.34 (d, J=
8.0 Hz, 1H), 7.30–7.26 (m, 1H), 4.71 (s, 3H); 13C NMR
(100 MHz, CDCl3): d=146.5, 139.2, 135.4, 134.6, 134.0,
129.9, 129.8, 128.3, 126.5, 124.8, 52.5; LR-MS (EI, 70 eV):
m/z (%)=293 (88), 229 (100), 193 (89), 228 (66); HR-MS
(ESI): m/z=310.0375, calcd. for C22H19N2O4 (M+H)+:
310.0299.
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1-(2-Methoxyphenyl)-2-(phenylsulfonyl)propan-1-one
oxime (3ka): yield: 25.0 mg (41%); white solid; mp 166.9–
1
167.88C (uncorrected); H NMR (400 MHz, acetone-d6): d=
10.87 (s, 1H), 7.68 (d, J=8.0 Hz, 2H), 7.62–7.59 (m, 1H),
7.49–7.45 (m, 2H), 7.32–7.28 (m, 1H), 7.24 (d, J=7.6 Hz,
1H), 6.94–6.90 (m, 1H), 6.81 (d, J=8.4 Hz, 1H), 4.96 (s,
2H), 3.72 (s, 3H); 13C NMR (100 MHz, acetone-d6): d=
157.3, 147.1, 140.4, 133.3, 130.9, 130.6, 128.7, 128.0, 123.8,
120.3, 110.8, 54.8, 52.6; LR-MS (EI, 70 eV): m/z (%)=289
(13), 134 (100), 148 (64), 147 (41); HR-MS (ESI): m/z=
306.0781. calcd. for C15H16NO4S (M+H)+: 306.0795.
1-(Naphthalen-2-yl)-2-(phenylsulfonyl)ethan-1-one oxime
(3la): yield: 35.8 mg (55%); white solid; mp 177.9–178.98C
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1
(uncorrected); H NMR (400 MHz, acetone-d6): d=11.04 (s,
1H), 8.20 (s, 1H), 7.92–7.88 (m, 3H), 7.87–7.84 (m, 3H),
7.65–7.62 (m, 1H), 7.54–7.51 (m, 4H), 5.04 (s, 2H);
13C NMR (100 MHz, acetone-d6): d=146.5, 140.5, 133.7
(2C), 133.1, 132.2, 128.9, 128.6, 128.3, 127.8, 127.6, 127.0,
126.7, 126.4, 123.6, 51.6; LR-MS (EI, 70 eV): m/z (%)=309
(89), 244 (100), 245 (84), 141 (52); HR-MS (ESI): m/z=
326.0837, calcd. for C18H16NO3S (M+H)+: 326.0845.
1-(4-Methoxyphenyl)-2-(phenylsulfonyl)propan-1-one
oxime (3ma): yield: 39.6 mg (62%); white solid; mp 179.9–
180.78C (uncorrected); 1H NMR (400 MHz, CDCl3): d=
8.16 (s, 1H), 7.84 (d, J=8.0 Hz, 2H), 7.63–7.59 (m, 1H),
7.52–7.48 (m, 2H), 7.35 (d, J=12 Hz, 2H), 6.88 (d, J=
12 Hz, 2H), 4.35–4.30 (m, 1H), 3.82 (s, 3H), 1.62(d, J=
8.0 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=160.1, 151.9,
137.4, 133.7, 129.8, 129.3, 128.9, 124.1, 113.6, 66.3, 55.3, 13.9,
52.6; LR-MS (EI, 70 eV): m/z (%)=288 (13), 107 (100), 147
(63), 77 (45); HR-MS (ESI): m/z=320.0943, calcd. for
C16H18NO4S (M+H)+: 320.0951.
3-Chloro-1-phenyl-2-(phenylsulfonyl)propan-1-one oxime
(3na): yield: 32.9 mg (51%); white solid; mp 161.9–162.78C
1
(uncorrected); H NMR (400 MHz, CDCl3): d=7.69 (d, J=
8.0 Hz, 2H), 7.64–7.61 (m, 3H), 7.46–7.36 (m, 5H), 5.27–
5.24 (m, 1H), 5.15–5.12 (m, 1H), 4.66–4.61 (m, 1H);
13C NMR (100 MHz, CDCl3): d=152.5, 135.6, 134.7, 130.8,
129.1, 128.9, 128.7, 127.7, 127.1, 72.8, 72.6; LR-MS (EI,
70 eV): m/z (%)=307 (13), 104 (100), 141 (45), 77 (67);
HR-MS (ESI): m/z=324.0470, calcd. for C15H1535ClNO3S
(M+H)+: 324.0456.
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Acknowledgements
We thank the NSFC (Nos. 21402046 and 21472039) and
Hunan Provincial Natural Science Foundation of China (No.
13 JJ2018) for financial support. Dr R.- J. Song. also thanks
the Fundamental Research Funds for the Central Universities
and Hunan Province Science and Technology Project (grant
number 2015JC3052).
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8 Copper-Mediated 1,2-Difunctionalization of Styrenes with
Sodium Arylsulfinates and tert-Butyl Nitrite: Facile Access
to a-Sulfonylethanone Oximes
Adv. Synth. Catal. 2016, 358, 1 – 8
Ji Yang, Yan-Yun Liu, Ren-Jie Song, Zhi-Hong Peng,*
Jin-Heng Li*
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