Cross coupling of sulfonyl radicals with silver-based carbenes: A simple approach to β-carbonyl arylsulfones

Article abstract of DOI:10.1039/d0ob00091d

A coupling reaction between sulfonyl radicals and silver-based carbenes has been well established. This simple radical-carbene coupling (RCC) process provided an efficient approach to a variety of β-carbonyl arylsulfones from sodium arylsulfinates and diazo compounds, and was characterized by wide substrate scope, easy scale-up, simple manipulation, accessible starting materials, and mild reaction conditions.

Full text of DOI:10.1039/d0ob00091d

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DOI: 10.1039/D0OB00091D
ARTICLE
Cross Coupling of Sulfonyl Radical with Silver-Based Carbene: A
Simple Approach to β-Carbonyl Arylsulfones
Received 00th January 20xx,
Accepted 00th January 20xx
Hanghang Wang, Pengcheng Lian, Yonggao Zheng, Jingjing Li, Xiaobing Wan*
DOI: 10.1039/x0xx00000x
A coupling reaction between sulfonyl radical and silver-based carbene has been well established. This simple radical-
carbene coupling (RCC) process provided an efficient approach to a variety of β-carbonyl arylsulfones from sodium
arylsulfinates and diazo compounds, which was distinguished by wide substrate scopes, easy scale-up, simple
manipulation, accessible starting materials, and mild reaction conditions.
radical acceptors (Scheme 1a).9g,9h,10d-j As a continuation of our
research interest in exploiting the cross coupling of radicals
with carbenes, we reported herein the construction of
Introduction
Radicals are generally considered as highly reactive and
multifunctional intermediates,1 which play vital roles in a wide
range of transformations such as functionalization of alkenes,2
alkynes,3 and (hetero)arenes4 and C–H bond5 etc. On the other
hand, transition-metal carbenes,6 usually generated in situ
from metal-induced decomposition of diazo compounds, are
also highly efficient species, which are confirmed by X–H
insertion,7a-c cross-coupling,7d cyclization and ylide reactions.7e-
arylsulfone using this strategy as shown in Scheme 1b. Cross-
coupling of sulfonyl radical II with a transition metal carbene
yields intermediate III, which then provides the desired β-
carbonyl arylsulfones by protonlysis. To the best of our
knowledge, there have been no reports of cross-coupling of
sulfonyl radical and metal-carbene to form arylsulfone
compounds.11 Considering the important use of arylsulfone
compounds and the shortcomings of existing methods, this
methodology provides a valuable alternative for their synthesis.
k
Although great progress have been made in the research of
radicals or transition metal carbenes, reactions based-upon
radical-carbene coupling strategy still in its infancy. This might
be due to the high reactivity and low concentration of radicals
and carbenes, making them difficult to achieve highly selective
cross-couplings. Clearly, synthetic strategies based upon
O
H-abstraction, Carbonylation
Alkenylation, Arylation etc.
S
I
Ar
(a)
ONa
SET
acceptors
l
Previous work
radical-carbene coupling (RCC) reactions will provide
a
M
O
S
O
S
radica
R2
conceptually novel and efficient approach to multifunctional
molecules. In recent years, we have obtained a series of
functional molecules such as β-ester-γ-amino ketones,8a,b
indoles,8c isoxazolines,8d and perfluoroalkanesulfinate esters8e
through this strategy, and initially verified its potential in
synthetic chemistry.
R1
Ar
Ar
O
O
RCC
O
reac
ti
II
O
O
on
R2
R2
O
O
S
Protonlysis
(b)
Ar
S
H
R1
Ar
M
O
R1
O
This work
III
Arylsulfone motifs are ubiquitous in biologically active
molecules, drugs and functional materials and also served as
versatile building blocks in many transformations.9 Thererfore,
a handful of methods have been developed to introduce
arylsulfonyl groups into organic molecules with sulfonylation
reagents.10 Among these reagents, sodium arylsulfinate is a
stable, inexpensive and easy to prepare compound that can
form sulfonyl radical by single electron transfer (SET) process,
making it a classical sulfonylation reagent for a variety of
Scheme 1 Synthetic application of sodium arylsulfinate.
Results and discussion
Considering that AgNO3/K2S2O8 were often used to generate
sulfonyl radical from sodium benzensulfinate 1a,10e,h,j we
tested their reaction with ethyl diazoacetate 2a to form β-
ester sulfones 3aa. With this in mind, we firstly screened a
range of solvents (For details, see Supporting Information,
Table S1, entries 1–6) and found trace amount of desired
product 3aa in MeCN. To our delight, the yield of 3aa could be
increased to 36% by the 1:1 mixture of MeCN and H2O as
reaction medium (Table S1, entry 7). This result prompted us
to adjust the ratio of MeCN to H2O, and the best result was
*Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry,
Chemical Engineering and Materials Science, Soochow University, Suzhou 215123,
P. R. China. E-mail: wanxb@suda.edu.cn
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
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obtained at a ratio of 10:1 (Table S1, entry 10). Next, we were compatible with this reaction. To our delight, the
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DOI: 10.1039/D0OB00091D
screened the amount of K2S2O8 used. To our surprise, even substrate bearing internal olefin was also good reaction
with 0.5 equivalents of K2S2O8, the yield of 3aa could be partner for this transformation and the product 3ak was
further increased to 68% (Table 1, entry 1). Other silver obtained in satisfactory output. α-Fully substituted diazo
catalysts and oxidants resulted in a reduced 3aa yield (Table 1, compounds 2m and 2n were well tolerated in this reaction,
entries 2-7). A series of N, N-bidentate ligands could promote furnishing the corresponding product 3am and 3an in 71% and
the formation of product 3aa (Table 1, entries 8-10). Control 66% yields, respectively. This transformation was also
experiments showed that both AgNO3 and K2S2O8 were illustrated with diazo amide and delivered the target product
essential to this coupling reaction (Table 1, entries 18-19), 3ap in 46% yield. To showcase the synthetic utility of this
indicating sulfonyl radical and silver-based carbene were methodology, diazo ester 2o from epiandrosterone was
involved in this transformation. After extensive screenings, we utilized as the substrate, leading to the target product 3ao in
found the optimum conditions: using 10 mol% AgNO3, 10 satisfactory 61% yield.
mol% 1,10-phenanthroline and 0.5 equiv. K2S2O8, reacting in Table 2 Scope of diazo compoundsa,b
MeCN/H2O at 70 oC for 4 h to obtain the coupling product 3aa
in a high yield of 80% (Table 1, entry 13).
O
O
O
SO2Na
AgNO3, 1,10-Phen,
K2S2O8
N2
S
R2
+
R2
O
MeCN/H2O = 10:1
air, 70 oC, 4 h
R1
R1
Table 1 Optimization of the reaction conditionsa
1a
2
3ab-3ap
SO2Na
O
O
Catalyst, Additive
O
O
O
O
O
O
O
+
N2
S
S
MeCN/H2O = 10:1 (2 mL)
70 oC, 4 h
S
S
OEt
OnBu
OEt
OiPr
O
O
O
O
O
3ab, 76%
3ac, 70%
3ad, 72%
1a
2a
3aa
Yield [%]b
Entry
Catalyst (mol%)
Additive
Ligand (mol%)
Ph
TMS
O
O
O
O
O
S
O
S
___
___
___
___
___
___
___
S
1
2
AgNO3 (20)
CF3CO2Ag (20)
AgOAc (20)
Ag2CO3 (20)
AgF (20)
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
Na2S2O8
(NH4)2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
68
62
58
63
59
65
48
76
73
68
77
77
80
72
68
70
57
< 5
< 5
O
O
O
O
O
O
3ae, 87%
3af, 87%
3ag, 72%
3
4
O
O
O
S
O
Ph
O
O
5
S
S
S
6
AgNO3 (20)
AgNO3 (20)
AgNO3 (20)
AgNO3 (20)
AgNO3 (20)
AgNO3 (20)
AgNO3 (20)
AgNO3 (10)
AgNO3 (5)
O
O
OBn
Ph
O
O
O
O
7
3ah, 81%
3ai, 66%
3aj, 80%
8
L1 (20)
L2 (20)
L3 (20)
L1 (15)
L1 (10)
L1 (10)
L1 (10)
L4 (10)
L5 (10)
L6 (10)
L1 (10)
L1 (10)
9
O
O
O
O
O
O
O
10
11
12
13
14
15
16
17
18
19
S
S
S
O
O
O
O
O
3ak, 55%
3al, 74%
3am, 71%
O
H
O
O
O
O
S
AgNO3 (10)
AgNO3 (10)
O
S
O
H
N
Ph
OEt
H
O
O
S
O
O
Ph
AgNO3 (10)
___
3an, 66%
3ao, 61%
3ap, 46%
K2S2O8
___
AgNO3 (10)
aReaction conditions: 1a (0.5 mmol), 2 (1.0 mmol), AgNO3
aUnless otherwise noted, all the reactions were run with 1a
(0.5 mmol), 2a (1 mmol) and additive (0.25 mmol) in
MeCN/H2O = 10: 1 (2.0 mL) at 70 oC under air. bisolated yields.
L1 = 1,10-phenanthroline, L2 = 2,2'-bipyridine, L3 = 2,2':6',2''-
terpyridine, L4 = 4,7-dimethoxy-1,10-phenanthroline, L5 = 4,7-
diphenyl-1,10-phenanthroline, L6 = 3,8-dibromo-1,10-phenan-
throline.
(0.05 mmol), 1,10-Phen (0.05 mmol), K2S2O8 (0.25 mmol),
stirred in MeCN/H2O = 10: 1 (2 mL) at 70 C for 4 h under air.
bIsolated yields.
o
Next, we tried to expand the substrate scope by
investigating different sodium sulfinate, as shown in Table 3.
Satisfactorily, the benzene ring carrying both electron-
withdrawing and electron-donating groups were well
tolerated, affording the corresponding β-carbonyl arylsulfones
3ba-3ia in moderate to good yields. The halogens such as F, Cl,
and Br at para- or ortho- positions were tolerated to this
process and gave the desired products in good yields (3ea-3ga,
3ia). The reaction revealed low efficiency when thienyl-
substituted sodium arylsulfinate (3ja) was used as substrate.
Unfortunately, naphthyl and alkyl-substituted sodium sulfinate
failed to get the corresponding products 3ka and 3la. To
further demostrate the practicability of this coupling reaction,
With the optimal reaction conditions in hand, we set out to
explore the substrate scope of this transformation. A varity of
α-diazo carbonyl compounds were tested and the results are
listed in Table 2. It turned out that all the selected α-diazo
carbonyl compounds could take part in this transformation
well, leading to the corresponding products in moderate to
excellent yields (3ab-3ap). Notably, functional groups such as
naphthyl (3af), TMS (3ag), thienyl (3ah) and methyl ether (3al)
2 | J. Name., 2012, 00, 1-3
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the template reaction was carried on 10 mmol scale and the indicating that cross-coupling of the sulfonyl radical and silver-
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desired product 3aa was obtained in 74% isolated yield, as based carbene occurred in the reaction.DIOnI:o1r0d.1e0r39to/Dd0OetBe0r0m09in1De
shown in Scheme 2.
the source of hydrogen in the β-carbonyl arylsulfones,
MeCN/D2O or CD3CN/H2O were used as solvent for this
transformation and the results indicated that water
participates in the final protonation process (Scheme 3d).
Taken together, these results provided clear evidence that the
in situ generation of sulfonyl radical and silver-based carbene
and their highly selective cross-coupling were invovled in this
β-carbonyl arylsulfones formation reaction.
Table 3 Scope of sodium sulfinatesa,b
O
O
O
AgNO3, 1,10-Phen, K2S2O8
R
N2
S
R
SO2Na
+
OEt
OEt
O
MeCN/H2O = 10:1
air, 70 oC, 4 h
1
2a
3aa-3ja
MeO
O
O
O
O
O
O
S
S
S
O
O
OEt
OEt
standard conditions
3.0 equiv TEMPO
OEt
O
(a)
O
O
1a
+
2a
S
OEt
O
3aa, 80%
3ba, 63%
3ca, 54%
3aa, < 5%
tBu
F
Cl
O
O
O
O
S
O
S
O
S
1a
2a
OEt
OEt
OEt
O
O
O
+
standard conditions
O
(b)
3ea, 62%
3da, 51%
3fa, 65%
S
O
Br
Br
F3C
O
O
O
O
S
O
S
O
S
4
OEt
OEt
OEt
O
O
O
3ga, 59%
tBu
3ia, 57%
1a
2a
3ha, 53%
O
standard conditions
+
(c)
O
OEt
O
S
O
O
S
O
O
S
OEt
S
O
5
tBu
OEt
O
OEt
O
Detected in the presence of Ag catalyst
Not detected in the absence of Ag catalyst
3la, <5%
3ka, <5%
3ja, 25%
aReaction conditions: 1a (0.5 mmol), 2 (1.0 mmol), AgNO3
N2
O
O
(0.05 mmol), 1,10-Phen (0.05 mmol), K2S2O8 (0.25 mmol),
standard conditions
OEt
1a
+
(d)
S
o
stirred in MeCN/H2O = 10: 1 (2 mL) at 70 C for 4 h under air.
OEt
O
O
H/D
bIsolated yields.
CH3CN/D2O = 10:1
CD3CN/H2O = 10:1
[D]-3am
[H]-3am
AgNO3 (10 mol%)
1,10-Phen (10 mol%)
K2S2O8 (50 mol%)
O
SO2Na
O
O
Scheme 3 Probe for the possible mechanism.
N2
+
S
OEt
OEt
MeCN/H2O = 10:1 (40 mL)
70 oC, 4 h
O
Based upon above results and literatures, a plausible
reaction mechanism was proposed, as shown in Scheme 4.
Sulfonyl radical A was produced by the single electron transfer
oxidation of sodium sulfinate 1 promoted by K2S2O8,10d,h-j and
then cross coupled with silver carbene B12 to form the
1a, 10 mmol
2a, 20 mmol
3aa
1.67g, 74% yield
Scheme 2 Gram-Scale Reaction.
Further experiments were conducted to gain insight into the
mechanism of this β-carbonyl arylsulfones formation reaction.
The formation of product 3aa was inhibited significantly by
adding 2,2,6,6-tetramethylpiperidinoxy (TEMPO) to the
reaction mixture (Scheme 3a). The addition of 1,1-
diphenylethylene to the reaction system delivered the sulfonyl
radical adduct 4 (Scheme 3b). By adding 4-tert-butylstyrene to
the reaction system under the standard conditions, the
cyclopropanation product 5 was detected by LCMS. However,
it failed to detect the cyclopropanation product 5 in the
absence of Ag catalyst (Scheme 3c). The results indicated the
Ag catalyst was essential and Ag-based carbene was generated
in situ in this transformation. When 2,6-di-tert-butyl-4-
methylphenol (BHT) was subjected to the reaction system, the
adduct 6 of sulfonyl radical and BHT was obtained in 10% yield
(see Supporting Information, Scheme S3). It is particularly
worth mentioning that compound 7 was detected by LCMS,
intermediate C. Finally, the intermediate
protonolysis and gave the desired β-carbonyl arylsulfones 3.
C underwent
N2
OEt
H
O
2
O
S
Ar
ONa
[Ag]
[Ag]
1
N2
2-
S2O8
OEt
O
B
EtO
EtO
O
S
O
S
O
S
O
O
H
H2O
Ar
Ar
Ag
Ar
H
radical-carbene
coupling
O
H
H
O
2-
O
SO4
[Ag]
A
C
3
Scheme 4 Proposed Reaction Mechanism.
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J. Name., 2013, 00, 1-3 | 3
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(400 MHz, CDCl3) δ 7.96-7.94 (m, 2H), 7.71-7.67 (Vmie,w1AHrtic),le7O.n6li0ne-
7.56 (m, 2H), 4.15 (s, 2H), 4.07 (t, J = 6.7DHOzI:,120H.10),319/.D505O-1B.04080(9m1D,
2H), 1.31-1.22 (m, 2H), 0.87 (t, J = 7.4 Hz, 3H). 13C NMR (100
MHz, CDCl3) δ 162.2, 138.6, 134.1, 129.0, 128.2, 65.9, 60.7,
30.0, 18.6, 13.3. HRMS (ESI-TOF): Anal. Calcd. For
C12H16O4S+Na+: 279.0662, Found: 279.0668. IR (neat, cm-1): υ
2960, 2937, 2875, 1736, 1448, 1279, 1150, 1083.
Cyclohexyl 2-(phenylsulfonyl)acetate (3ad) petroleum
ether/ ethylacetate = 5:1, colorless oil, 72% yield (101.3 mg).
1H NMR (400 MHz, CDCl3) δ 7.97-7.94 (m, 2H), 7.71-7.67 (m,
1H), 7.60-7.56 (m, 2H), 4.76-4.57 (m, 1H), 4.12 (s, 2H), 1.77-
1.64 (m, 4H), 1.53-1.48 (m, 1H), 1.37-1.18 (m, 5H). 13C NMR
(100 MHz, CDCl3) δ 161.7, 138.7, 134.1, 129.1, 128.4, 75.0,
61.1, 31.0, 25.0, 23.3. HRMS (ESI-TOF): Anal. Calcd. For
C14H18O4S+Na+: 305.0818, Found: 305.0822. IR (neat, cm-1): υ
3065, 2937, 2860, 1731, 1448, 1281, 1150, 1083.
Conclusions
In summary, by careful control of the reaction conditions, we
achieved a highly selective cross-coupling of sulfonyl radicals
with silver-based carbene to form β-carbonyl arylsulfones. This
strategy was also featured by simple manipulation, easy scale-
up, wide substrate scopes and mild reaction conditions.
Investigations on other radical carbene coupling (RCC)
reactions are underway in our laboratory.
Experimental
General information
All manipulations were carried out under air atmosphere.
Column chromatography was generally performed on silica gel
(300-400 mesh) and reactions were monitored by thin layer
chromatography (TLC) using UV light to visualize the course of
the reactions. The 1H NMR (400MHz), 13C NMR (100 MHz) data
were recorded using CDCl3 as solvent at room temperature.
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.
Phenethyl 2-(phenylsulfonyl)acetate (3ae) petroleum
ether/ ethylacetate = 5:1, white solid, 87% yield (131.6 mg),
o
1
melting point: 69.5-71.5 C. H NMR (400 MHz, CDCl3) δ 7.89-
7.87 (m, 2H), 7.65-7.61 (m, 1H), 7.53-7.49 (m, 2H), 7.28-7.24
(m, 2H), 7.22-7.18 (m, 1H), 7.13-7.11 (m, 2H), 4.25 (t, J = 7.1
Hz, 2H), 4.09 (s, 2H), 2.82 (t, J = 7.1 Hz, 2H). 13C NMR (100 MHz,
CDCl3) δ 162.1, 138.4, 136.8, 134.1, 129.0, 128.6, 128.3, 128.2,
126.5, 66.4, 60.6, 34.3. HRMS (ESI-TOF): Anal. Calcd. For
C16H16O4S+Na+: 327.0662, Found: 327.0652. IR (neat, cm-1): υ
3005, 2968, 2935, 1737, 1448, 1270, 1161, 1082.
General procedures
Sodium arylsulfinates (0.5 mmol), AgNO3 (0.05 mmol), 1,10-
phen (0.05 mmol) and K2S2O8 (0.25 mmol) were added to test
tube charged with stir bar. MeCN/H2O =10:1 (2.0 mL) and
diazo compound (1.0 mmol) were added via syringe. The
reaction mixture was heated at 70 °C for 4 h, which was then
quenched with saturated Na2SO3 solution and extracted with
ethyl acetate (20 mL × 3). The organic layers were combined
and dried with anhydrous Na2SO4. Removal of the organic
solvent followed by flash column chromatographic purification
afforded the desired products using petroleum and ethyl
acetate.
2-(naphthalen-1-yl)ethyl 2-(phenylsulfonyl)acetate (3af)
petroleum ether/ ethylacetate = 5:1, white solid, 87% yield
1
(154.2 mg), melting point: 71.4-72.9 oC. H NMR (400 MHz,
CDCl3) δ 7.94 (d, J = 8.0 Hz, 1H), 7.88-7.83 (m, 3H), 7.73 (d, J =
8.0 Hz, 1H), 7.61-7.57 (m, 1H), 7.52-7.45 (m, 4H), 7.39-7.35 (m,
1H), 7.27-7.26 (m, 1H), 4.38 (t, J = 7.3 Hz, 2H), 4.09 (s, 2H), 3.29
(t, J = 7.3 Hz, 2H). 13C NMR (100 MHz, CDCl3) δ 162.2, 138.5,
134.2, 133.7, 132.7, 131.7, 129.1, 128.8, 128.3, 127.5, 127.0,
126.2, 125.6, 125.4, 123.2, 66.0, 60.8, 31.6. HRMS (ESI-TOF):
Anal. Calcd. For C20H18O4S+Na+: 377.0818, Found: 377.0817. IR
(neat, cm-1): υ 3060, 3005, 2968, 2935, 1733, 1448, 1270,
1160.
2-(trimethylsilyl)ethyl 2-(phenylsulfonyl)acetate (3ag)
petroleum ether/ ethylacetate = 5:1, colorless oil, 72% yield
(107.3 mg). 1H NMR (400 MHz, CDCl3) δ 7.97-7.94 (m, 2H),
7.69-7.67 (m, 1H), 7.60-7.56 (m, 2H), 4.18-4.14 (m, 2H), 4.11 (s,
2H), 0.93-0.89 (m, 2H), 0.01 (s, 9H). 13C NMR (100 MHz, CDCl3)
δ 162.3, 138.7, 134.1, 129.1, 128.4, 64.7, 60.9, 17.0, -1.8.
HRMS (ESI-TOF): Anal. Calcd. For C13H20O4SSi+Na+: 323.0744,
Found: 323.0743. IR (neat, cm-1): υ 3066, 2954, 2899, 1736,
1448, 1274, 1150, 1084.
2-(thiophen-2-yl)ethyl 2-(phenylsulfonyl)acetate (3ah)
petroleum ether/ ethylacetate = 5:1, yellowish oil, 81% yield
(125.0 mg). 1H NMR (400 MHz, CDCl3) δ 7.93-7.90 (m, 2H),
7.68-7.65 (m, 1H), 7.57-7.53 (m, 2H), 7.14-7.13 (m, 1H), 6.92-
6.90 (m, 1H), 6.80-6.79 (m, 1H), 4.28 (t, J = 6.8 Hz, 2H), 4.13 (s,
2H), 3.05 (t, J = 6.8 Hz, 2H). 13C NMR (100 MHz, CDCl3) δ 162.1,
138.8, 138.5, 134.2, 129.1, 128.3, 126.9, 125.6, 124.0, 66.1,
60.7, 28.6. HRMS (ESI-TOF): Anal. Calcd. For C14H14O4S2+Na+:
333.0226, Found: 333.0226. IR (neat, cm-1): υ 3104, 3006,
2962, 2853, 1736, 1449, 1270, 1160.
Ethyl 2-(phenylsulfonyl)acetate (3aa) petroleum ether/
ethylacetate = 5:1, colorless oil, 80% yield (91.0 mg), 10.0
1
mmol, 74% yield (1.67 g). H NMR (400 MHz, CDCl3) δ 7.97-
7.95 (m, 2H), 7.72-7.68 (m, 1H), 7.61-7.57 (m, 2H), 4.17-4.12
(m, 4H), 1.19 (t, J = 7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ
162.2, 138.7, 134.2, 129.2, 128.5, 62.3, 61.0, 13.8. HRMS (ESI-
TOF): Anal. Calcd. For C10H12O4S+Na+: 251.0349, Found:
251.0353. IR (neat, cm-1): υ 3066, 2984, 2926, 2852, 1736,
1447, 1276, 1149.
Isopropyl 2-(phenylsulfonyl)acetate (3ab) petroleum ether/
1
ethylacetate = 6:1, colorless oil, 76% yield (91.4 mg). H NMR
(400 MHz, CDCl3) δ 7.97-7.94 (m, 2H), 7.71-7.67 (m, 1H), 7.60-
7.57 (m, 2H), 4.99-4.93 (m, 1H), 4.12 (s, 2H), 1.15 (d, J = 6.3 Hz,
6H). 13C NMR (100 MHz, CDCl3) δ 161.6, 138.6, 134.1, 129.0,
128.3, 70.2, 61.0, 21.2. HRMS (ESI-TOF): Anal. Calcd. For
C11H14O4S+Na+: 265.0505, Found: 265.0511. IR (neat, cm-1): υ
3067, 2984, 2940, 2881, 1731, 1448, 1278, 1151.
Butyl 2-(phenylsulfonyl)acetate (3ac) petroleum ether/
1
ethylacetate = 6:1, colorless oil, 70% yield (88.6 mg). H NMR
4 | J. Name., 2012, 00, 1-3
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Organic & Biomolecular Chemistry
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Benzyl 2-(phenylsulfonyl)acetate (3ai) petroleum ether/
ethylacetate = 5:1, colorless oil, 66% yield (94.1 mg). H NMR dro-1H-cyclopenta[a]phenanthren-3-yl DOI:21-0(.p10h3e9n/Dy0lsOuBlf0o0n09y1l)D-
(400 MHz, CDCl3) δ 7.86-7.83 (m, 2H), 7.64-7.60 (m, 1H), 7.49- acetate (3ao) petroleum ether/ ethylacetate = 5:1, white solid,
7.45 (m, 2H), 7.35-7.31 (m, 3H), 7.25-7.23 (m, 2H), 5.09 (s, 2H), 61% yield (141.1 mg), melting point: 146.2-148.1 C. H NMR
4.15 (s, 2H). 13C NMR (100 MHz, CDCl3) δ 162.1, 138.4, 134.3, (400 MHz, CDCl3) δ 7.96-7.94 (m, 2H), 7.71-7.68 (m, 1H), 7.60-
134.1, 129.1, 128.54, 128.47, 128.4, 128.3, 67.8, 60.8. HRMS 7.57 (m, 2H), 4.71-4.65 (m, 1H), 4.09 (s, 2H), 2.47-2.40 (m, 1H),
(ESI-TOF): Anal. Calcd. For C15H14O4S+Na+: 313.0505, Found: 2.11-2.01 (m, 1H), 1.92-1.91 (m, 1H), 1.77 -1.13 (m, 16H), 0.98-
313.0507. IR (neat, cm-1): υ 3065, 3006, 2943, 2849, 1737, 0.94 (m, 1H), 0.85 (s, 3H), 0.82 (s, 3H), 0.71-0.68 (m, 1H). 13C
(3S,8R,9S,10S,13S,14S)-10,13-dimethyl-17-oxohexadecahy-
View Article Online
1
o
1
1448, 1273, 1148.
NMR (100 MHz, CDCl3) δ 221.0, 161.7, 138.6, 134.1, 129.0,
Benzhydryl 2-(phenylsulfonyl)acetate (3aj) petroleum 128.4, 75.8, 61.1, 54.0, 51.1, 47.6, 44.3, 36.3, 35.7, 35.4, 34.8,
ether/ ethylacetate = 5:1, yellowish oil, 80% yield (145.1 mg). 33.3, 31.3, 30.5, 28.0, 26.8, 21.6, 20.3, 13.6, 12.0. HRMS (ESI-
1H NMR (400 MHz, CDCl3) δ 7.76-7.74 (m, 2H), 7.57-7.53 (m, TOF): Anal. Calcd. For C27H36O5S +Na+: 495.2176, Found:
1H), 7.40-7.36 (m, 2H), 7.32-7.24 (m, 10H), 6.82 (s, 1H), 4.17 (s, 495.2160. IR (neat, cm-1): υ 3010, 2928, 2848, 1742, 1448,
2H). 13C NMR (100 MHz, CDCl3) δ 161.4, 138.7, 138.2, 134.1, 1279, 1160, 1086.
129.1, 128.4, 128.3, 128.1, 127.1, 78.9, 60.9. HRMS (ESI-TOF):
N,N-dibenzyl-2-(phenylsulfonyl)acetamide (3ap) petroleum
Anal. Calcd. For C21H18O4S+Na+: 389.0818, Found: 389.0804. IR ether/ ethylacetate = 5:1, white solid, 46% yield (86.0 mg),
(neat, cm-1): υ 3063, 3007, 2929, 2853, 1738, 1448, 1265, melting point: 83.9-85.6 C. H NMR (400 MHz, CDCl3) δ 7.90-
o
1
1149. 7.88 (m, 2H), 7.65-7.62 (m, 1H), 7.53-7.49 (m, 2H), 7.36-7.26
But-2-en-1-yl 2-(phenylsulfonyl)acetate (3ak) petroleum (m, 6H), 7.24-7.22 (m, 2H), 7.11 (d, J = 7.1 Hz, 2H), 4.65 (s, 2H),
ether/ ethylacetate = 5:1, colorless oil, 55% yield (69.5 mg). 1H 4.58 (s, 2H), 4.26 (s, 2H). 13C NMR (100 MHz, CDCl3) δ 162.1,
NMR (400 MHz, CDCl3) δ 7.96-7.93 (m, 2H), 7.71-7.67 (m, 1H), 138.7, 136.1, 135.4, 134.0, 129.02, 128.99, 128.6, 128.4, 128.0,
7.59-7.56 (m, 2H), 5.79-5.70 (m, 1H), 5.48-5.40 (m, 1H), 4.64- 127.8, 127.5, 126.1, 59.8, 50.8, 49.0. HRMS (ESI-TOF): Anal.
4.63 (m, 0.3H), 4.50-4.48 (m, 1.7H), 4.144 (s, 0.3H), 4.137 (s, Calcd. For C22H21NO3S+Na+: 402.1134, Found: 402.1136. IR
1.7H), 1.70-1.68 (m, 2.55H), 1.66-1.64 (m, 0.45H). 13C NMR (neat, cm-1): υ 3086, 3002, 2955, 2916, 1650, 1445, 1284,
(100 MHz, CDCl3) δ 162.1, 162.0, 138.5, 134.13, 134.10, 132.6, 1142, 1089.
130.7, 129.05, 129.03, 128.41, 128.38, 123.6, 122.7, 66.7, 61.5,
Ethyl 2-tosylacetate (3ba) petroleum ether/ ethylacetate =
60.8, 17.6, 12.9. HRMS (ESI-TOF): Anal. Calcd. For 6:1, colorless oil, 63% yield (75.6 mg). 1H NMR (400 MHz,
C12H14O4S+Na+: 277.0505, Found: 277.0517. IR (neat, cm-1): υ CDCl3) δ 7.82 (d, J = 8.3 Hz, 2H), 7.37 (d, J = 8.3 Hz, 2H), 4.15 (q,
3064, 3009, 2944, 2856, 1736, 1448, 1273, 1149.
J = 7.1 Hz, 2H), 4.10 (s, 2H), 2.46 (s, 3H), 1.20 (t, J = 7.1 Hz, 3H).
3-methoxypropyl 2-(phenylsulfonyl)acetate (3al) petroleum 13C NMR (100 MHz, CDCl3) δ 162.4, 145.3, 135.7, 129.7, 128.5,
ether/ ethylacetate = 3:1, colorless oil, 74% yield (100.2 mg). 62.3, 61.0, 21.6, 13.8. HRMS (ESI-TOF): Anal. Calcd. For
1H NMR (400 MHz, CDCl3) δ 7.97-7.91 (m, 2H), 7.72-7.68 (m, C11H14O4S+Na+: 265.0505, Found: 265.0515. IR (neat, cm-1): υ
1H), 7.61-7.57 (m, 2H), 4.18 (t, J = 6.5 Hz, 2H), 4.14 (s, 2H), 3.36 2983, 2929, 2854, 1737, 1400, 1276, 1147, 1084.
(t, J = 6.5 Hz, 1H), 3.30 (s, 3H), 1.85-1.79 (m, 2H). 13C NMR (100
Ethyl
2-((4-methoxyphenyl)sulfonyl)acetate
(3ca)
MHz, CDCl3) δ 162.2, 138.6, 134.2, 129.1, 128.3, 68.4, 63.4, petroleum ether/ ethylacetate = 4:1, colorless oil, 54% yield
1
60.8, 58.5, 28.4. HRMS (ESI-TOF): Anal. Calcd. For (68.8 mg). H NMR (400 MHz, CDCl3) δ 7.87 (d, J = 9.0 Hz, 2H),
C12H16O5S+Na+: 295.0611, Found: 295.0619. IR (neat, cm-1): υ 7.03 (d, J = 9.0 Hz, 2H), 4.15 (q, J = 7.1 Hz, 2H), 4.09 (s, 2H),
3065, 2930, 2878, 1737, 1448, 1278, 1151, 1083.
3.89 (s, 3H), 1.21 (t, J = 7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3)
Ethyl 2-(phenylsulfonyl)propanoate (3am) petroleum δ 164.1, 162.5, 130.7, 130.1, 114.3, 62.2, 61.1, 55.6, 13.8.
ether/ ethylacetate = 6:1, colorless oil, 71% yield (85.3 mg). 1H HRMS (ESI-TOF): Anal. Calcd. For C11H14O5S+Na+: 281.0454,
NMR (400 MHz, CDCl3) δ 7.91-7.88 (m, 2H), 7.71-7.67 (m, 1H), Found: 281.0458. IR (neat, cm-1): υ 3101, 2983, 2943, 2844,
7.60-7.56 (m, 2H), 4.11 (dq, J = 0.6, 7.2 Hz, 2H), 4.06 (q, J = 7.2 1736, 1259, 1143, 1085.
Hz, 1H), 1.58 (d, J = 7.2 Hz, 3H), 1.15 (t, J = 7.2 Hz, 3H). 13C NMR
Ethyl
2-((4-(tert-butyl)phenyl)sulfonyl)acetate
(3da)
(100 MHz, CDCl3) δ 166.1, 136.9, 134.1, 129.2, 128.9, 65.3, petroleum ether/ ethylacetate = 6:1, colorless oil, 51% yield
1
62.1, 13.7, 11.6. HRMS (ESI-TOF): Anal. Calcd. For (70.9 mg). H NMR (400 MHz, CDCl3) δ 7.87 (d, J = 8.6 Hz, 2H),
C11H14O4S+Na+: 265.0505, Found: 265.0509. IR (neat, cm-1): υ 7.59 (d, J = 8.6 Hz, 2H), 4.17-4.11 (m, 4H), 1.35 (s, 9H), 1.17 (t, J
3066, 2985, 2942, 1734, 1448, 1260, 1145, 1083.
= 7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 162.3, 158.2, 135.7,
Ethyl 2-(phenylsulfonyl)butanoate (3an) petroleum ether/ 128.3, 126.1, 62.1, 61.0, 35.2, 30.9, 13.7. HRMS (ESI-TOF):
1
ethylacetate = 6:1, colorless oil, 66% yield (83.6 mg). H NMR Anal. Calcd. For C14H20O4S+Na+: 307.0975, Found: 307.0981. IR
(400 MHz, CDCl3) δ 7.91-7.88 (m, 2H), 7.71-7.67 (m, 1H), 7.60- (neat, cm-1): υ 3065, 2964, 2872, 1738, 1467, 1270, 1153,
7.56 (m, 2H), 4.11 (dq, J = 0.6, 7.2 Hz, 2H), 4.06 (q, J = 7.2 Hz, 1082.
1H), 1.58 (d, J = 7.2 Hz, 3H), 1.15 (t, J = 7.2 Hz, 3H). 13C NMR
Ethyl 2-((4-fluorophenyl)sulfonyl)acetate (3ea) petroleum
(100 MHz, CDCl3) δ 166.1, 136.9, 134.1, 129.2, 128.9, 65.3, ether/ ethylacetate = 6:1, colorless oil, 62% yield (75.2 mg). 1H
62.1, 13.7, 11.6. HRMS (ESI-TOF): Anal. Calcd. For NMR (400 MHz, CDCl3) δ 8.01-7.96 (m, 2H), 7.30-7.24 (m, 2H),
C12H16O4S+Na+: 279.0662, Found: 279.0669. IR (neat, cm-1): υ 4.18-4.13 (m, 4H), 1.21 (t, J = 7.1 Hz, 3H). 13C NMR (100 MHz,
3069, 2979, 2852, 1731, 1451, 1187, 1162, 1079.
CDCl3) δ 166.0 (d, J = 257.2 Hz), 162.2, 134.6 (d, J = 3.2 Hz),
131.5 (d, J = 9.8 Hz), 116.4 (d, J = 22.8 Hz), 62.3, 60.9, 13.8. 19
F
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Organic & Biomolecular Chemistry
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ARTICLE
NMR (376 MHz, CDCl3) δ -102.4. HRMS (ESI-TOF): Anal. Calcd.
Journal Name
A
Project Funded by the Priority Academic Program
View Article Online
For C10H11FO4S+Na+: 269.0254, Found: 269.0258. IR (neat, cm- Development of Jiangsu Higher Education Institutions (PAPD),
DOI: 10.1039/D0OB00091D
1): υ 3107, 3073, 2986, 2943, 1736, 1494, 1292, 1147.
NSFC (21971175, 21572148).
Ethyl 2-((4-chlorophenyl)sulfonyl)acetate (3fa) petroleum
ether/ ethylacetate = 6:1, colorless oil, 65% yield (84.4 mg). 1H
NMR (400 MHz, CDCl3) δ 7.92-7.88 (m, 2H), 7.58-7.55 (m, 2H),
4.18-4.13 (m, 4H), 1.21 (t, J = 7.1 Hz, 2H). 13C NMR (100 MHz,
CDCl3) δ 162.1, 140.9, 137.0, 130.0, 129.4, 62.4, 60.7, 13.7.
HRMS (ESI-TOF): Anal. Calcd. For C10H1135ClO4S+Na+: 284.9959,
Found: 284.9968; Anal. Calcd. For C10H1137ClO4S+Na+:
286.9929, Found: 286.9917. IR (neat, cm-1): υ 3093, 2985,
2941, 1736, 1475, 1277, 1151, 1084.
Notes and references
1
For selected reviews, see: (a) C. P. Jasperse, D. P. Curran and
T. L. Fevig, Chem. Rev., 1991, 91, 1237; (b) A. Studer, Chem.
Soc. Rev., 2004, 033, 267; (c) M. Yan, J. C. Lo, J. T. Edwards
and P. S. Baran, J. Am. Chem. Soc., 2016, 138, 12692; (d) J.
Xie, H. Jin and A. S. K. Hashmi, Chem. Soc. Rev., 2017, 46,
5193; (e) P. Sivaguru, Z. Wang, G. Zanoni and X. Bi, Chem.
Soc. Rev., 2019, 48, 2615.
2
For selected examples on functionalization of alkene via
radical process, see: (a) B. Yang, X.-H. Xu and F.-L. Qing, Org.
Lett., 2015, 17, 1906; (b) E. Shi, J. Liu, C. Liu, Y. Shao, H.
Wang, Y. Lv, M. Ji, X. Bao and X. Wan, J. Org. Chem., 2016,
81, 5878; (c) J. Hou, A. Ee, H. Cao, H.-W. Ong, J.-H. Xu and J.
Wu, Angew. Chem. Int. Ed., 2018, 57, 17220; (d) G. S. Sauer
and S. Lin, ACS Catal., 2018, 8, 5175; (e) X. Tang and A.
Studer, Angew. Chem. Int. Ed., 2018, 57, 814; (f) J.-S. Lin, T.-
T. Li, J.-R. Liu, G.-Y. Jiao, Q.-S. Gu, J.-T. Cheng, Y.-L. Guo, X.
Hong and X.-Y. Liu, J. Am. Chem. Soc., 2019, 141, 1074.
For selected examples on functionalization of alkyne via
radical process, see: (a) Q. Lu, J. Zhang, G. Zhao, Y. Qi, H.
Wang and A. Lei, J. Am. Chem. Soc., 2013, 135, 11481; (b) A.
Maji, A. Hazra and D. Maiti, Org. Lett., 2014, 16, 4524; (c) J.
Hou, A. Ee, W. Feng, J.-H. Xu, Y. Zhao and J. Wu, J. Am. Chem.
Soc., 2018, 140, 5257; (d) W. Jud, C. O. Kappe and D. Cantillo,
Org. Biomol. Chem., 2019, 17, 3529; (e) B. Wang, Z. Yan, L.
Liu, J. Wang, Z. Zha and Z. Wang, Green Chem., 2019, 21,
205.
Ethyl 2-((4-bromophenyl)sulfonyl)acetate (3ga) petroleum
ether/ ethylacetate = 6:1, white solid, 59% yield (89.9 mg),
o
1
melting point: 39.4-40.5 C. H NMR (400 MHz, CDCl3) δ 7.82
(d, J = 8.7 Hz, 2H), 7.73 (d, J = 8.7 Hz, 2H), 4.18-4.13 (m, 4H),
1.21 (t, J = 7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 162.1,
137.5, 132.3, 130.0, 129.5, 62.3, 60.6, 13.7. HRMS (ESI-TOF):
Anal. Calcd. For C10H1179BrO4S+Na+: 328.9454, Found:
328.9456; Anal. Calcd. For C10H1181BrO4S+Na+: 330.9433,
Found: 330.9441. IR (neat, cm-1): υ 3093, 2987, 2850, 1732,
1463, 1268, 1147, 1079.
3
4
Ethyl 2-((4-(trifluoromethyl)phenyl)sulfonyl)acetate (3ha)
petroleum ether/ ethylacetate = 6:1, colorless oil, 53% yield
1
(77.8 mg). H NMR (400 MHz, CDCl3) δ 8.12 (d, J = 8.2 Hz, 2H),
7.87 (d, J = 8.2 Hz, 2H), 4.20 (s, 2H), 4.16 (q, J = 7.1 Hz, 2H),
1.20 (t, J = 7.1 Hz, 2H). 13C NMR (100 MHz, CDCl3) δ 162.0,
142.1, 135.7 (q, J = 33.2 Hz), 129.3, 126.2 (q, J = 3.6 Hz), 123.0
(q, J = 274.2 Hz), 62.5, 60.5, 13.7. 19F NMR (376 MHz, CDCl3) δ -
63.3. HRMS (ESI-TOF): Anal. Calcd. For C11H11F3O4S+Na+:
319.0222, Found: 319.0223. IR (neat, cm-1): υ 3106, 2988 2944,
1739, 1404, 1279, 1154, 1086.
For selected examples on functionalization of (hetero)arenes
via radical process, see: (a) L. Song, L. Zhang, S. Luo and J.-P.
Cheng, Chem. Eur. J., 2014, 20, 14231; (b) J. Genovino, Y.
Lian, Y. Zhang, T. O. Hope, A. Juneau, Y. Gagné, G. Ingle and
M. Frenette, Org. Lett., 2018, 20, 3229; (c) B. Yang, D. Yu, X.-
H. Xu and F.-L. Qing, ACS Catal., 2018, 8, 2839; (d) W. Jud, S.
Maljuric, C. O. Kappe and D. Cantillo, Org. Lett., 2019, 21,
7970.
Ethyl 2-((2-bromophenyl)sulfonyl)acetate (3ia) petroleum
ether/ ethylacetate = 6:1, white solid, 63% yield (75.6 mg),
o
1
melting point: 44.0-45.2 C. H NMR (400 MHz, CDCl3) δ 8.17-
8.14 (m, 1H), 7.80-7.78 (m, 1H), 7.57-7.51 (m, 2H), 4.49 (s, 2H),
4.10 (q, J = 7.1 Hz, 2H), 1.12 (t, J = 7.1 Hz, 3H). 13C NMR (100
MHz, CDCl3) δ 161.8, 137.6, 135.2, 135.0, 132.2, 127.8, 120.5,
62.1, 58.1, 13.5. HRMS (ESI-TOF): Anal. Calcd. For
C10H1179BrO4S+Na+: 328.9454, Found: 328.9456; Anal. Calcd.
For C10H1181BrO4S+Na+: 330.9433, Found: 330.9447. IR (neat,
cm-1): υ 3090, 3003, 2948, 1729, 1281, 1159, 1094, 1024.
Ethyl 2-(thiophen-2-ylsulfonyl)acetate (3ja) petroleum
ether/ ethylacetate = 5:1, colorless oil, 25% yield (29.0 mg). 1H
NMR (400 MHz, CDCl3) δ 7.82-7.80 (m, 1H), 7.77-7.76 (m, 1H),
7.20-7.18 (m, 1H), 4.23 (s, 2H), 4.18 (q, J = 7.1 Hz, 2H), 1.22 (t, J
= 7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 162.0, 139.0, 135.1,
134.9, 127.8, 62.2, 61.8, 13.6. HRMS (ESI-TOF): Anal. Calcd. For
C8H10O4S2+Na+: 256.9913, Found: 256.9922. IR (neat, cm-1): υ
3100, 2985, 2941, 1735, 1467, 1277, 1145, 1090.
5
6
(a) F.-L. Zhang, Y.-F. Wang and S. Chiba, Org. Biomol. Chem.,
2013, 11, 6003; (b) Q. Qin and S. Yu, Org. Lett., 2015, 17,
1894; (c) G. J. Choi, Q. Zhu, D. C. Miller, C. J. Gu and R. R.
Knowles, Nature, 2016, 539, 268; (d) X.-Q. Hu, J.-R. Chen and
W.-J. Xiao, Angew. Chem. Int. Ed., 2017, 56, 1960; (e) A. Hu,
J.-J. Guo, H. Pan, H. Tang, Z. Gao and Z. Zuo, J. Am. Chem.
Soc., 2018, 140, 1612.
For selected reviews on carbene chemistry, see: (a) D. M.
Hodgson, F. Y. T. M. Pierard and P. A. Stupple, Chem. Soc.
Rev., 2001, 30, 50; (b) H. M. L. Davies and R. E. J. Beckwith,
Chem. Rev., 2003, 103, 2861; (c) M. P. Doyle, R. Duffy, M.
Ratnikov and L. Zhou, Chem. Rev., 2010, 110, 704; (d) Q.
Xiao, Y. Zhang and J. Wang, Acc. Chem. Res., 2013, 46, 236;
(e) A. Ford, H. Miel, A. Ring, C. N. Slattery, A. R. Maguire and
M. A. McKervey, Chem. Rev., 2015, 115, 9981; (f) Q.-Q.
Cheng, Y. Deng, M. Lankelma and M. P. Doyle, Chem. Soc.
Rev., 2017, 46, 5425; (g) Y. Xia, D. Qiu and J. Wang, Chem.
Rev., 2017, 117, 13810; (h) Y. Xiang, C. Wang, Q. Ding and Y.
Peng, Adv. Synth. Catal., 2019, 361, 919.
For selected examples on X–H insertion, see: (a) M. Austeri,
D. Rix, W. Zeghida and J. Lacour, Org. Lett., 2011, 13, 1394;
(b) Q.-Q. Cheng, S.-F. Zhu, Y.-Z. Zhang, X.-L. Xie and Q.-L.
Zhou, J. Am. Chem. Soc., 2013, 135, 14094; (c) D. Chen, X.
Zhang, W.-Y. Qi, B. Xu and M.-H. Xu, J. Am. Chem. Soc., 2015,
137, 5268. For selected examples on cross-coupling, see: (d)
F. Ye, X. Ma, Q. Xiao, H. Li, Y. Zhang and J. Wang, J. Am.
Chem. Soc., 2012, 134, 5742; For selected examples on
7
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
6 | J. Name., 2012, 00, 1-3
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Organic & Biomolecular Chemistry
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Journal Name
ARTICLE
cyclization and ylide reactions, see: (e) S. Son and G. C. Fu, J.
Am. Chem. Soc., 2007, 129, 1046; (f) B. V. S. Reddy, E. P.
Reddy, B. Sridhar and Y. J. Rao, RSC Adv., 2016, 6, 50497; (g)
T. Douglas, A. Pordea and J. Dowden, Org. Lett., 2017, 19,
6396; (h) A. N. Koronatov, N. V. Rostovskii, A. F. Khlebnikov
and M. S. Novikov, J. Org. Chem., 2018, 83, 9210; (i) H. Li, X.
Wu, W. Hao, H. Li, Y. Zhao, Y. Wang, P. Lian, Y. Zheng, X. Bao
and X. Wan, Org. Lett., 2018, 20, 5224; (j) D. Zhang, L. Lin, J.
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