A palladium-catalyzed coupling reaction of aryl nonaflates, sulfur dioxide, and hydrazines

Article abstract of DOI:10.1039/c5ob02514a

A facile route to synthesise N-aminosulfonamides through a palladium-catalyzed coupling reaction of aryl nonaflates, sulfur dioxide, and hydrazines is reported. This transformation proceeds in the presence of Pd(OAc)₂/XantPhos, and TBAB in 1,4-dioxane at 80°C, leading to the corresponding N-aminosulfonamides in moderate to good yields. The reaction scope has been demonstrated, and good functional tolerance is observed. A plausible mechanism is proposed through the insertion of sulfur dioxide.

Full text of DOI:10.1039/c5ob02514a

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DOI: 10.1039/C5OB02514A
Organic & Biomolecular Chemistry
A palladium-catalyzed coupling reaction of aryl nonaflates, sulfur
dioxide, and hydrazines
Received 00th January 20xx,
Yuanyuan An,a Hongguang Xia,b,* and Jie Wua,c,
*
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
A facile route to N-aminosulfonamides through a palladium-catalyzed coupling reaction of aryl nonaflates, sulfur dioxide,
and hydrazines is reported. This transformation proceeds in the presence of Pd(OAc)2/XantPhos, and TBAB in 1,4-dioxane
at 80 °C, leading to the corresponding N-aminosulfonamides in moderate to good yields. The reaction scope has been
demonstrated, and good functional tolerance is observed. A plausible mechanism is proposed through the insertion of
sulfur dioxide.
metal-free conditions.6c An alternative route for the synthesis
of aryl N-aminosulfonamides was developed as well via a
palladium-catalyzed three-component reaction of aryl halides,
Introduction
Palladium-catalyzed cross-coupling reactions are among the
most highly powerful approaches for the efficient construction
of carbon-carbon bonds and carbon-heteroatom bonds.1
Among the electrophiles utilized in palladium-catalyzed cross-
coupling reactions, “pseudohalides” are attractive since they
can be readily prepared from aryl alcohols or ketones.2 This
development significantly expanded the range of compatible
electrophiles in coupling reactions and further enhanced the
synthetic utility of this approach. Recently, we have involved
the cross-coupling reactions of sulfonates.3 The easy
availability of sulfonates prompted us to expand their further
applications.
sulfur dioxide, and hydrazines.6b Consistent with our
continuing interest in the cross-coupling reactions of
sulfonates and fixation of sulfur dioxide, we concieved that
sulfonates could act as electrophiles as well in the palladium-
catalyzed insertion of sulfur dioxide. Considering the reactivity
and easy availability, aryl nonaflates were chosen as substrates
for reaction development (Scheme 1).
previous work
R2
R2
[Pd] (cat.) or
metal-free conditions
O2
S
X
H2N N
N
+
R3
R1
R3
N
R1
H
SO2
Currently, insertion of sulfur dioxide into small molecules
have attracted growing interests in organic synthesis,
4-7
since
X = I, Br, B(OH)2, N2BF4
the sulfonyl group can be found in many natural products,
pharmaceuticals, agrochemical molecules, and materials.8 For
example, cafenstrole is known as the herbicide, and
bicalutamide is employed for the treatment of prostate
cancer.8 Moreover, this functional group has been utilized
broadly in organic synthesis due to its versatile reactivity.9
Recently, we developed several efficient routes for the
incorporation of sulfur dioxide into small molecules including
transition metal catalyzed sulfonylation and radical process
(Scheme 1).6 For instance, aryl N-aminosulfonamides could be
this work
R2
R2
O2
S
ONf
+
H2N N
[Pd] (cat.)
N
R3
N
R3
R1
R1
H
SO2
Scheme 1 Generation of aryl N-aminosulfonamides via insertion of sulfur
dioxide
Due to the disadvantages of gaseous state of sulfur dioxide, the
source of sulfur dioxide includes DABCO·(SO2)2 (named: DABSO)4
and inorganic metal sulfites was considered. Since the palladium-
catalyzed coupling reaction usually proceeded under base
conditions and the release of sulfur dioxide from inorganic metal
sulfites should be performed in the presence of an acid, we
therefore selected DABCO·(SO2)2 as the source of sulfur dioxide
during the transformation. This reagent developed by Willis,5a has
been utilized widely due to its stability at bench and easy
availability. Encouraged by these results, we thus started to explore
generated
through
a
reaction
of
aryldiazonium
tetrafluoroborates, sulfur dioxide, and hydrazines under
a.Department of Chemistry, Fudan University, 220 Handan Road, Shanghai 200433,
China. E-mail: jie_wu@fudan.edu.cn
b.Department of Biochemistry and Molecular Biology, Zhejiang University School of
Medicine, Hangzhou 310058, China. Email: hongguangxia@zju.edu.cn
c.State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic
Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032,
China
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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Organic & Biomolecular Chemistry
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Journal Name
the palladium-catalyzed coupling reaction of aryl nonaflates, sulfur
dioxide, and hydrazines.
11
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
XantPhos
XantPhos
XantPhos
XantPhos
TBAB
TBAB
TBAB
TBAB
NMVPiew Article5O7nline
DOI: 10.1039/C5OB02514A
12
DMF
40
70
13b
14c
1,4-dioxane
Results and discussion
1,4-dioxane
trace
A model reaction of phenyl nonaflate 1a, sulfur dioxide, and
morpholin-4-amine 2a was initially investigated (Table 1). At
the outset, the reaction was performed in the presence of
palladium chloride (10 mol %), XPhos (10 mol %) and TBAB (2.0
equiv.) in 1,4-dioxane at 100 °C (Table 1, entry 1). However,
the result was not promising and only a trace amount of
product was detected. A similar result was observed when the
ligand was changed to tricyclohexylphosphine (Table 1, entry
2). To our delight, the reaction proceeded smoothly when
XantPhos was employed as the ligand, leading to the desired
N-aminosulfonamide 3a in 45% yield (Table 1, entry 3). Further
exploration of bases revealed that the yield was lower when
TBAB was replaced by TBAC, TBAI, TEAB, or sodium carbonate
(Table 1, entries 4-7). Gratifyingly, the result was dramatically
improved when palladium acetate was used as the catalyst
(Table 1, entry 8). No better yields were obtained when other
palladium catalysts were screened (Table 1, entries 9 and 10).
Next, we examined other solvents in the reaction (Table 1,
entries 11 and 12). However, 1,4-dioxane was demonstrated
as the best choice. Interestingly, the yield was increased to
70% when the reaction was occurred at 80 °C (Table 1, entry
13). However, the reaction was inert when the temperature
was changed to 60 °C (Table 1, entry 14).
a
b
Isolated yield based on phenyl nonaflate 1a. The reaction was
performed at 80 °C. c The reaction occurred at 60 °C.
With the optimized conditions in hand, we next explored
the scope of this palladium-catalyzed coupling reaction of aryl
nonaflates 1, sulfur dioxide, and hydrazines 2. The
corresponding results are presented in Table 2. It was found
that all reactions worked smoothly to produce the desired
products in moderate to good yields. Aryl nonaflates 1
participated successfully in the transformation, including the
substrates substituted by electron-donating and electron-
withdrawing groups. Different functional groups including
methyl, methoxy, fluoro, chloro, and trifluoromethyl groups
attached on the aromatic ring of aryl nonaflates 1 were
tolerated under the standard conditions. For example, 4-
chlorophenyl nonaflate reacted with sulfur dioxide and
morpholin-4-amine 2a gave rise to the corresponding product
3g in 48% yield. During the transformation, the chloro group
was remained, which was not involved in the reaction. The
reaction was also workable when sterically hindered 2-
methylphenyl nonaflate was employed as the substrate,
affording the expected product 3i in 45% yield. Other
hydrazines were employed in the palladium-catalyzed coupling
reaction of aryl nonaflate 1 and sulfur dioxide in the meantime.
As expected, all reactions proceeded well to afford the
corresponding products. For instance, the coupling reaction of
phenyl nonaflate 1a, sulfur dioxide, and 1-ethyl-1-
phenylhydrazine generated the desired N'-ethyl-N'-
phenylbenzenesulfonohydrazide 3m in 51% yield.
Table 1. Initial studies for the palladium-catalyzed coupling reaction of
phenyl nonaflate 1a, sulfur dioxide, and morpholin-4-amine 2a.
[Pd] (10 mol %)
ligand (10 mol %)
O
H2N N
O
O2
S
ONf
N
+
N
2a
H
base, solvent
100 !C
1a
DABCO (SO2)2
3a
Entry
[Pd]
Ligand
Base
Solvent
Yield
(%)a
Table 2. Scope exploration of palladium-catalyzed coupling reaction of aryl
nonaflates 1, sulfur dioxide, and hydrazines 2a
1
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
PdCl2
XPhos
TBAB
TBAB
TBAB
TBAC
TBAI
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
trace
trace
45
2
PCy3
3
XantPhos
XantPhos
XantPhos
XantPhos
XantPhos
XantPhos
XantPhos
XantPhos
4
33
5
33
6
TEAB
Na2CO3
TBAB
TBAB
TBAB
26
7
trace
59
8
Pd(OAc)2
Pd(PPh3)4
9
28
10
Pd(CO2CF3)2
41
2 | J. Name., 2012, 00, 1-3
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Journal Name
R2
R3
Scheme 2. A plausible mechanism for the palladium-catalyzed coupling
R2
N
Pd(OAc)2 (10 mol %)
XantPhos (10 mol %)
reaction of aryl nonaflates 1, sulfur dioxide, and hydrazines 2View Article Online
ONf
O2
S
H2N
N
2
DOI: 10.1039/C5OB02514A
R1
+
N
R3
R1
H
TBAB, 1,4-dioxane
DABCO (SO2)2
O
1
3
80 !
C
Conclusions
O
O
O2
S
O2
O2
S
In conclusion, we have developed a convenient route to N-
aminosulfonamides through a palladium-catalyzed coupling
reaction of aryl nonaflates, sulfur dioxide, and hydrazines. This
N
O
S
N
N
N
N
N
H
H
H
3a, 70% yield
3b, 47% yield
3c, 72% yield
transformation
proceeds
in
the
presence
of
Pd(OAc)2/XantPhos (10 mol %), and TBAB in 1,4-dioxane at
80 °C, leading to the corresponding N-aminosulfonamides in
moderate to good yields. The reaction scope has been
demonstrated, and good functional tolerance is observed. The
easy availability of substrates and mild reaction conditions of
this approach would enable this protocol to be attractive for
further applications.
O
O
O
O
O2
S
O2
S
N
H
O2
N
N
S
N
N
N
H
H
tBu
H3CO
Cl
3e, 67% yield
3d, 63% yield
3f, 48% yield
O
O2
S
O
O2
S
O2
N
N
S
N
N
N
N
H
H
H
F3C
F
3g, 36% yield
3h, 40% yield
3i, 45% yield
Experimental Section
O
General experimental methods
O
O2
S
N
H
O2
O2
N
S
N
O
O
S
N
N
Unless otherwise stated, all commercial reagents were
used as received. All solvents were dried and distilled
according to standard procedures. Flash column
chromatography was performed using silica gel (60-Å pore size,
N
Ph
H
H
Ph
3j, 40% yield
3k, 40% yield
3l, 50% yield
Ph
O2
O2
S
32–63μm,
standard
grade).
Analytical
thin–layer
S
N
N
N
Ph
N
Ph
chromatography was performed using glass plates pre-coated
with 0.25 mm 230–400 mesh silica gel impregnated with a
fluorescent indicator (254 nm). Thin layer chromatography
plates were visualized by exposure to ultraviolet light. Organic
solutions were concentrated on rotary evaporators at ~20 Torr
at 25–35°C. Nuclear magnetic resonance (NMR) spectra are
recorded in parts per million from internal tetramethylsilane
on the δ scale. 1H and 13C NMR spectra were recorded in CDCl3
on a Bruker DRX-400 spectrometer operating at 400 MHz and
100 MHz, respectively. All chemical shift values are quoted in
ppm and coupling constants quoted in Hz. High resolution
mass spectrometry (HRMS) spectra were obtained on a
micrOTOF II Instrument.
H
H
3n, 45% yield
3m, 51% yield
a Isolated yield based on aryl nonaflate 1.
A possible mechanism of this palladium-catalyzed coupling
reaction of aryl nonaflates 1, sulfur dioxide, and hydrazines 2 is
provided in Scheme 2. We reasoned that an oxidative addition
of palladium(0) to aryl nonaflate 1 would occur firstly to
generate Pd(II) species A. Subsequently, the insertion of sulfur
dioxide to Pd(II) A would happen to produce intermediate B. In
the presence of a base, the nucleophilic attack of hydrazine 2
to Pd(II)
B would afford the corresponding aryl N-
General experimental procedure for the palladium-catalyzed
coupling reaction of aryl nonaflates 1, sulfur dioxide, and
hydrazines 2
aminosulfonamide 3 with the release of Pd(0), which would
then re-enter the catalytic cycle.
R2
N
ONf
Aryl nonaflate 1 (0.3 mmol) and hydrazine 2 (0.6 mmol, 2
equiv.) was added to a solution of DABCO•(SO2)2 (0.3 mmol, 1
equiv.), Pd(OAc)2 (0.03 mmol, 10 mol %), XantPhos (0.03
mmol, 10 mol %), and TBAB (0.6 mmol, 2 equiv.) in 1,4-dioxane
(2.5 mL) under N2 atmosphere. The mixture was stirred at
80 °C for 8-10 hours. After completion of the reaction as
indicated by TLC, the solvent was evaporated and the residue
was purified directly by flash column chromatograph
(EaOAc/n-hexane, 1: 2) to give the desired N-
aminosulfonamide 3.
O2
S
Pd(0)
R1
N
H
R3
R1
1
3
O
O
PdII
PdII
S
X
R1
C
R2
R1
HN
A
N
R2
base
R2
O
O
PdII
S
R1
N-Morpholinobenzenesulfonamide (3a).6c Yield: 70%, yellow
solid; 1H NMR (400 MHz, CDCl3) δ 2.62 (t, J = 4.6 Hz, 4H), 3.60
(t, J = 4.6 Hz, 4H), 3.84 (s, 1H), 7.53 (t, J = 7.5 Hz), 7.61 (t, J =
H2N
N
R3
SO2
X
2
B
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6c
7.4 Hz), 7.99 (d, J = 7.2 Hz); 13C NMR (100 MHz, CDCl3) δ 56.6, N-Morpholino-[1,1'-biphenyl]-4-sulfonamide (3k). Yield: 40%,
View Article Online
66.6, 128.1, 128.8, 133.1, 138.6.
yellow solid; 1H NMR (400 MHz, CDCl3) δD2O.6I:710(t.1,0J39=/C45.6OBH0z2,5414HA),
3-Methyl-N-morpholinobenzenesulfonamide (3b).6c Yield: 47%, 3.63 (t, J = 4.6 Hz, 4H), 5.70 (s, 1H), 7.41-7.45 (m, 1H), 7.47-
yellow solid; 1H NMR (400 MHz, CDCl3) δ 2.44 (s, 3H), 2.62 (t, J 7.51 (m, 2H), 7.62-7.64 (m, 2H), 7.74 (d, J = 8.6 Hz, 2H), 8.04 (d,
= 4.4 Hz, 4H), 3.61 (t, J = 4.4 Hz, 4H), 5.58 (s, 1H), 7.41(d, J = 4.8 J = 8.5 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 56.8, 66.6, 127.3,
Hz, 2H), 7.77-7.79 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 21.3,
127.4, 128.6, 128.6, 129.1, 137.2, 139.1, 146.0.
N'-Methyl-N'-phenylbenzenesulfonohydrazide (3l).6c Yield: 50%,
brown solid; H NMR (400 MHz, CDCl3) δ 2.94 (s, 3H), 6.36 (s,
56.7, 66.6, 125.2, 128.4, 128.7, 133.9, 138.4, 139.0; HRMS (ESI)
calcd for C11H16N2O3S: 279.0774 (M + Na+), found: 279.0775.
1
3-Methoxy-N-morpholinobenzenesulfonamide (3c).6c Yield:
1H), 6.84 (dd, J1 = 8.0 Hz, J2 = 11.0 Hz, 3H), 7.15 (t, J = 8.3 Hz,
1
72%, yellow solid; H NMR (400 MHz, CDCl3) δ 2.64 (t, J = 4.6
2H) 7.48 (t, J = 7.7 Hz, 2H), 7.58 (t, J = 7.4 Hz, 1H), 7.95 (d, J =
7.4 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 42.7, 114.4, 120.9,
128.1, 128.9, 129.1, 133.3, 138.5, 149.6.
N'-Ethyl-N'-phenylbenzenesulfonohydrazide (3m).6c Yield: 51%,
Hz, 4H), 3.62 (t, J = 4.6 Hz, 4H), 3.87 (s, 3H), 5.86 (s, 1H), 7.12-
7.15(m, 1H), 7.43 (t, J = 8.0 Hz， 1H), 7.49 (t, J = 2.0 Hz，
1H) ， 7.56 (d, J= 7.8 Hz, 1H); 13C NMR(100 MHz, CDCl3) δ 55.7,
56.6, 66.6, 112.6, 119.6, 120.2, 129.9, 139.8, 159.7.
yellow solid; 1H NMR (400 MHz, CDCl3) δ 1.00 (t, J = 7.1 Hz, 3H),
4-Methoxy-N-morpholinobenzenesulfonamide (3d).6c Yield:
1
3.41-3.49 (m, 2H), 6.67 (s, 1H), 6.80 (dd, J1 = 7.6 Hz, J2 = 12.6
Hz, 3H), 7.12 (t, J = 8.0 Hz, 2H), 7.44 (t, J = 7.7 Hz, 2H), 7.53 (t, J
63%, yellow solid; H NMR (400 MHz, CDCl3) δ 2.63 (t, J = 4.4
Hz, 4H), 3.62 (t, J = 4.3 Hz, 4H), 3.89 (s, 3H), 5.56 (s, 1H), 6.99 (d,
= 7.4 Hz, 1H), 7.92 (d, J = 7.3 Hz, 2H); 13C NMR (100 MHz, CDCl3)
J = 8.9 Hz, 2H), 7.90 (d, J = 8.8 Hz, 2H); 13C NMR (100 MHz,
δ 9.5, 49.2, 113.6, 115.1, 120.8, 128.1, 128.9, 133.2, 138.7,
147.6.
N'-Benzyl-N'-phenylbenzenesulfonohydrazide (3n).6c Yield:
CDCl3) δ 55.6, 56.7, 114.0, 128.8, 130.3, 163.2.
4-(tert-Butyl)-N-morpholinobenzenesulfonamide (3e).6c Yield:
1
67%, brown solid; H NMR (400 MHz, CDCl3) δ 1.35 (s, 9H),
1
45%, yellow solid; H NMR (400 MHz, CDCl3) δ 4.56 (s, 2H),
2.64 (t, J = 4.6 Hz, 4H), 3.61 (t, J = 4.6 Hz, 4H), 5.75 (s, 1H), 7.53
(d, J = 8.6 Hz), 7.89 (d, J = 8.6 Hz); 13C NMR (100 MHz, CDCl3) δ
6.36 (s, 1H), 6.85-6.93 (m, 3H), 7.04-7.06 (m, 2H), 7.16 (t, J =
8.3 Hz, 2H), 7.27 (t, J = 3.3 Hz, 3H), 7.47 (t, J = 7.6 Hz, 2H), 7.57
31.0, 35.2, 56.7, 66.6, 125.8, 128.0, 135.6, 157.0.
(t, J = 7.4 Hz, 1H), 7.94 (d, J = 7.3 Hz, 2H); 13C NMR (100 MHz,
4-Chloro-N-morpholinobenzenesulfonamide (3f).6c Yield: 48%,
CDCl3) δ 58.1, 115.3, 121.0, 128.0, 128.0, 128.3, 128.6, 128.8,
129.0, 133.3, 134.4, 138.8, 148.6.
yellow solid; 1H NMR (400 MHz, CDCl3) δ 2.65 (t, J = 4.5 Hz, 4H),
3.62 (t, J = 4.6 Hz, 4H), 5.53 (s, 1H), 7.50(d, J = 8.6 Hz, 2H), 7.91
(d, J = 8.6 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 56.7, 66.6,
125.8, 127.9, 129.1, 129.6.
Acknowledgements
Financial support from National Natural Science Foundation of
4-Fluoro-N-morpholinobenzenesulfonamide (3g).6c Yield: 36%,
brown solid; 1H NMR (400 MHz, CDCl3) δ 2.64 (t, J = 4.5 Hz, 4H),
China (Nos. 21372046 and 21532001) and the Science &
3.62 (t, J = 4.4 Hz, 4H), 5.52 (s, 1H), 7.21(t, J = 8.5 Hz, 2H), 7.98-
8.01 (m, 2H); 13C NMR (100 MHz, CD3OD) δ 56.3, 66.4, 116.7 (d,
JF = 22.9 Hz), 131.1 (d, JF = 9.5 Hz), 136.1, 164.9 (d, JF = 250.7
Hz).
Technology Commission of Shanghai Municipality (No.
12JC1403800) is gratefully acknowledged.
N-Morpholino-4-(trifluoromethyl)benzenesulfonamide (3h).6c
Yield: 40%, brown solid; 1H NMR (400 MHz, CDCl3) δ 2.66 (t, J =
4.5 Hz, 4H), 3.63 (t, J = 4.5 Hz, 4H), 5.61 (s, 1H), 7.80 (d, J = 8.2
Hz, 2H), 8.11 (d, J = 8.2 Hz, 2H); 13C NMR (100 MHz, CDCl3)
142.3, 134.9 (q, J = 33.4 Hz), 128.6, 126.0 (d, J = 3.1 Hz), 124.5,
66.5, 56.8.
2-Methyl-N-morpholinobenzenesulfonamide (3i).6c Yield: 45%,
yellow solid; 1H NMR (400 MHz, CDCl3) δ 2.66 (t, J = 4.6 Hz, 4H),
2.70 (s, 3H), 3.58 (t, J = 4.5 Hz, 4H), 5.52 (s, 1H), 7.30-7.36 (m,
2H), 7.47-7.50 (m, 1H), 8.07 (d, J = 7.4 Hz, 1H); 13C NMR (100
MHz, CDCl3) δ 20.6, 56.7, 66.5, 126.1, 131.0, 132.3, 133.2,
136.4, 138.0.
Notes and references
1
For selected reviews, see: a) J. C. Seechurn, M. O. Kitching, T.
J. Colacot and V. Snieckus, Angew. Chem. Int. Ed. 2012, 51,
5062; b) X.-F. Wu, P. Anbarasan, H. Neumann and M. Beller,
Angew. Chem. Int. Ed. 2010, 49, 9047; c) A. Roglans, A. Pla-
Quintana and M. Moreno-Manas, Chem. Rev. 2006, 106,
4622; d) N. Miyaura and A. Suzukint, Chem. Rev. 1995, 95,
2457; e) L.-X. Yin and J. Liebscher, Chem. Rev. 2007, 107, 133;
f) Transition Metal Reagents and Catalysts, Edited by J. Tsuji,
John Wiley & Sons, Ltd, 2000.
2
3
For selected reviews, see: a) J. Högermeier and H.-U. Reissig,
Adv. Synth. Catal. 2009, 351, 2747; b) P. J. Stang, M. Hanack
and L. R. Subrmanian, Synthesis 1982, 85; c) K. Ritter,
Synthesis 1993, 735.
For selected examples, see: a) L. Zhang and J. Wu, J. Am.
Chem. Soc. 2008, 130, 12250; b) Y. Luo and J. Wu,
Organometallics 2009, 28, 6823; c) L. Zhang, J. Qing, P. Yang
and J. Wu, Org. Lett. 2008, 10, 4971; d) L. Zhang and J. Wu,
Adv. Synth. Catal. 2008, 350, 2409.
For reviews: a) G. Liu, C. Fan and J. Wu, Org. Biomol. Chem.
2015, 13,1592; b) P. Bisseret and N. Blanchard, Org. Biomol.
Chem. 2013, 11, 5393; c) A. S. Deeming, E. J. Emmett, C. S.
Richards-Taylor and M. C. Willis, Synthesis 2014, 46, 2701.
N-Morpholinobenzo[d][1,3]dioxole-5-sulfonamide (3j). Yield:
40%, white solid; 1H NMR (400 MHz, CDCl3) δ 2.66 (t, J = 4.6 Hz,
4H), 3.64 (t, J = 4.6 Hz, 4H), 5.42 (s, 1H), 6.10 (s, 2H), 6.90 (d, J
= 8.2 Hz, 1H), 7.38 (d, J = 1.6 Hz, 1H), 7.54 (dd, J1 = 1.7 Hz, J2 =
8.2 Hz); 13C NMR (100 MHz, CDCl3) δ 56.8, 66.6, 102.3, 108.1,
108.3, 116.2, 124.0, 156.0, 156.6; HRMS (ESI) calcd for
C11H14N2O5S: 287.0696 (M + H+), found: 287.0694.
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4 | J. Name., 2012, 00, 1-3
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Page 5 of 5
Organic & Biomolecular Chemistry
Journal Name
5
a) B. Nguyen, E. J. Emmet, M. C. Willis, J. Am. Chem. Soc.
View Article Online
DOI: 10.1039/C5OB02514A
2010, 132, 16372; b) E. J. Emmet, C. S. Garcia-Rubia, B.
Nguyen, A. B. Garcia-Rubia, R. Hayter and M. C. Willis, Org.
Biomol. Chem. 2012, 10, 4007; c) L. Martial, Synlett 2013, 24,
1595; d) W. Li, H. Li, P. Langer, M. Beller and X.-F. Wu, Eur. J.
Org. Chem. 2014, 3101; e) W. Li, M. Beller and X.-F. Wu,
Chem. Commun. 2014, 50, 9513; f) X. Wang, L. Xue and Z.
Wang, Org. Lett. 2014, 16, 4056; g) A. S. Deeming, C. J.
Russell and M. C. Willis, Angew. Chem. Int. Ed. 2015, 54,
1168.
6
7
a) S. Ye and J. Wu, Chem. Commun. 2012, 48, 7753; b) S. Ye
and Wu, J. Chem. Commun. 2012, 48, 10037; c) D. Zheng, Y.
An, Z. Li and J. Wu, Angew. Chem. Int. Ed. 2014, 53, 2451; d)
S. Ye, H. Wang, Q. Xiao, Q. Ding and J. Wu, Adv. Synth. Catal.
2014, 356, 3225; e) Y. An, D. Zheng and J. Wu, Chem.
Commun. 2014, 50, 11746; f) Y. Luo, X. Pan, C. Chen, L. Yao
and J. Wu, Chem. Commun. 2015, 51, 180; g) D. Zheng, Y. Li,
Y. An and J. Wu, Chem. Commun. 2014, 50, 8886.
a) C. C. Chen and J. Waser, Org. Lett. 2015, 17, 736; b) A. S.
Deeming, C. J. Rusell, A. J. Hennessy and M. C. Willis, Org.
Lett. 2014, 16, 150; c) B. N. Rocke, K. B. Bahnck, M. Herr, S.
Lavergne, V. Mascitti, C. Perreault, J. Polivkova and A.
Shavnya, Org. Lett. 2014, 16, 154; d) E. J. Emmett, B. R.
Hayter and M. C. Willis, Angew. Chem. Int. Ed. 2013, 52,
12679; e) E. J. Emmett, B. R. Hayter and M. C. Willis, Angew.
Chem . Int. Ed. 2014, 38, 10204; f) A. Shavnya, S. B. Coffey, A.
C. Smith and V. Mascitti, Org. Lett. 2013, 15, 6226; g) M. W.
Johnson, S. W. Bagley, N. P. Mankad, R. G. Bergman, V.
Mascitti and F. D. Toste, Angew. Chem. Int. Ed. 2014, 53,
4404; h) A. Shavnya, K. D. Hesp, V. Mascitti and A. C. Smith,
Angew. Chem. Int. Ed. 2015, 54, 13571; i) A. S. Deeming, C. J.
Russell and M. C. Willis, Angew. Chem. Int. Ed. 2015,
DOI: 10.1002/anie.201508370.
8
9
a) P. Tfelt-Hansen, P. De Vries and P. R. Saxena, Drugs 2000,
60, 1259; b) P. F. Schnellhammer, Expert Opin. Pharmacother.
2002, 3, 1313; c) G. Mitchell, D. W. Bartlett, T. E. M. Fraser, T.
R. Hawkes, D. C. Holt, J. K. Townson and R. A. Wichert, Pest
Manage. Sci. 2001, 57, 120; d) P. Boger, J. Pestic. Sci. 2003,
28, 324.
N. S. Simpkins, Sulfones in Organic Synthesis, Pergamon
Press, Oxford, 1993.
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