Iron halide-mediated regio- and stereoselective halosulfonylation of terminal alkynes with sulfonylhydrazides: Synthesis of (E)-β-chloro and bromo vinylsulfones

Article abstract of DOI:10.1021/jo401581n

Halosulfonylation of terminal alkynes was achieved with sulfonylhydrazides as the sulfonyl precursor and inexpensive iron halide as halide source in the presence of TBHP, allowing the regio- and stereoselective generation of (E)-β-chloro and bromo vinylsu

Full text of DOI:10.1021/jo401581n

Note
pubs.acs.org/joc
Iron Halide-Mediated Regio- and Stereoselective Halosulfonylation
of Terminal Alkynes with Sulfonylhydrazides: Synthesis of (E)‑β-
Chloro and Bromo Vinylsulfones
Xiaoqing Li,* Xinhua Shi, Mingwu Fang, and Xiangsheng Xu*
College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310014, People’s Republic of
China
S
* Supporting Information
ABSTRACT: Halosulfonylation of terminal alkynes was
achieved with sulfonylhydrazides as the sulfonyl precursor
and inexpensive iron halide as halide source in the presence of
TBHP, allowing the regio- and stereoselective generation of
(E)-β-chloro and bromo vinylsulfones.
a
Table 1. Optimized Reaction Conditions
unctionalized alkenes are one of the most broadly existing
Fstructural motifs present in organic molecules. The
difunctionalization of alkynes represents a particularly useful
contribution to their synthesis.1 In this context, halosulfonyla-
tion of terminal alkynes has attracted considerable attention2,3
because both the vinyl halide4 and vinyl sulfone moiety5 in the
resulting β-halide vinylsulfones are important intermediates in
organic synthesis. Generally, sulfonyl bromides and iodides
were applied as halosulfonylation reagents under thermal or
photochemical conditions.2 Alternative copper-catalyzed meth-
ods using more practical sulfonyl chlorides are also
investigated.3 Recently, Nakamura and co-workers demon-
strated a highly regio- and stereoselective Fe(acac)2-catalyzed
chlorosulfonylation with aromatic sulfonyl chlorides.6 However,
the usage of a phosphine ligand and harsh reaction conditions
restricted their practical utility on a larger scale process. In
recent years, we have focused our efforts on the construction of
sulfone-containing molecules based on sulfonyl radical addition
using sulfonylhydrazides as the sulfonyl precursor.7 It has been
found that FeCl3 could act as Cl source in some radical
reactions.8 In light of these factors, we hypothesized that the
combination of sulfonylhydrazides with FeCl3 might be utilized
to allow chlorosulfonylation of alkynes. Herein, we present a
full account of this work including extension to bromo-
sulfonylation by using FeBr3 as the Br source.
We initially examined the chlorosulfonylation of phenyl-
acetylene 1a with p-toluenesulfonylhydrazide (TsNHNH2) 2a
and FeCl3·6H2O in the presence of 2 equiv of TBHP as the
oxidant (Table 1). After screening the loading of FeCl3·6H2O
(entries 1−3), 2.0 equiv afforded the best result, providing (E)-
β-chloro vinylsulfone 3aa in 95% yield (entry 2). Notably, this
reaction exhibited high selectivity, and no other isomers were
observed. The reaction worked equally well with anhydrous
FeCl3 (entry 4), whereas no desired product was isolated by
using LiCl as the chloride source (entry 5). Reducing the
amount of TsNHNH2 led to a lower yield (entry 6). The
reaction in water did not work (entry 7), while other solvents,
entry
Cl source (equiv)
solvent
yield (%)
1
2
3
4
5
FeCl3·6H2O (1.5)
FeCl3·6H2O (2.0)
FeCl3·6H2O (2.5)
FeCl3 (2.0)
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
H2O
74
95
87
94
LiCl (2.0)
trace
88
b
6
FeCl3·6H2O (2.0)
FeCl3·6H2O (2.0)
FeCl3·6H2O (2.0)
FeCl3·6H2O (2.0)
FeCl3·6H2O (2.0)
FeCl3·6H2O (2.0)
7
8
trace
83
EtOAc
DCE
9
64
10
11
toluene
dioxane
67
68
a
Reaction conditions: alkynes (0.5 mmol), sulfonylhydrazides (1.4
equiv), Cl source, and TBHP (2 equiv, 70% water solution) in
CH3CN (2 mL) at 80 °C for 3 h. 1.2 equiv of TsNHNH2 was used.
b
such as EtOAc, DCE, toluene, and dioxane, were less effective
(entries 8−11).
Encouraged by these results, we applied the above chloro-
sulfonylation protocol to a range of alkynes 1 and arylsulfonyl-
hydrazides 2 (Table 2). The scope of arylsulfonylhydrazides 2
was initially explored in the presence of phenylacetylene 1a.
Gratifyingly, introduction of Me, MeO, and halogen groups
into the phenyl ring of sulfonylhydrazides was well-tolerated,
and the chlorosulfonylation products were isolated in good to
excellent yield. Then, the scope of alkynes 1 was explored in the
reaction with TsNHNH2 (2a). Aromatic alkynes with a wide
range of functional groups, such as Me, (CH2)4CH3, MeO,
CH3(CH2)4O, F, Cl, Br, and CF3, were well-tolerated (products
Received: July 21, 2013
Published: August 27, 2013
© 2013 American Chemical Society
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The Journal of Organic Chemistry
Note
a
Table 2. FeCl3·6H2O-Mediated Chlorosulfonylation of Alkynes with Sulfonylhydrazides
a
Reaction conditions: alkynes (0.5 mmol), sulfonylhydrazides (1.4 equiv), FeCl3·6H2O (2 equiv), and TBHP (2 equiv, 70% water solution) in
CH3CN (2 mL) at 80 °C for 3 h.
3ba−3ma). The majority of the alkynes with para-substitutions
gave good yields, while the ortho- and meta-substituted alkynes
afforded a slightly lower yield. Thiophenyl-substituted alkyne
could also be employed in this reaction to afford the product
3na in moderate yields. Notably, aliphatic alkyne successfully
underwent halosulfonylation give 3oa, albeit in a low yield.
However, the internal alkyne failed in the reaction to give the
desired product 3pa due to the steric effect. To our delight, the
known compounds are formed in higher yields under milder
reaction conditions compared with the reported method.9
Inspired by the excellent results above, we initiated further
studies of bromosulfonylation by replacing FeCl3·6H2O with
FeBr3. As described in Table 3, with various alkynes and
sulfonylhydrazides examined in the chlorosulfonylation reaction
(Table 2), the desired (E)-β-bromo vinylsulfones were
successfully achieved in the presence of FeBr3 under the
optimal reaction conditions. Generally, bromosulfonylation
exhibited slightly lower reactivity than chlorosulfonylation,
giving moderate yields.
release of molecular nitrogen.4 The iron halide also acted as a
Lewis acid to activate the alkynes. Subsequently, the radical
addition of sulfonyl radicals to the Fe-coordinated alkynes (A)
from the opposite side of the Fe moiety at the terminal position
would lead to regio- and stereoselective formation of the
Fe(IV) intermediate (B). Finally, reductive elimination of
Fe(IV) intermediate B occurred to afford the (E)-β-halo-
vinylsulfones with the generation of the Fe(II) catalyst.
Notably, the formation of sulfonyl halide (C) was detected in
the halosulfonylation, which probably was due to the direct
trapping of the sulfonyl radicals with a halide atom of the iron
halide.8 Thus we speculated that the difference in the reactivity
between chlorosulfonylation and bromosulfonylation might
result from the easier abstraction of Br than Cl by sulfonyl
radicals.
In summary, we have developed a highly regio- and
stereoselective oxidative halosulfonylation of alkynes using
sulfonylhydrazides as the sulfonyl precursor and inexpensive
iron halide as the halide source. It provides efficient and general
access to both (E)-β-chloro and bromo vinylsulfones.
On the basis of the above results and literature reports,4,6,10
the proposed mechanism is illustrated in Scheme 1. Initially, the
tert-butoxyl and tert-butylperoxy radicals were generated in an
iron catalyst−TBHP catalytic system.10 Then, hydrogen
abstraction of sulfonylhydrazides by the resultant radicals
generated sulfonyl radicals from a series of steps with the
EXPERIMENTAL SECTION
■
General Procedures. All reagents and solvents were used without
purification. FeCl3·6H2O and FeCl3 was purchased from Sinopharm
Chemical (≥99 and ≥97%, respectively). FeBr3 was purchased from
1
J&K Chemical (97%). Melting points are uncorrected. The H NMR
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dx.doi.org/10.1021/jo401581n | J. Org. Chem. 2013, 78, 9499−9504

The Journal of Organic Chemistry
Note
a
Table 3. FeBr3-Mediated Bromosulfonylation of Alkynes with Sulfonylhydrazides
a
Reaction conditions: alkynes (0.5 mmol), sulfonylhydrazides (1.4 equiv), FeBr3 (2 equiv), and TBHP (2 equiv, 70% water solution) in CH3CN (2
mL) at 80 °C for 3 h.
are given in hertz. High-resolution mass spectra (HRMS) were
obtained on a TOF MS instrument with APCI source.
Scheme 1. Proposed Mechanism
Typical Procedure for the Synthesis of (E)-β-Halo-
vinylsulfones. To a solution of sulfonylhydrazides (0.7 mmol),
FeCl3·6H2O, or FeBr3 (1.0 mmol) in CH3CN (2 mL) were added
alkynes (0.5 mmol) and TBHP (1.0 mmol, 70% water solution), and
the mixture was stirred at 80 °C for 3 h. After removal of solvent under
reduced pressure, the residue was purified by chromatography
(petroleum/ethyl acetate = 20:1) to give the desired products.
(E)-1-((2-Chloro-2-phenylvinyl)sulfonyl)-4-methylbenzene (3aa):6
1
white solid (138.8 mg, 95%); mp 97−98 °C; H NMR (500 MHz,
CDCl3) δ 7.50 (d, J = 8.3 Hz, 2H), 7.42 (m, 1H), 7.39−7.33 (m, 4H),
7.20 (d, J = 8.2 Hz, 2H), 6.92 (s, 1H), 2.39 (s, 3H); 13C NMR (125
MHz, CDCl3) δ 147.9, 144.6, 137.6, 134.4, 131.0, 130.6, 129.6, 128.8,
128.0, 127.8, 21.6.
(E)-(1-Chloro-2-(phenylsulfonyl)vinyl)benzene (3ab): white solid
(108.5 mg, 78%); mp 73−74 °C; 1H NMR (500 MHz, CDCl3) δ 7.61
(dd, J = 8.5, 1.2 Hz, 2H), 7.56−7.52 (m, 1H), 7.44−7.40 (m, 2H),
7.40−7.32 (m, 5H), 6.95 (s, 1H); 13C NMR (125 MHz, CDCl3) δ
148.5, 140.5, 134.3, 133.5, 130.9, 130.7, 129.0, 128.8, 128.1, 127.7;
HRMS (APCI) calcd for C14H12ClO2S (M + H)+ 279.0247, found
279.0244.
(E)-1-((2-Chloro-2-phenylvinyl)sulfonyl)-4-methoxybenzene
(3ac):6 white solid (126.4 mg, 82%); mp 104−106 °C; 1H NMR (500
MHz, CDCl3) δ 7.53 (d, J = 8.9 Hz, 2H), 7.42 (m, 1H), 7.39−7.34 (m,
4H), 6.93 (s, 1H), 6.85 (d, J = 8.9 Hz, 2H), 3.84 (s, 3H); 13C NMR
(125 MHz, CDCl3) δ 163.7, 147.5, 134.4, 132.0, 131.4, 130.6, 130.0,
128.9, 128.0, 114.2, 55.7.
(E)-1-Chloro-4-((2-chloro-2-phenylvinyl)sulfonyl)benzene (3ad):6
1
white solid (125.0 mg, 80%); mp 107−108 °C; H NMR (500 MHz,
and 13C NMR spectra were recorded at 25 °C in CDCl3 at 500 and
125 MHz, respectively, with TMS as the internal standard. Chemical
shifts (δ) are expressed in parts per million, and coupling constants J
CDCl3) δ 7.50 (d, J = 8.7 Hz, 2H), 7.45−7.41 (m, 1H), 7.36−7.33 (m,
6H), 6.94 (s, 1H); 13C NMR (125 MHz, CDCl3) δ 149.0, 140.3,
138.9, 134.1, 130.9, 130.7, 129.2, 129.2, 128.8, 128.1.
9501
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Note
(E)-1-Bromo-4-((2-chloro-2-phenylvinyl)sulfonyl)benzene (3ae):
white solid (161.3 mg, 90%); mp 103−104 °C; 1H NMR (500
MHz, CDCl3) δ 7.50 (d, J = 8.7 Hz, 2H), 7.43 (t, J = 2.1 Hz, 2H), 7.41
(d, J = 1.8 Hz, 1H), 7.34 (d, J = 1.6 Hz, 2H), 7.34 (s, 2H), 6.94 (s,
1H); 13C NMR (125 MHz, CDCl3) δ 149.0, 139.4, 134.1, 132.2,
130.8, 130.6, 129.2, 128.8, 128.7, 128.0; HRMS (APCI) calcd for
C14H11BrClO2S (M + H)+ 356.9352, found 356.9348.
137.5, 137.0, 132.7, 131.4, 130.3, 129.8, 128.3, 127.8, 21.6; HRMS
(APCI) calcd for C15H13BrClO2S (M + H)+ 370.9508, found
370.9503.
(E)-1-(1-Chloro-2-tosylvinyl)-2-methylbenzene (3ka): white solid
(105.5 mg, 69%); mp 80−81 °C; 1H NMR (500 MHz, CDCl3) δ 7.38
(d, J = 8.3 Hz, 2H), 7.30 (m, 1H), 7.17 (dd, J = 7.6, 5.3 Hz, 3H),
7.13−7.08 (m, 2H), 7.00 (s, 1H), 2.40 (s, 3H), 2.08 (s, 3H); 13C NMR
(125 MHz, CDCl3) δ 148.4, 144.6, 137.4, 135.9, 133.9, 132.6, 130.3,
130.2, 129.6, 128.6, 127.9, 125.5, 21.6, 19.1; HRMS (APCI) calcd for
C16H16ClO2S (M + H)+ 307.0560, found 307.0557.
(E)-1-((2-Chloro-2-(p-tolyl)vinyl)sulfonyl)-4-methylbenzene (3ba):
1
white solid (125.5 mg, 82%); mp 135−137 °C; H NMR (500 MHz,
CDCl3) δ 7.54 (d, J = 8.3 Hz, 2H), 7.31 (d, J = 8.2 Hz, 2H), 7.22 (d, J
= 8.0 Hz, 2H), 7.17 (d, J = 7.9 Hz, 2H), 6.86 (s, 1H), 2.40 (s, 3H),
2.39 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 148.2, 144.6, 141.2,
137.8, 131.5, 130.3, 129.6, 128.9, 128.7, 127.8, 21.6, 21.5; HRMS
(APCI) calcd for C16H16ClO2S (M + H)+ 307.0560, found 307.0557.
(E)-1-((2-Chloro-2-(4-pentylphenyl)vinyl)sulfonyl)-4-methyl-
benzene (3ca): pale oil (154.7 mg, 85%); 1H NMR (500 MHz,
CDCl3) δ 7.50 (d, J = 8.3 Hz, 2H), 7.31 (d, J = 8.2 Hz, 2H), 7.18 (d, J
= 8.0 Hz, 2H), 7.15 (d, J = 8.3 Hz, 2H), 6.89 (s, 1H), 2.64−2.61 (m,
2H), 2.38 (s, 3H), 1.65−1.61 (m, 2H), 1.37−1.33 (m, 4H), 0.92 (t, J =
7.0 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 148.3, 146.2, 144.4,
137.8, 131.6, 130.5, 129.5, 129.0, 128.0, 127.8, 35.8, 31.5, 30.9, 22.5,
21.6, 14.0; HRMS (APCI) calcd for C20H24ClO2S (M + H)+ 363.1186,
found 363.1182.
(E)-1-Chloro-2-(1-chloro-2-tosylvinyl)benzene (3la): white solid
1
(114.8 mg, 70%); mp 112−114 °C; H NMR (500 MHz, CDCl3) δ
7.52 (d, J = 8.3 Hz, 2H), 7.37−7.31 (m, 4H), 7.23 (d, J = 8.0 Hz, 2H),
6.97 (s, 1H), 2.41 (s, 3H); 13C NMR (126 MHz, CDCl3) δ 144.9,
144.7, 137.0, 133.5, 133.0, 132.2, 131.4, 130.6, 129.7, 129.6, 128.0,
126.6, 21.6; HRMS (APCI) calcd for C15H13Cl2O2S (M + H)+
327.0013, found 327.0011.
(E)-1-(1-Chloro-2-tosylvinyl)-3,5-bis(trifluoromethyl)benzene
(3ma): white solid (130.9 mg, 61%); mp 169−170 °C; 1H NMR (500
MHz, CDCl3) δ 7.93 (s, 1H), 7.78 (s, 2H), 7.50 (d, J = 8.2 Hz, 2H),
7.25 (d, J = 8.1 Hz, 2H), 7.09 (s, 1H), 2.41 (s, 3H); 13C NMR (125
MHz, CDCl3) δ 145.6, 143.4, 136.9, 136.4, 133.8, 131.7 (q, J = 33.9
Hz), 130.0, 129.0 (d, J = 2.8 Hz), 127.7, 124.1 (m), 122.8 (q, J = 271.4
Hz), 21.5; HRMS (APCI) calcd for C17H12ClF6O2S (M + H)+
429.0151, found 429.0149.
(E)-1-((2-Chloro-2-(4-methoxyphenyl)vinyl)sulfonyl)-4-methyl-
benzene (3da):6 white solid (118.7 mg, 74%); mp 85−86 °C; H
1
NMR (500 MHz, CDCl3) δ 7.55 (d, J = 8.3 Hz, 2H), 7.41 (d, J = 8.9
Hz, 2H), 7.22 (d, J = 8.0 Hz, 2H), 6.87 (d, J = 8.9 Hz, 2H), 6.83 (s,
1H), 3.85 (s, 3H), 2.40 (s, 3H); 13C NMR (125 MHz, CDCl3) δ
161.7, 148.0, 144.5, 137.9, 131.0, 129.7, 129.6, 127.7, 126.5, 113.4,
55.4, 21.6.
(E)-1-((2-Chloro-2-(4-(pentyloxy)phenyl)vinyl)sulfonyl)-4-methyl-
benzene (3ea): pale oil (110.3 mg, 52%); 1H NMR (500 MHz,
CDCl3) δ 7.56 (d, J = 8.3 Hz, 2H), 7.41 (d, J = 8.8 Hz, 2H), 7.22 (d, J
= 8.1 Hz, 2H), 6.86 (d, J = 8.8 Hz, 2H), 6.84 (s, 1H), 3.99 (t, J = 6.5
Hz, 2H), 2.40 (s, 3H), 1.83−1.79 (m, 2H), 1.48−1.40 (m, 4H), 0.96
(t, J = 7.1 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 161.2, 148.0,
144.4, 137.8, 130.9, 129.6, 129.4, 127.6, 126.1, 113.7, 68.1, 28.7, 28.1,
22.3, 21.5, 13.9; HRMS (APCI) calcd for C20H24ClO3S (M + H)+
379.1135, found 379.1132.
(E)-2-(1-Chloro-2-tosylvinyl)thiophene (3na): brown solid (72.6
mg, 49%); mp 54−57 °C; 1H NMR (500 MHz, CDCl3) δ 7.79 (dd, J
= 3.8, 1.1 Hz, 1H), 7.65 (d, J = 8.3 Hz, 2H), 7.54 (dd, J = 5.1, 1.1 Hz,
1H), 7.25 (d, J = 7.8 Hz, 2H), 7.05 (dd, J = 5.0, 3.8 Hz, 1H), 6.82 (s,
1H), 2.40 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 144.8, 139.9,
137.6, 135.3, 133.8, 131.5, 129.7, 129.3, 127.6, 127.4, 21.6; HRMS
(APCI) calcd for C13H12ClO2S2 (M + H)+ 298.9967, found 298.9964.
(E)-1-((2-Chlorohept-1-en-1-yl)sulfonyl)-4-methylbenzene (3oa):
1
pale oil (51.3 mg, 36%); H NMR (500 MHz, CDCl3) δ 7.78 (d, J
= 8.3 Hz, 2H), 7.36 (d, J = 8.0 Hz, 2H), 6.52 (s, 1H), 2.95−2.91 (m,
2H), 2.45 (s, 3H), 1.62−1.56 (m, 2H), 1.32 (m, 4H), 0.89 (t, J = 6.9
Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 154.4, 144.8, 138.5, 130.0,
128.9, 127.4, 34.8, 30.9, 27.2, 22.3, 21.6, 13.8; HRMS (APCI) calcd for
C14H20ClO2S (M + H)+ 287.0873, found 287.0868.
(E)-1-((2-Chloro-2-(4-fluorophenyl)vinyl)sulfonyl)-4-methyl-
(E)-1-((2-Bromo-2-phenylvinyl)sulfonyl)-4-methylbenzene
benzene (3fa):6 white solid (128.3 mg, 83%); mp 98−99 °C; H
1
(4aa):11 white solid (89.5 mg, 53%); mp 94−96 °C; H NMR (500
1
NMR (500 MHz, CDCl3) δ 7.53 (d, J = 8.3 Hz, 2H), 7.41 (dd, J = 8.9,
5.2 Hz, 2H), 7.24 (dd, J = 8.4, 0.5 Hz, 2H), 7.05 (t, J = 8.7 Hz, 2H),
6.91 (s, 1H), 2.41 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 164.0 (d, J
= 250.6 Hz), 146.7, 144.9, 137.6, 131.3, 131.2, 130.4 (d, J = 3.4 Hz),
129.8, 127.7, 115.3 (d, J = 22.0 Hz), 21.6.
MHz, CDCl3) δ 7.49 (d, J = 8.3 Hz, 2H), 7.40−7.37 (m, 1H), 7.33
(dd, J = 4.9, 1.5 Hz, 4H), 7.20 (d, J = 8.0 Hz, 2H), 7.14 (s, 1H), 2.40
(s, 3H); 13C NMR (125 MHz, CDCl3) δ 144.6, 138.3, 137.5, 136.1,
134.3, 130.4, 129.7, 128.6, 128.0, 127.9, 21.6.
(E)-(1-Bromo-2-(phenylsulfonyl)vinyl)benzene (4ab):11 white solid
1
(E)-1-Chloro-4-(1-chloro-2-tosylvinyl)benzene (3ga): white solid
(128.9 mg, 79%); mp 96−98 °C; 1H NMR (500 MHz, CDCl3) δ 7.54
(d, J = 8.3 Hz, 2H), 7.34 (s, 4H), 7.25 (d, J = 8.0 Hz, 2H), 6.91 (s,
1H), 2.41 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 146.3, 144.9,
137.5, 137.0, 132.7, 131.4, 130.3, 129.8, 128.3, 127.8, 21.6; HRMS
(APCI) calcd for C15H13Cl2O2S (M + H)+ 327.0013, found 327.0015.
(E)-1-Bromo-4-(1-chloro-2-tosylvinyl)benzene (3ha): white solid
(64.5 mg, 40%); mp 77−78 °C; H NMR (500 MHz, CDCl3) δ 7.59
(dd, J = 8.3, 1.1 Hz, 2H), 7.54 (dd, J = 11.7, 4.2 Hz, 1H), 7.41−7.36
(m, 3H), 7.33−7.29 (m, 4H), 7.17 (s, 1H); 13C NMR (125 MHz,
CDCl3) δ 140.4, 138.8, 136.0, 134.2, 133.6, 130.5, 129.0, 128.6, 128.1,
127.8.
(E)-1-((2-Bromo-2-phenylvinyl)sulfonyl)-4-methoxybenzene
1
(4ac): white solid (106.5 mg, 60%); mp 96−98 °C; H NMR (500
1
(139.6 mg, 75%); mp 101−103 °C; H NMR (500 MHz, CDCl3) δ
MHz, CDCl3) δ 7.51 (d, J = 8.9 Hz, 2H), 7.39−7.31 (m, 5H), 7.15 (s,
1H), 6.85 (d, J = 8.9 Hz, 2H), 3.84 (s, 3H); 13C NMR (125 MHz,
CDCl3) δ 163.7, 137.8, 136.2, 134.7, 131.9, 130.3, 130.0, 128.6, 128.0,
114.3, 55.7; HRMS (APCI) calcd for C15H14BrO3S (M + H)+
352.9847, found 352.9844.
7.54 (d, J = 8.3 Hz, 2H), 7.49 (d, J = 8.5 Hz, 2H), 7.27 (d, J = 8.5 Hz,
2H), 7.24 (d, J = 8.0 Hz, 2H), 6.91 (s, 1H), 2.40 (s, 3H); 13C NMR
(125 MHz, CDCl3) δ 146.3, 145.0, 137.4, 133.2, 131.5, 131.3, 130.5,
129.8, 127.8, 125.3, 21.6; HRMS (APCI) calcd for C15H13BrClO2S (M
+ H)+ 370.9508, found 370.9506.
(E)-1-((2-Bromo-2-phenylvinyl)sulfonyl)-4-chlorobenzene (4ad):
1
(E)-1-Chloro-3-(1-chloro-2-tosylvinyl)benzene (3ia): white solid
(109.9 mg, 67%); mp 87−89 °C; 1H NMR (500 MHz, CDCl3) δ 7.51
(d, J = 8.3 Hz, 2H), 7.340−7.37 (m, 1H), 7.31 (d, J = 5.0 Hz, 2H),
7.23 (dd, J = 14.5, 6.4 Hz, 3H), 6.96 (s, 1H), 2.41 (s, 3H); 13C NMR
(125 MHz, CDCl3) δ 145.8, 145.0, 137.3, 135.9, 134.1, 132.2, 130.6,
129.8, 129.39, 128.5, 127.8, 127.2, 21.6; HRMS (APCI) calcd for
C15H13Cl2O2S (M + H)+ 327.0013, found 327.0011.
(E)-1-Bromo-3-(1-chloro-2-tosylvinyl)benzene (3ja): white solid
(128.4 mg, 69%); mp 91−92 °C; 1H NMR (500 MHz, CDCl3) δ 7.54
(d, J = 8.3 Hz, 2H), 7.34 (s, 4H), 7.25 (d, J = 8.3 Hz, 2H), 6.91 (s,
1H), 2.41 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 146.3, 144.9,
white solid (86.2 mg, 48%); mp 124−125 °C; H NMR (500 MHz,
CDCl3) δ 7.50−7.47 (m, 2H), 7.42−7.48 (m, 1H), 7.36−7.31 (m,
4H), 7.28 (dd, J = 8.3, 1.3 Hz, 2H), 7.16 (s, 1H); 13C NMR (125
MHz, CDCl3) δ 140.3, 139.4, 138.8, 135.9, 134.1, 130.6, 129.3, 129.3,
128.6, 128.1; HRMS (APCI) calcd for C14H11BrClO2S (M + H)+
356.9352, found 356.9348.
(E)-1-Bromo-4-((2-bromo-2-phenylvinyl)sulfonyl)benzene (4ae):
1
white solid (74.4 mg, 37%); mp 121−123 °C; H NMR (500 MHz,
CDCl3) δ 7.51 (d, J = 8.7 Hz, 2H), 7.42−7.38 (m, 3H), 7.35−7.32 (m,
2H), 7.29−7.26 (m, 2H), 7.16 (s, 1H); 13C NMR (125 MHz, CDCl3)
δ 139.5, 139.3, 135.9, 134.0, 132.3, 130.6, 129.3, 128.9, 128.6, 128.1;
9502
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The Journal of Organic Chemistry
Note
HRMS (APCI) calcd for C14H11Br2O2S (M + H)+ 400.8847, found
400.8843.
= 3.8, 1.2 Hz, 1H), 7.62 (d, J = 8.3 Hz, 2H), 7.53 (dd, J = 5.1, 1.2 Hz,
1H), 7.25 (d, J = 8.0 Hz, 2H), 7.07 (s, 1H), 7.04 (dd, J = 5.1, 3.8 Hz,
1H), 2.40 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 144.8, 137.3,
137.1, 133.3, 133.3, 131.3, 129.7, 129.4, 127.7, 127.3, 21.6; HRMS
(APCI) calcd for C13H12BrO2S2 (M + H)+ 342.9462, found 342.9465.
(E)-1-((2-Bromohept-1-en-1-yl)sulfonyl)-4-methylbenzene
(4la):12 pale oil (59.6 mg, 36%); 1H NMR (500 MHz, CDCl3) δ 7.71
(d, J = 8.3 Hz, 2H), 7.29 (d, J = 8.0 Hz, 2H), 6.68 (s, 1H), 2.98−2.95
(m, 2H), 2.38 (s, 3H), 1.54−1.50 (m, 2H), 1.25 (m, 4H), 0.83 (t, J =
6.9 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 146.7, 144.9, 138.3,
132.1, 130.1, 127.5, 36.8, 30.8, 28.1, 22.4, 21.7, 13.9.
(E)-1-((2-Bromo-2-(p-tolyl)vinyl)sulfonyl)-4-methylbenzene
(4ba):12 white solid (89.2 mg, 51%); mp 125−126 °C; 1H NMR (500
MHz, CDCl3) δ 7.52 (d, J = 8.3 Hz, 2H), 7.25 (d, J = 8.2 Hz, 2H),
7.22 (d, J = 8.0 Hz, 2H), 7.15 (d, J = 7.9 Hz, 2H), 7.08 (s, 1H), 2.40
(s, 3H), 2.38 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 144.6, 140.9,
138.7, 137.6, 133.7, 133.3, 129.7, 128.7, 128.6, 127.8, 21.6, 21.5.
(E)-1-((2-Bromo-2-(4-pentylphenyl)vinyl)sulfonyl)-4-methyl-
benzene (4ca): pale oil (101.6 mg, 50%); 1H NMR (500 MHz,
CDCl3) δ 7.47 (d, J = 8.3 Hz, 2H), 7.24 (d, J = 8.2 Hz, 2H), 7.16 (d, J
= 8.0 Hz, 2H), 7.12 (t, J = 4.1 Hz, 3H), 2.63−2.59 (m, 2H), 2.37 (s,
3H), 1.66−1.59 (m, 2H), 1.39−1.31 (m, 4H), 0.91 (t, J = 7.0 Hz, 3H);
13C NMR (125 MHz, CDCl3) δ 145.9, 144.5, 138.8, 137.5, 136.5,
ASSOCIATED CONTENT
■
S
* Supporting Information
134.0, 129.6, 128.8, 128.0, 127.8, 35.8, 31.5, 30.9, 22.5, 21.6, 14.0;
HRMS (APCI) calcd for C20H24BrO2S (M + H)+ 407.0680, found
407.0684.
1
Copies of H and 13C NMR spectra for all products. This
material is available free of charge via the Internet at http://
pubs.acs.org.
(E)-1-((2-Bromo-2-(4-methoxyphenyl)vinyl)sulfonyl)-4-methyl-
benzene (4da):12 white solid (99.5 mg, 54%); mp 101−103 °C; H
1
NMR (500 MHz, CDCl3) δ 7.53 (d, J = 8.3 Hz, 2H), 7.34 (d, J = 8.8
Hz, 2H), 7.21 (d, J = 8.0 Hz, 2H), 7.06 (s, 1H), 6.84 (d, J = 8.8 Hz,
2H), 3.83 (s, 3H), 2.39 (s, 3H); 13C NMR (125 MHz, CDCl3) δ
161.4, 144.6, 138.7, 137.7, 133.1, 130.8, 129.7, 128.2, 127.8, 113.3,
55.4, 21.6.
AUTHOR INFORMATION
Corresponding Author
*E-mail: xqli@zjut.edu.cn, future@zjut.edu.cn.
Notes
■
(E)-1-((2-Bromo-2-(4-fluorophenyl)vinyl)sulfonyl)-4-methyl-
The authors declare no competing financial interest.
benzene (4ea):12 white solid (64.2 mg, 36%); mp 89−91 °C; H
1
NMR (500 MHz, CDCl3) δ 7.52 (d, J = 8.3 Hz, 2H), 7.37−7.34 (m,
2H), 7.24 (d, J = 8.1 Hz, 2H), 7.13 (s, 1H), 7.03 (t, J = 8.6 Hz, 2H),
2.41 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 163.7 (d, J = 250.6 Hz),
144.9, 137.4, 136.9, 134.6, 132.1 (d, J = 3.4 Hz), 131.0 (d, J = 8.7 Hz),
129.8, 127.8, 115.2 (d, J = 22.0 Hz), 21.6.
ACKNOWLEDGMENTS
■
We thank the National Natural Science Foundation of China
(21102130) and the Key Innovation Team of Science &
Technology in Zhejiang Province (2010R50018 and
2011R50017) for financial support.
(E)-1-((2-Bromo-2-(4-chlorophenyl)vinyl)sulfonyl)-4-methyl-
1
benzene (4fa): white solid (140.8 mg, 76%); mp 123−124 °C; H
NMR (500 MHz, CDCl3) δ 7.52 (d, J = 8.3 Hz, 2H), 7.32 (d, J = 8.7
Hz, 2H), 7.28 (d, J = 8.7 Hz, 2H), 7.24 (d, J = 8.1 Hz, 2H), 7.13 (s,
1H), 2.41 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 145.0, 137.3,
136.7, 136.5, 134.8, 134.5, 130.1, 129.8, 128.3, 127.8, 21.6; HRMS
(APCI) calcd for C15H13BrClO2S (M + H)+ 370.9508, found
370.9505.
REFERENCES
■
(1) For recent selected examples of difunctionalization of terminal
alkyne, see: (a) Goossen, L. J.; Rodríguez, N.; Goossen, K. Angew.
Chem., Int. Ed. 2009, 48, 9592. (b) Mizuno, A.; Kusama, H.; Iwasawa,
N. Angew. Chem., Int. Ed. 2009, 48, 8318. (c) Sha, F.; Huang, X. Angew.
Chem., Int. Ed. 2009, 48, 3458. (d) Ye, L.; Cui, L.; Zhang, G.; Zhang, L.
J. Am. Chem. Soc. 2010, 132, 3258. (e) Dutta, B.; Gilboa, N.; Marek, I.
J. Am. Chem. Soc. 2010, 132, 5588. (f) Zhang, C.; Jiao, N. J. Am. Chem.
Soc. 2010, 132, 28. (g) Kuang, J.; Ma, S. J. Am. Chem. Soc. 2010, 132,
1786. (h) Li, Y.; Liu, X.; Ma, D.; Liu, B.; Jiang, H. Adv. Synth. Catal.
2012, 354, 2683. (i) Chen, Z.; Li, J.; Jiang, H.; Zhu, S.; Li, Y.; Qi, C.
Org. Lett. 2010, 12, 3262.
(E)-1-Bromo-4-(1-bromo-2-tosylvinyl)benzene (4ga): white solid
1
(141.5 mg, 68%); mp 137−139 °C; H NMR (500 MHz, CDCl3) δ
7.52 (d, J = 8.3 Hz, 2H), 7.48 (d, J = 8.5 Hz, 2H), 7.25 (d, J = 8.1 Hz,
2H), 7.21 (d, J = 8.5 Hz, 2H), 7.13 (s, 1H), 2.42 (s, 3H); 13C NMR
(125 MHz, CDCl3) δ 145.0, 137.3, 136.5, 135.0, 134.8, 131.3, 130.2,
129.8, 127.8, 125.0, 21.7; HRMS (APCI) calcd for C15H13Br2O2S (M
+ H)+ 414.9003, found 414.9001.
(2) (a) Amiel, Y. Tetrahedron Lett. 1971, 8, 661. (b) Amiel, Y. J. Org.
Chem. 1971, 36, 3691. (c) Amiel, Y. J. Org. Chem. 1971, 36, 3697.
(d) Liu, X.; Duan, X.; Pan, Z.; Han, Y.; Liang, Y. Synlett 2005, 11,
1752.
(3) (a) Truce, W. E.; Wolf, G. C. J. Org. Chem. 1971, 36, 1727.
(b) Amiel, Y. J. Org. Chem. 1974, 39, 3867.
(E)-1-Bromo-3-(1-bromo-2-tosylvinyl)benzene (4ha): white solid
(97.5 mg, 47%); mp 111−112 °C; H NMR (500 MHz, CDCl3) δ
7.51−7.47 (m, 3H), 7.31−7.29 (m, 1H), 7.25−7.21 (m, 4H), 7.18 (s,
1H), 2.42 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 145.0, 137.8,
137.1, 135.7, 135.6, 133.2, 130.9, 129.8, 129.6, 127.9, 127.3, 121.9,
21.7; HRMS (APCI) calcd for C15H13Br2O2S (M + H)+ 414.9003,
found 414.9006.
1
(4) For recent selected examples, see: (a) Corbet, J. P.; Mignani, G.
Chem. Rev. 2006, 106, 2651. (b) Cahiez, G.; Moyeux, A. Chem. Rev.
2010, 110, 1435. (c) Amatore, C.; Jutand, A. Acc. Chem. Res. 2000, 33,
314. (d) Bettinger, H. F.; Filthaus, M. J. Org. Chem. 2007, 72, 9750.
(e) Uchiyama, M.; Furuyama, T.; Kobayashi, M.; Matsumoto, Y.;
Tanaka, K. J. Am. Chem. Soc. 2006, 128, 8404. (f) Boukouvalas, J.;
Loach, R. P. J. Org. Chem. 2008, 73, 8109.
(5) For recent selected examples, see: (a) Kumar, R.; Kumar, T.;
Mobin, S. M.; Nambothiri, I. N. N. J. Org. Chem. 2013, 78, 5073.
(b) Opekar, S.; Pohl, R.; Eigner, V.; Beier, P. J. Org. Chem. 2013, 78,
4573. (c) Urones, B.; Arrayas, R. G.; Carretero, J. C. Org. Lett. 2013,
15, 1120. (d) Suresh, R. C.; Wieczysty, M. D.; Khan, I.; Lam, H. W.
Org. Lett. 2013, 15, 570. (e) Zhao, P.; Beaudry, C. M. Org. Lett. 2013,
15, 402. (f) Huang, Z.; Kaur, J.; Bhardwaj, A.; Alsaleh, N. J. Med. Chem.
2012, 55, 10262.
(E)-1-(1-Bromo-2-tosylvinyl)-2-chlorobenzene (4ia): white solid
1
(91.4 mg, 49%); mp 97−98 °C; H NMR (500 MHz, CDCl3) δ 7.53
(d, J = 8.3 Hz, 2H), 7.35−7.31 (m, 4H), 7.24 (d, J = 8.0 Hz, 2H), 7.16
(s, 1H), 2.42 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 145.0, 136.8,
135.9, 135.0, 134.3, 131.9, 131.2, 130.1, 129.8, 129.7, 128.0, 126.6,
21.7; HRMS (APCI) calcd for C15H13BrClO2S (M + H)+ 370.9508,
found 370.9507.
(E)-1-(1-Bromo-2-tosylvinyl)-3,5-bis(trifluoromethyl)benzene
1
(4ja): white solid (123.2 mg 54%); mp 147−149 °C; H NMR (500
MHz, CDCl3) δ 7.88 (s, 1H), 7.71 (s, 2H), 7.48 (d, J = 8.3 Hz, 2H),
7.30 (s, 1H), 7.24 (d, J = 8.1 Hz, 2H), 2.41 (s, 3H); 13C NMR (125
MHz, CDCl3) δ 145.6, 138.1, 137.1, 136.7, 133.0, 131.7 (q, J = 33.8
Hz), 130.0, 128.7 (d, J = 3.2 Hz), 127.7, 123.8 (m), 122.7 (q, J = 271.3
Hz), 21.5; HRMS (APCI) calcd for C17H12BrF6O2S (M + H)+
472.9646, found 472.9641.
(6) Zeng, X.; Ilies, L.; Nakamura, E. Org. Lett. 2012, 14, 954.
(7) (a) Li, X.; Xu, X.; Zhou, C. Chem. Commun. 2012, 48, 12240.
(b) Li, X.; Xu, X.; Hu, P.; Xiao, X.; Zhou, C. J. Org. Chem. 2013, 78,
(E)-2-(1-Bromo-2-tosylvinyl)thiophene (4ka): brown solid (71.9
mg, 42%); mp 84−86 °C; 1H NMR (500 MHz, CDCl3) δ 7.67 (dd, J
9503
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Note
7343. (c) Li, X.; Xu, X.; Tang, Y. Org. Biomol. Chem. 2013, 11, 1739.
(d) Li, X.; Xu, X.; Shi, X. Tetrahedron Lett. 2013, 54, 3071.
(8) Taniguchi, T.; Fujii, T.; Ishibashi, H. J. Org. Chem. 2010, 75,
8126.
(9) The compounds 3aa, 3ac, 3ad, 3da, and 3fa are synthesized in
66, 55, 67, 52, and 63% yields, respectively, in ref 6.
(10) Liu, W.; Li, Y.; Liu, K.; Li, Z. J. Am. Chem. Soc. 2011, 133,
10756.
(11) Taniguchi, N. Synlett 2011, 1308.
(12) Gilmore, K.; Gold, B.; Alabugin, L. V. Aust. J. Chem. 2013, 66,
336.
9504
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