Solvent Controlled Transformation between Sulfonyl Hydrazides and Alkynes: Divergent Synthesis of Benzo[b]thiophene-1,1-dioxides and (E)-β-iodo Vinylsulfones

Article abstract of DOI:10.1002/adsc.201801258

A green, efficient and controllable transformation between sulfonyl hydrazides and alkynes leading to benzo[b]thiophene-1,1-dioxides and (E)-β-iodo vinylsulfones via radical pathway has been developed. The reaction occurs rapidly in the presence of simply H₂O₂ and KI without the help of any transition metal. The chemoselectivity of the reaction is determined by the solvent in which the process is performed: TFE favors the cyclic product, while H₂O medium generates the iodosulfonylative product. Notably, this protocol also represents the first direct approach to the aggregation-induced-emmision (AIE) active benzo[b]thiophene-1,1-dioxides from readily available sulfonyl hydrazides and alkynes in one step. (Figure presented.).

Full text of DOI:10.1002/adsc.201801258

Title: Solvent Controlled Transformation between Sulfonyl Hydrazides
and Alkynes: Divergent Synthesis of Benzo[b]thiophene-1,1-
dioxides and (E)-β-iodo Vinylsulfones
Authors: Yue Ma, Kun Wang, Dong Zhang, and Peng Sun
This manuscript has been accepted after peer review and appears as an
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201801258
Link to VoR: http://dx.doi.org/10.1002/adsc.201801258

10.1002/adsc.201801258
Advanced Synthesis & Catalysis
UPDATE
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Solvent Controlled Transformation between Sulfonyl
Hydrazides and Alkynes: Divergent Synthesis of
Benzo[b]thiophene-1,1-dioxides and (E)-β-iodo Vinylsulfones
Yue Ma,a,b Kun Wang,a,b Dong Zhang,a Peng, Sun a*
a
Artemisinin Research Center and Institute of Chinese Materia Medica, China Academy of Chinese Medical Sciences,
Beijing 100700, P. R. China
Email: psun@icmm.ac.cn
These authors contributed equally to this work
b
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract.
A
green, efficient and controllable
transformation between sulfonyl hydrazides and alkynes
leading to benzo[b]thiophene-1,1-dioxides and (E)-β-iodo
vinylsulfones via radical pathway has been developed. The
reaction occurs rapidly in the presence of simply H2O2 and
KI without the help of any transition metal. The
chemoselectivity of the reaction is determined by the
solvent in which the process is performed: TFE favors the
cyclic product, while H2O medium generates the
iodosulfonylative product. Notably, this protocol also
represents the first direct approach to the aggregation-
induced-emmision (AIE) active benzo[b]thiophene-1,1-
dioxides from readily available sulfonyl hydrazides and
alkynes in one step.
Keywords: Solvent; Metal-free; Benzo[b]thiophene-1,1-
dioxides; iodo vinylsulfones; AIE
In the last few decades, radical based reactions have
become one of the most powerful instruments for the
synthetic community.[1,2] Even significant progress
has been made in this field, switchable radical based
reactions to obtain skeletal divergent products in
controllable manners remain relatively unexplored
and challenging due to the highly reactive nature of
free radicals.[3] These reactions are of great value for
Scheme 1. The existing approaches to construct
benzo[b]thiophene-1,1-dioxides and β-iodo vinylsulfones.
green
chemistry
and
organic
synthesis.
Benzo[b]thiophene-1,1-dioxides represent a class of
interesting organosulfur compounds which exhibit
wide applications in pharmaceuticals,[4] organic
synthesis[5], and optoelectronic materials.[6] The most
frequent approach to prepare benzo[b]thiophene-1,1-
dioxides rely on the oxidation of the pre-synthesized
benzo[b]thiophenes,[7] which suffer from tedious
steps, poor yield and limited functional group
2-substituted benzo[b]thiophene -1,1-dioxides were
developed by Wu and coworkers (Scheme 1a). As we
know,
a
straightforward synthetic route to
from readily
benzo[b]thiophene-1,1-dioxides
available organosulfur species and simple alkynes
remain unexplored. The iodosulfonylation of alkynes
employing sulfonic acid derivatives have been well
established as efficient methodologies to obtain iodo
vinylsulfones (Scheme 1b).[10] Among these elegant
examples, Wan and Liu reported a Cu-mediated
stereoselective Z-iodosulfonylation of terminal
alkynes employing sulfonyl hydrazides in 2016.[11]
tolerance.
Recently,
two
Cu-catalyzed
of 2-
insertion/cyclization
reactions
alkynylaryldiazonium[8] and (2-alkynylaryl)boronic
Acids[9] with DABCO-bis(sulfur dioxide) offering
1
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10.1002/adsc.201801258
Advanced Synthesis & Catalysis
Next, a KI/BPO mediated E-iodosulfonylation of
terminal alkynes were achieved by Wei and Liu in
2017.[12] Despite these successes, their study was
focused on the iodosulfonylation of internal alkynes.
The iodosulfonylation of internal alkynes, especially
diphenyl-alkynes, using sulfonyl hydrazides remain
rarely reported. Herein, we disclose a controllable
radical reaction between sulfonyl hydrazides and
alkynes offering benzo[b]thiophene-1,1-dioxides and
When 0.1 mmol of iodine was loaded to the reaction
system, 77% of 3a was obtained (Table 1, Entry 7). Iodine
was also examined in H2O to offer 4a as the single product
(see Surpporting Information Table 1, Entry 1). 3a and 4a
were obtained in 19%, and 10% yields respectively when
TBAI was applied (Table 1, Entry 8). Later, the amounts of
KI were also tested and the yield of 3a increased to 82%
with a reduction of KI to 0.05 mmol (Table 1, Entries 9-
11). To improve the yield of 4a, we increased the
amount of KI to 1.5 equivalents and screened a
variety of solvents (comprehensive screening was
provided in Supporting Information). The use of THF
increased the yield of 4a to 47% (Table 1, Entry 12).
When H2O was used as solvent, 4a was obtained with
a yield of 85% (Table 1, Entry 16).
With the optimized conditions in hand, the
substrate scope of the addition/cyclization reaction
was studied as shown in Table 2. First of all, a series
of sulfonyl hydrazides was investigated. When
benzenesulfonyl hydrazide (1b) was tested in
conditions A, 75% of 3b was produced. Substrate
which are with sterically bulky tert-butyl at the para-
position performed smoothly to give 85% yield (3c).
An excellent yield of 89% was obtained when a
strong electron-donating methoxyl group substituted
benzenesulfonyl hydrazide was examined (3d). A
trifluoromethyl group at the para-position did not
influence the process, and the corresponding product
3e was prepared in the yield of 63%. Substrate with a
strong electronic-withdrawing nitro group failed to
produce 3f. These results indicated that the electron
density of the benzene ring is of great importance for
(E)
-
β
-iodo vinylsulfones. This protocol exhibits
selectivity, operational simplicity,
excellent
scalability, and good yields. Only environmentaly
benign KI and H2O2 were necessary to generate the
two precious products without the use of toxic
transition metal. Additionally, the photo-physical
properties of the selected product 3c were studied to
confirm the AIE nature of the skeleton.
We began our investigations employing 4-
methylbenzenesulfonohydrazide, 1a, and 1,2-
diphenylethyne, 2a, as the model substrates. To our
delight, 11% of 3a was obtained when the reaction
was conducted with of 0.5 equivalents of KI, and 4.0
equivalents of TBHP in 2,2,2-trifluoroethanol (TFE)
(Table 1, Entry 1). Peroxide oxidants, such as DTBP,
and H2O2, were examined to increase the yield to
79% (Table 1, Entries 2-3). The screening of other
oxidants such as Iodobenzene diacetate (PIDA),
K2S2O8 and Oxone did not improve the yield of 3a,
yet, iodosulfonylative product, 4a, was produced in
yields of no more than 20% (Table 1, Entries 4-6).
Table 1. Optimization of conditions. a, b
Table 2. Substrate scope of the addition/cyclization
reaction.a, b
Entry Oxidant
Solvent
Iodine
source
Yield Yield
(3a)
(4a)
KI
KI
KI
KI
KI
KI
I2
TBAI
KI
KI
/
KI
KI
KI
KI
KI
1
2
3
4
5
6
7
8
TBHP
DTBP
H2O2
PIDA
K2S2O8
Oxone
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
TFE
TFE
TFE
TFE
TFE
TFE
TFE
TFE
TFE
11%
20%
79%
Nd.
35%
30%
77%
19%
82%
60%
Nd.
Nd.
23%
Nd.
Nd.
17%
19%
Nd.
10%
Nd.
Nd.
Nd.
47%
15%
55%
Nd.
9c
10d
11
12e
13e
14e
15e
TFE
TFE
THF
CH3CN
Toluene
DMF
H2O
Nd.
Nd.
Nd.
Nd.
16e
Nd.
85%
a)
Reaction conditions: 1a (0.4 mmol, 2.0 equiv), 2a (0.2
mmol, 1.0 equiv), oxidant (0.8 mmol, 4.0 equiv), iodine
a) Reaction conditions A: 1a (0.4 mmol, 2.0 equiv), 2a (0.2
o
source (0.1 mmol, 0.5 equiv), solvent (2 mL), 100 C, 2
b)
hours under air atmosphere. Isolated yield. c) 0.05 mmol
mmol, 1.0 equiv), H2O2 (0.8 mmol, 4.0 equiv), KI (0.1
o
KI was used. d) 0.02 mmol KI was used. e) 0.3 mmol iodine
source was used.
mmol, 0.5 equiv), TFE (2 mL), 100 C, 2 hours under air
atmosphere. b) Isolated yield.
2
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10.1002/adsc.201801258
Advanced Synthesis & Catalysis
In the past decade, the developments of novel
organic luminescent materials with AIE properties
have attracted considerable attention.[14] To confirm
the AIE nature of the benzo[b]thiophene-1,1-dioxides
generated herein, 3c was picked as a representative
example and its photoluminescent (PL) spectra of
solid powder (for PL spectra of solid powder of 3c,
see Supproting Information) and in mixtures of
THF/water (scheme 2) with different fractions of
water (fw) were investigated. When the fw was no
more than 60%, the PL emission remained very weak.
After increasing the fw to 65%, an emission peak
appeared. A dramatic enhancement in luminescence
was observed when the water fraction was increased
to 80%. These observation clearly identified the AIE
nature of 3c.
the product generation. Multi-substituted product 3g
was also obtained in 83% yield. When 3,4-dimethoxy
substrate was examined in the system, 3h and 3l were
generated in the ratio of 1:2 and totally 90% yield. 3j
was also synthesized through our method with a yield
of 76%, and its structure was identified by single-
crystal X-ray analysis.[13] Next, various symmetric
internal alkynes were examined to generate
corresponding products in yields of 0% to 81% (3k-
3o). In particular, bromo- and chloro-substituted
products were prepared smoothly, which provides the
possibility for further functionalizations. Terminal
alkynes such as phenylacetylene and ethyl propiolate
were also examined, but failed to yield desired cyclic
products.
Next, the scope of the iodosulfonylation reaction
was expanded and summarized in Table 3. Firstly,
alkyl, alkoxyl substituted benzenesulfonyl hydrazides
were examined to give corresponding products in the
yield of 85% to 93% (4a-4c). Halo-substituted
products 4d-4g were synthesized in 67%, 70%, 63%,
58% yields respectively. Benzenesulfonyl hydrazides
bearing trifluoromethyl and trifluoromethoyl in the
para-position offered correponding products 4h and
4i in the yields of 67% and 75%. Alkylsulfonyl
hydrazide was also examined to offer 4j in 85% yield.
Apart from the substrate with a strong electronic-
withdrawing nitro group, diphenylalkynes performed
smoothly in the optimized conditions B to generate
corresponding products in the yields of 65% to 86%.
4p and 4q were also obtained in the yield of 92% and
95%. To expand the application of our method, the
generated iodo vinylsulfone product 4a was also
functionalized via Pd-catalyzed phenylation. The
structure of the product was identified by single-
crystal X-ray analysis (for details, see Supporting
Information).
fw(vol%)
90%
80%
70%
67%
65%
62%
60%
50%
40%
30%
20%
10%
80000
60000
40000
20000
0
300
400
500
Wavelength (nm)
600
Scheme 2. PL spectra of 3c in THF-water mixtures with
different water fractions (fw).
Next, experiments were performed to get some
insight into the possible mechanism of the reaction,
as shown in Scheme 3. When 3.0 equivalents of free
radical scavenger TEMPO were added to the reaction
system, the reaction was completely inhibited, which
indicated that our protocol should involve a radical
pathway (Scheme 3a). To identify the intermediates
of the reactions, control experiments were carried out
to generate 5 and 6 in the two standard conditions
(Scheme 3b). When 5 and 2a were treated with the
standard conditions, 3a and 4a were obtained in over
80% yields. Moreover, 6 was also isolated in the
yields of about 10% (Scheme 3c). When 5 was
subjected to the standard conditions, 6 was generated
in the yields of 71% and 80% (Scheme 3d). The
examinations of 6 in the standard conditions
generated 3a and 4a in the yields of 93% and 97%
respectively (Scheme 3e). The results of these
experiments indicated that the 5 and 6 generated from
the substrate 1 were the intermediates of the
transformations. Unsymmetrical thiosulfonate 7 was
also tested in standard conditions to offer 3d and 4c
(Scheme 3f). It has been reported that the strong H-
bond donor (HBD) solvents, such as hexafluoro-2-
propanol, and TFE might prove useful for the
cyclizations of radicals reactions.[15] To confirm the
role of TFE in the regulation of the reaction
selectivity, experiments were performed in the
mixture of TFE/water with different fractions of TFE
Table 3. Substrate scope of the iodosulfonylation
reaction.a, b
a) Reaction conditions B: 1a (0.4 mmol, 2.0 equiv), 2a (0.2
mmol, 1.0 equiv), H2O2 (0.8 mmol, 4.0 equiv), KI (0.3
o
mmol, 1.5 equiv), H2O (2 mL), 100 C, 2 hours under air
atmosphere. b) Isolated yield.
3
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10.1002/adsc.201801258
Advanced Synthesis & Catalysis
(fT) (for details, see Supporting Information). The
yield of 3a decreased significantly with the reduction
of fT. When fT was decreased to 40%, 3a was not
detected in the reaction system, while 4a was
obtained as the single product. Moreover, other
solvents with similar properties, such as HFIP, and 4-
(CF3)-PhCH2OH were also examined to offer 3a.
TFE medium could decrease the activation energy of
the cyclization reaction. When the reaction was
performed in TFE, intra-molecular cyclization of Z-
(8) happened to produce 9. Further oxidization and
deprotonation processes gave the cyclic product 3.
However, when the reaction was conducted in H2O,
E-(8) was captured by generated I2 to deliver 4.
Scheme 4. Plausible reaction pathway.
In conclusion, a green, efficient and solvent-
controlled strategy has been developed for the
divergent synthesis of benzo[b]thiophene-1,1-
dioxides and (E)-β-iodovinylsulfones from readily
available sulfonyl hydrazides and alkynes via radical
pathway for the first time. Remarkably, the AIE
properties of the generated benzo[b]thiophene-1,1-
dioxides were confirmed and a series of novel AIE-
active molecules were obtained via our method.
Further applications of the method in medicinal and
other fields are under investigation.
Experimental Section
Scheme 3. Mechanism study.
Conditions A: A sealed tube was charged with alkynes (0.2
mmol, 1.0 equiv), sulfonyl hydrazides (0.4 mmol, 2.0
equiv), KI (0.05 mmol, 25 mmol%), 30% H2O2 (0.8 mmol,
4.0 equiv) and 2.0 mL TFE. The reaction mixture was
Based on the experiments above and previous
reports,[16] the mechanism of the reaction was
proposed as shown in Scheme 4. Firstly, iodine was
generated from the oxidization of the KI, which later
mediated the transformation from sulfonyl hydrazides
substrates 1 to the intermediates 5 and 6.[17] The
o
vigorously stirred at 100 C (oil temperature) for 2 hours.
After cooling to room temperature, the reaction mixture
was quenched with 10 mL saturated ammonium chloride
solution and then diluted with ethyl acetate (20 mL). The
organic layer was washed with distilled water and brine
successively. After the solvent been removed under
reduced pressure, the rude product was purified by flash
chromatography on silica gel to afford the desired
benzo[b]thiophene-1,1- dioxides.
intermediate
5
could be further oxidized to
Conditions B：A sealed tube was charged with alkynes
(0.2 mmol, 1.0 equiv), sulfonyl hydrazides (0.4 mmol, 2.0
equiv), KI (0.3 mmol, 1.5 equiv), 30% H2O2 (0.8 mmol,
4.0 equiv) and 2.0 mL H2O. The reaction mixture was
intermediate 6 in the presence of H2O2. Subsequently,
the free radical intermediate 7 was produced from the
intermediate 6. Next, the addition of 7 to alkyne
substrate 2 yielded the vinyl radicals 8 which has Z
and E two isomers.[18] TFE could serve as a strong
HBD to increase the persistence of the vinyl radical 8
and decrease its ability to react with I2. Meanwhile,
the solvation of both reactants and transition states in
o
vigorously stirred at 100 C (oil temperature) for 2 hour.
After cooling to room temperature, the reaction mixture
was quenched with 10 mL saturated ammonium chloride
solution and then diluted with ethyl acetate (20 mL). The
organic layer was washed with distilled water and brine
successively. After the solvent been removed under
reduced pressure, the rude product was purified by flash
4
This article is protected by copyright. All rights reserved.

10.1002/adsc.201801258
Advanced Synthesis & Catalysis
chromatography on silica gel to afford the desired (E)-β-
iodo vinylsulfones.
Chem. 2017, 2017, 4405-4413; f) Y. Wang, R. Wu, S.
Zhao, Z. Qian, Y. Su, C. Huo, Org. Bioorg. Chem.
2018, 16, 1667-1671.
Acknowledgements
[8] Y. Luo, X. Pan, C. Chen, L. Yao, J. Wu, Chem.
Commun. 2015, 51, 180-182.
Generous financial support from the National Natural Science
Foundation of China (21702235, 81641002), the Fundamental
Research Funds for the Central Public Welfare Research
Institutes (ZZ10-024, ZXKT17053), Major National Science and
Technology Program of China for Innovative Drug
(2017ZX09101002-001-001). We also thank Mr. Sean Spurlin at
Auburn University for the help of preparing the manuscript.
[9] Y. Mao, D. Zheng, H. Xia, J. Wu, Org. Chem. Front.
2016, 3, 693-696.
[10] For recent examples of halosulfonylation of alkynes,
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5
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10.1002/adsc.201801258
Advanced Synthesis & Catalysis
UPDATE
Solvent Controlled Transformation between
Sulfonyl Hydrazides and Alkynes: Divergent
Synthesis of Benzo[b]thiophene-1,1-dioxides and
(E)-β-iodo Vinylsulfones
Adv. Synth. Catal. Year, Volume, Page – Page
Yue Ma, Kun Wang, Dong Zhang, Peng, Sun *
6
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