MnO2-Promoted Oxidative Radical Sulfonylation of Haloalkynes with Sulfonyl Hydrazides: C(sp)–S Bond Formation towards Alkynyl Sulfones

Article abstract of DOI:10.1002/asia.201700550

A catalyst-free oxidative radical sulfonylation of haloalkynes with sulfonyl hydrazides is reported. It represents an example of C(sp)?S bond formation using sulfonyl hydrazides as sulfonyl radical sources. Various alkynyl sulfones were synthesized in moderate to good yields. Having MnO₂ as the oxidant is very critical for this transformation. Remarkably, the self-coupling reaction of haloalkynes through C(sp)?C(sp) bond formation is significantly inhibited under the standard reaction conditions.

Full text of DOI:10.1002/asia.201700550

DOI: 10.1002/asia.201700550
Communication
Sulfonylation
MnO2-Promoted Oxidative Radical Sulfonylation of Haloalkynes
with Sulfonyl Hydrazides: C(sp)–S Bond Formation towards
Alkynyl Sulfones
Pengquan Chen, Chuanle Zhu,* Rui Zhu, Wanqing Wu, and Huanfeng Jiang*[a]
ed alkyl sulfone compounds via C(sp3)ÀS bond formation
(Scheme 1a),[11] while their reactions with CÀC triple bonds de-
Abstract: A catalyst-free oxidative radical sulfonylation of
haloalkynes with sulfonyl hydrazides is reported. It repre-
livered the corresponding vinyl sulfone derivatives smoothly
through C(sp2)ÀS bond formation (Scheme 1b).[12] Typically,
these two types of transformations involved transition metal
catalysts, such as Fe and Cu complexes or iodide catalysts, to
ensure reactivity and selectivity, and have found broad applica-
tions in the field of synthetic and medicinal chemistry. Howev-
er, the reaction of sulfonyl radicals derived from sulfonyl hydra-
zides, which provides alkynyl sulfones as products via C(sp)ÀS
bond formation has not been reported yet, despite the fact
that alkynyl sulfones are significant motifs in the field of syn-
thetic and medicinal chemistry.[13]
sents an example of C(sp)ÀS bond formation using sulfo-
nyl hydrazides as sulfonyl radical sources. Various alkynyl
sulfones were synthesized in moderate to good yields.
Having MnO2 as the oxidant is very critical for this trans-
formation. Remarkably, the self-coupling reaction of hal-
oalkynes through C(sp)ÀC(sp) bond formation is signifi-
cantly inhibited under the standard reaction conditions.
Organosulfones are a class of highly valuable compounds and
have emerged as privileged building blocks in the area of
pharmaceutical and agrochemical chemistry because of their
impressive biological activities such as anti-HIV, anticancer, and
antibacterial.[1] Owing to their readily removable ability via vari-
ous desulfonylation methods, they also serve as significant syn-
thetic intermediates in numerous natural-product total synthe-
ses.[2] Therefore, the development of efficient and practical
methods for the synthesis of organosulfones has received con-
siderable attention over the past decades.[3] Generally, the gen-
eration of a sulfonyl radical and its addition to unsaturated
carbonÀcarbon bonds, such as CÀC double bonds and CÀC
triple bonds, represents one of the most popular and promis-
ing methods to construct sulfone derivatives. Among various
sulfonyl radical sources such as sulfonyl halides,[4] arylsulfinic
acids,[5] arylsulfinic azides,[6] arylsulfinic cyanides,[7] sodium sulfi-
nates[8] and SO2,[9] sulfonyl hydrazides, which are non-corrosive,
do not have unpleasant odor, are compatible with water, and
provide readily available synthons, have emerged as a friendly
and powerful source of sulfonyl radicals under oxidative condi-
tions.[10] Generally, the reactions of these sulfonyl radicals de-
rived from sulfonyl hydrazides with CÀC double bonds afford-
Scheme 1. Oxidative radical sulfonylation of unsaturated bonds with sulfonyl
hydrazides.
Owing to the sp hybridization of the CÀC triple bonds and
the connected halogen atoms, haloalkynes have been served
as practical and versatile building blocks and found broad ap-
plications in the area of synthetic and material chemistry.[14] As
our recent interest for the synthesis of sulfone derivatives,[15] as
well as our continuous effort on exploiting the potential reac-
tivities and synthetic applications of haloalkynes,[14] herein, we
report a catalyst-free oxidative radical sulfonylation of haloal-
kynes with sulfonyl hydrazides. To the best of our knowledge,
it represents the first example for C(sp)ÀS bond formation with
sulfonyl radicals derived from sulfonyl hydrazides. Using MnO2
as the oxidant is very critical for this transformation, delivering
various alkynyl sulfones in moderate to good yields. Addition-
ally, the self-coupling products of haloalkynes through C(sp)À
C(sp) bond formation were significantly inhibited.[16]
[a] P. Chen, Dr. C. Zhu, R. Zhu, Prof. Dr. W. Wu, Prof. Dr. H. Jiang
Key Laboratory of Functional Molecular Engineering of Guangdong Prov-
ince
School of Chemistry and Chemical Engineering
South China University of Technology
Guangzhou 510640 (P.R. China)
E-mail: cechlzhu@scut.edu.cn
jianghf@scut.edu.cn
Supporting information and the ORCID identification number(s) for the au-
thor(s) of this article can be found under https://doi.org/10.1002/
asia.201700550.
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At the outset of our studies, we investigated this catalyst-
free oxidative radical sulfonylation of haloalkynes with bro-
moalkyne 2a and sulfonyl hydrazide 4a as the starting materi-
als in DMA (dimethylacetamide) at 908C, using TBHP (tert-butyl
hydroperoxide) as an oxidant, which is known to promote the
generation of sulfonyl radicals from sulfonyl hydrazides
(Table 1, entry 1).[10] Unfortunately, none of the desired produc-
t 5a was detected by GC-MS or NMR analysis. As expected, no
reaction happened in the absence of oxidants (Table 1,
entry 2). Next, diverse oxidants such as BQ (benzoquinone),
DDQ (2,3-dicyano-5,6-dichlorobenzoquinone), TEMPO (2,2,6,6-
tetramethylpiperidine N-oxide), DTBP (di-tert-butyl peroxide), I2,
30% aq. H2O2, O2, K2S2O4, and MnO2 were investigated (Table 1,
entries 3–11). To our delight, MnO2 gave the desired produc-
t 5a in 79% isolated yield. It is worth noting that the organic
solvent was also very critical for this C(sp)ÀS bond formation
reaction. The use of other polar solvents such as DMF, DMSO,
NMP (N-methyl pyrrolidone), MeCN, and THF and nonpolar sol-
vents, such as 1,4-dioxane, DCE (1,2-dichloroethane) or tolu-
ene, were ineffective in this reaction, and led to a significantly
lower yield of 5a (Table 1, entries 12–19). By reducing the load-
ing of MnO2 to 3 equivalents, the yield of 5a decreased to
63% (Table 1, entry 20). Furthermore, when bromoalkyne 2a
was replaced with chloroalkyne 1a, no desired product was
observed (Table 1, entry 21). Interestingly, the isolated yield of
5a was further enhanced to 80% with iodoalkyne 3a as the re-
actant (Table 1, entry 22).
With the optimized conditions in hand, we next turned our
attention to the generality of this catalyst-free oxidative radical
sulfonylation of haloalkynes 3 with sulfonyl hydrazides 4
(Scheme 2). First, different haloalkynes 3 were investigated
with sulfonyl hydrazide 4a as the reaction partner. Both elec-
tron-donating groups (methyl, propyl, tert-butyl and methoxyl)
and electron-withdrawing groups (fluoro and chloro) on the
phenyl ring of haloalkynes 3 were tolerated under the stan-
dard reaction conditions, delivering the corresponding alkynyl
sulfones 5a–5j in good yields. 2-Ethynylthiophene-derived hal-
oalkyne was also applicable to this oxidative reaction system
and afforded 5k in 42% yield. Significantly, ethynylcyclopro-
pane-derived haloalkyne was also a good substrate, providing
alkynyl sulfone 5l in 58% yield. Furthermore, the substrate
scope was extended to different substituted sulfonyl hydra-
zides 4 with haloalkyne 3a as the reaction partner. Gratifyingly,
sulfonyl hydrazides with methyl, chloro or bromo groups on
the phenyl ring could deliver the corresponding alkynyl sul-
fones smoothly (5m–5o).
In 2010, we reported that the self-coupling reaction of io-
doalkynes could provide the corresponding diynes in high
yields.[16] To cast some light on the mechanism details of this
cross-coupling reaction, some control experiments were per-
formed. First, the competition reactions between self-coupling
of iodoalkyne 3a and cross-coupling of iodoalkyne 3a and sul-
fonyl hydrazide 4a were conducted at different reaction tem-
peratures. The reaction temperature could significantly influ-
ence the yields of the products (Figure 1). It is worth noting
that the yields of self-coupling product 6a were <1% in all of
these cases, while performing the reaction at 808C gave the
Table 1. Reaction optimizations.[a]
Entry
Haloalkynes
Oxidants
Solvent
Yield [%][b]
1
2
3
4
5
6
7
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
1a
3a
TBHP
–
BQ
DDQ
TEMPO
DTBP
I2
H2O2
O2
K2S2O4
MnO2
MnO2
MnO2
MnO2
MnO2
MnO2
MnO2
MnO2
MnO2
MnO2
MnO2
MnO2
DMA
DMA
DMA
DMA
DMA
DMA
DMA
DMA
DMA
DMA
DMA
DMF
DMSO
NMP
MeCN
THF
1,4-dioxane
DCE
toluene
DMA
DMA
DMA
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
8
80 (79)
39
n.d.
n.d.
6
8[c]
9
10
11
12
13
14
15
16
17
18
19
20[d]
21
22
20
8
n.d.
n.d
63
0
82 (80)
[a] A mixture of haloalkyne (0.3 mmol, 1 equiv), 4a (0.45 mmol, 1.5 equiv),
oxidant (4 equiv) and solvent (2 mL) was stirred at 808C for 24 h. [b] The
yields were determined by GC-MS with dodecane as an internal standard.
The numbers in the parentheses show the isolated yield. [c] 33% aq. H2O2.
[d] MnO2 (3 equiv). n.d.=not detected.
Figure 1. The influence of the reaction temperature.
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Scheme 2. Substrate scope of haloalkynes and sulfonyl hydrazides. Unless otherwise noted, the reaction conditions were: iodoalkynes 3 (0.3 mmol), sulfonyl
hydrazides 4 (1.5 equiv), MnO2 (4 equiv), and DMA (2 mL) at 808C for 24 h. [a] Isolated yield.
cross-coupling product 5a in 82% GC yield, which indicated
that the initial generation of an alkynyl radical was unlikely
under our reaction conditions. Furthermore, 2 equivalents of
TEMPO or BHT (butylhydroxytoluene) were added to the reac-
tion mixture of iodoalkyne 3a and sulfonyl hydrazide 4a under
standard reaction conditions, and product 5a was not ob-
served, further confirming the initial generation of a sulfonyl
radical (Scheme 3).
Scheme 4. Proposed mechanism.
In summary, we have reported a catalyst-free oxidative radi-
cal sulfonylation reaction of haloalkynes with sulfonyl hydra-
zides. It represents an example of C(sp)ÀS bond formation in-
Scheme 3. Control experiments.
volving sulfonyl hydrazides as the sulfonyl radicals source. Vari-
ous alkynyl sulfones were synthesized in moderate to good
On the basis of these experimental results and previous liter-
ature,[10,14,16] we tentatively proposed a possible reaction mech-
anism (Scheme 4). Sulfonyl radical A was generated from sulfo-
nyl hydrazide 4a under oxidative conditions. Subsequent inter-
molecular addition of the obtained sulfonyl radical A to iodoal-
kyne 3a gave a vinyl radical intermediate B, which further con-
verted to the final alkynyl sulfone product 5a, releasing an
iodo radical. The purple color of the obtained reaction mixture
indicated the generation of I2 under our reaction conditions.
yields. The identification of MnO2 as the oxidants is very critical
for the success of this transformation. Significantly, the self-
coupling reaction of haloalkynes through C(sp)ÀC(sp) bond for-
mation is significantly inhibited under the standard reaction
conditions. Efforts are currently underway in our laboratory to
investigate the mechanistic details, the synthetic applications
of this chemistry, and these results will be reported in due
course.
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Miura, A. Itoh, RSC Adv. 2014, 4, 13191–13194; d) H.-S. Li, G. Liu, J. Org.
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Experimental Section
General Procedure: A 25 mL oven-dried Schlenk tube equipped
with a magnetic stirring bar, iodoalkynes 3 (0.3 mmol), arylsulfonyl
hydrazides 4 (0.45 mmol), MnO2 (1.2 mmol) and DMA (2 mL) was
vigorously stirred at 808C for 24 h in an oil bath. After the reaction
ended, the resulting solution was cooled to room temperature,
added EtOAc (30 mL), washed with saturated Na2S2O3 aqueous so-
lution (3ꢁ10 mL). The organic phase was dried over anhydrous
Na2SO4, filtered and concentrated in vacuo. Further purification by
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Acknowledgements
We thank the National Program on Key Research Project
(2016YFA0602900), the National Natural Science Foundation of
China (21490572 and 21420102003), the Guangdong Natural
Science Foundation (2016A030310460), the Fundamental Re-
search Funds for the Central Universities (2015ZY001 and
2015ZM163), and the China Postdoctoral Science Foundation
Funded Project (2015M580717 and 2017T100623) for financial
support.
Keywords: alkynes · C(sp)-S bond formation · organosulfones ·
radical reactions · sulfonyl hydrazides
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Accepted manuscript online: May 17, 2017
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COMMUNICATION
Sulfonylation
Pengquan Chen, Chuanle Zhu,* Rui Zhu,
Wanqing Wu, Huanfeng Jiang*
&& – &&
MnO2-Promoted Oxidative Radical
Sulfonylation of Haloalkynes with
Sulfonyl Hydrazides: C(sp)–S Bond
Formation towards Alkynyl Sulfones
C(sp)ÀS Bond Formation: A catalyst-
free oxidative radical sulfonylation of
haloalkynes with sulfonyl hydrazides has
been developed. Various alkynyl sul-
fones were synthesized in moderate to
good yields, and MnO2 was used as the
oxidant.
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