Efficient synthesis of aliphatic sulfones by Mg mediated coupling reactions of sulfonyl chlorides and aliphatic halides

Article abstract of DOI:10.1039/c7ob00251c

Sulfonyl chlorides were reduced to anhydrous sulfinate salts with magnesium under sonication. These sulfinates were alkylated to sulfones with alkyl chlorides in the presence of catalytic sodium iodide under sonication. A variety of aliphatic sulfones was efficiently prepared by this one-pot two-step procedure.

Full text of DOI:10.1039/c7ob00251c

View Article Online
View Journal
Organic &
Biomolecular
Chemistry
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: Y. Fu, Q. Xu, Q. Li,
Z. Du, K. Wang, D. Huang and Y. Hu, Org. Biomol. Chem., 2017, DOI: 10.1039/C7OB00251C.
This is an Accepted Manuscript, which has been through the
Volume 14 Number
1 7 January 2016 Pages 1–372
Royal Society of Chemistry peer review process and has been
accepted for publication.
Organic &
Biomolecular
Chemistry
www.rsc.org/obc
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
author guidelines.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
ISSN 1477-0520
COMMUNICATION
Takeharu Haino et al.
Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
benzene
rsc.li/obc

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 1 of 5
View Article Online
DOI: 10.1039/C7OB00251C
Journal Name
ARTICLE
Efficient Synthesis of Aliphatic Sulfones by Mg Mediated Coupling
Reactions of Sulfonyl Chlorides and Aliphatic Halides
Received 00th January 20xx,
Accepted 00th January 20xx
Ying Fu,* Qin-Shan Xu, Quan-Zhou Li, Zhengyin Du, Ke-Hu Wang, Danfeng Huang and Yulai Hu
DOI: 10.1039/x0xx00000x
Sulfonyl chlorides were reduced to anhydrous sulfinate salts by magnesium under sonication. These sulfinates were
alkylated to sulfones by alkyl chlorides in the presence of catalytic sodium iodide under sonication. A variety of aliphatic
sulfones was efficiently prepared by this one-pot two-step procedure.
www.rsc.org/
1. Introdction
Sulfonyl group presents as a key structural motif in various
pharmaceutical, 1 agrochemical, 2 polymeric 3 compounds and
many important synthetic intermediates.4 As a consequence,
the development of general and environmentally benign
methods for sulfone synthesis has received significant
attention.5 Among them, protocols employing sulfonyl chloride
as sulfonylating agent, which comprise the Friedel-Crafts
sulfonylating of arenes,6 transition metal catalyzed coupling of
boronic acid7 and sulfonylation of organometallics8 etc. still
occupy an important place in practical sulfone compounds
synthesis (Scheme 1a). Undoubtedly, these protocols are
efficient albeit most of them are only suitable to arylsulfone
synthesis.
Scheme 1 Protocols for aliphatic sulfone synthesis employing
sulfonyl chlorides as sulfur sources
2. Results and discussion
The reductive cross-coupling of sulfonyl chlorides and
haloalkanes provides the most direct, atom economical and
clean methods for aliphatic sulfone synthesis. Nevertheless,
this concise methodology has not yet been fully developed
that so far only Zn,9 Fe-AlCl3,10 Sm-NiCl211 and telluride ion12
are employed to promote this type of cross-coupling in
aqueous media and only primary alkyl iodides and some
reactive bromides or chlorides are applicable substrates
(Scheme 1b). Based on our recent interests on C-S bond
formation employing sulfonyl chlorides as the sulfur source,13
we herein report an efficient one-pot, two-step process to
build a large variety of aliphatic sulfones through reductive
coupling of sulfonyl chlorides and aliphatic halides (Scheme 1c).
In sharp contrast to previous synthetic methods,9-12 the
prominent advantages of our method include employing cheap
aliphatic chlorides as the alkylating agents and isolation of
anhydrous sulfinate salt intermediates.
Previously, we reported a convenient synthesis of aromatic
sulfones based on CuI catalyzed coupling of arylsulfonyl
chlorides with organozinc reagents.8a On continuation of this
work, we were interested to perform these reactions by one-
pot protocol, with the expectation that organozinc would be in
situ formed and react with sulfonyl chloride to form sulfones
via a tandem one-pot fashion. Thus p-tosyl chloride 1a and
benzyl chloride 2a were selected as the representative
reactants to optimize the reaction conditions (Table 1). In the
presence of zinc metal, stirring the reaction mixture in THF
under argon at room temperature for 1h, sulfone 3a was not
formed whereas p-tosyl chloride 2a was totally consumed by
zinc metal within one hour, delivering a THF insoluble p-
tolylsulfinate zinc salt in 82% yield (entry 1). This unexpected
result implied that sulfonyl chlorides are much more reactive
species toward zinc metal than benzyl chlorides that under this
reaction condition, benzylzinc chloride was not formed at all.
With this information in hand, we quickly determined that,
under sonication, quantitative reduction of p-tosyl chloride 1a
can be achieved using magnesium turnings as a reductant in 1h
in THF at room temperature (25 °C). The THF-insoluble
magnesium p-tolylsulfinate salt could be isolated as white
Key Laboratory of Eco-Environment Related Polymer Materials of Ministry of
Education, College of Chemistry and Chemical Engineering, Northwest Normal
University, Lanzhou, 730070, China.
Fax: (+86)-(0)931-7971989; phone: (+86)-(0)931-7971533;
e-mail: fuying@iccas.ac.cn.
† Footnotes relaꢀng to the ꢀtle and/or authors should appear here.
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
Please do not adjust margins

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 2 of 5
View Article Online
DOI: 10.1039/C7OB00251C
ARTICLE
Journal Name
a, b
Table 1. Optimization of the reaction conditions
Table 2. Scope of aliphatic halides in the Mg-mediated coupling reactions a, b
O
Mg, )))), 1h
THF, RT
RCl/Br 2, NaI
p-TsCl
Ts
R
S
p-Tol
Oꢀ
THF/DMSO 3:1
60 C, )))), 1h
1a
3
Entry
1
Solvent
THF
M
Zn
T/oC
RT
3a/%
/
2
3
4
5
6
THF
DMF
DMSO
CH3CN
THF/DMSO
Mg
Mg
Mg
Mg
Mg
RT to reflux
RT to 60
RT to 60
RT to 60
RT to 60
<10
53
64
62
81c,d
a
Reaction conditions: M (1.2 mmol) was added into a solution of 1a (1
mmol) and 2a (1.2 mmol) in a designated solvent (3 ml). The suspension was
then stirred at room temperature for 1h, afterwards, the reaction mixture was
o
b
heated to 65 C for 1h. Isolated yields. c NaI (0.2 mmol) and DMSO (1 ml)
d
were added after reduction of 1a. Reaction was carried out in a one-pot,
two-step process under sonication.
Scheme 2. Synthesis of anhydrous magnesium sulfinate
chloride
a
Reaction conditions: A suspension of Mg (1.2 mmol) and 1a (1 mmol) in
THF (3 ml) was sonicated at room temperature for 1h. Afterwards, RCl 2 (1.2
mmol), NaI (0.2 mmol) and DMSO (1 ml) were added and the reaction
mixture was further sonicated at 60oC for 1h. b Isolated yields. c NaI (1 mmol)
powder in 92% yield (Scheme 2). To our best knowledge, this is
the first report on quick and straightforward preparation of
anhydrous sulfinate salts from sulfonyl chlorides.14
was added, afterwards, sonication was conducted at 60 oC for 4h. Alkyl
d
bromides were employed.
This encouraging result incited us to further convert the in
situ formed sulfinate magnesium salt into sulfone via a one-pot
process. However, the low solubility of magnesium sulfinate in
THF completely inhibited this type of conversion even under
refluxed condition (Table 1, entry 2). When a polar aprotic
solvent, such as DMF, DMSO or acetonitrile was employed
instead of THF as a solvent, a clear solution formed whereas
the desired sulfone 3a was not formed unless the reaction
system was heated to 60 °C. Simultaneously, significant
amount of unidentified byproducts were formed (entries 3-5).
Further reaction condition optimization showed that side
reactions could be largely suppressed by performing the
reaction in a one-pot, two-step process under sonication,
employing catalytic amount of NaI (0.2 equiv.) as an additive.
First, under sonication, p-tolylsulfonyl chloride 1a was
converted into its sulfinate salt with Mg in THF at room
temperature. Then, in the presence of a catalytic amount of
NaI and with DMSO as cosolvent (THF/DMSO 3:1, v/v), one-pot
benzylation of sulfinate salt was conducted under sonication at
60oC for one hour to give 3a in 81% isolated yield (entry 6).
With these optimized reaction conditions in hand, the scope of
aliphatic halides were then explored using p-tosyl chloride 1a
as the sulfonylating agent. As summarized in Table 2, benzylic
chlorides equipped with diverse functional groups (Cl, NO2, t-
Bu and OMe) were well applied under this optimized reaction
condition, affording the corresponding benzylic sulfones in 72%
to 84% yields (3b-3f). The substrate scope could be further
prepared from allyl chloride in 74% yield whereas propargyl
chloride, under same reaction condition, gave an inseparable
mixture of propargyl sulfone 3ja and 1,2-Propadienyl sulfone
1
3jb in 84% yield (3ja:3jb = 3:1, based on H NMR analysis). 2-
Chloromethylstyrenes, bearing either electron-withdrawing or
electron-donating groups at the ortho or para position,
worked quite well under the optimized reaction conditions,
affording the corresponding sulfones (3k-3n) in 71% to 77%
yields. 2-Chloroacetophenone and 2-chloroacetates are
reactive electrophiles and furnished the corresponding
sulfones (3o-3q) in high yields. Gratifyingly, primary alkyl
chlorides were well applied in this reaction system and gave
aliphatic sulfones (3r
& 3s) in moderate isolated yields.
Secondary alkyl bromide, as represented by 2-bromopropane,
proceeded this transformation sluggishly and only 37% yield of
sulfone 3t was obtained. Undoubtedly, bis-tosylation of α, ω-
dibromoalkanes were achieved without any difficulties (3u-w).
Encouraged by these successful results on aliphatic halides,
we subsequently set out to expand the scope of sulfonyl
chlorides. As shown in Table 3, a variety of aromatic sulfonyl
chlorides having halogen (4c
, 4f, 4p-4r), OMe (4e & 4h), nitro
(
4g & 4l) and amido (4i & 4j) groups could be employed in
these reaction systems, delivering aliphatic sulfones in good to
high yields. Again, allyl chloride reacted readily with aryl
sulfonyl chlorides to give β, γ-unsaturated sulfones (4d-4g) in
high yields. The reaction conditions were mild and no
isomerisation15 was induced. The hindrance effect of aromatic
sulfonyl chlorides was not obvious as the highly sterically
hindered 2,4,6-trimethylbenzenesulfonyl chloride could be
employed and reacted with ethyl 2-chloroacetate to produce
extended
(chloromethyl)thiophene, producing the corresponding
sulfones (3g 3h) in good yields. Allylic sufone 3i was easily
to
1-(chloromethyl)naphthalene
and
2-
&
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 3 of 5
View Article Online
DOI: 10.1039/C7OB00251C
Journal Name
ARTICLE
Table 3. Scope of sulfonyl chlorides in the Mg-mediated coupling reactionsa,b
Alkylsulfonyl chlorides represented as MsCl, n-BuSO2Cl and
n-OctSO2Cl participated these conversions as well which, after
reduction by magnesium metal, reacted with various aliphatic
chlorides smoothly and gave dialkyl sulfones (5c-5h) in 60%-
78% yields. Generally, with reactive aliphatic halides, e.g., MeI
(
(
4a, 4u & 5a), allyl chlorides (4d-4g
,
4v
,
5f), propargyl chlorides
4x
4h), benzylic chlorides (4k-4n) and 2-chloroesters (4o-4t
,
,
5h), alkylation of magnesium sulfinate salts could be finished in
one hour. For primary and secondary alkyl chorides/bromides,
better results were obtained after sonication the reaction
mixtures at 60 °C for 4h.
It should be emphasized here that this cross-coupling
methodology was more suitable to but not limited in aliphatic
sulfone synthesis. These in situ formed anhydrous magnesium
sulfinate salts were successfully applied in sulfonylating of
iodoarenes too (Scheme 3). Under CuI catalysis, p-tosyl
chloride 2a, after conversion into its magnesium sulfinate salt,
reacted readily with PhI 19 and 1-fluoro-4-iodobenzene to
furnish the desired diaryl sulfones (4a
& 4b) in moderate
isolated yields. Similarly, benzenesulfonyl chloride and
functionalized aromatic sulfonyl chlorides selected, bearing
amido and bromo groups, participated this transformation
smoothly and produced the corresponding diaryl sulfones (6c-
6f) in acceptable yields.
a
Reaction conditions: A suspension of Mg (1.2 mmol) and 1 (1 mmol) in
THF (3 ml) was sonicated at room temperature for 1h. 2 (1.2 mmol), NaI (0.2
mmol) and DMSO (1 ml) were then added and the reaction mixture was
further sonicated at 60oC for 1h. b Isolated yields. c NaI (1 mmol) was added
o
d
and sonication was conducted at 60 C for 4 h. MeI (2 equiv.) was used.e
f
Alkyl bromides were employed. An equimolar combination of Mg (1.2
mmol) and ZnCl2 (1.2 mmol) were used.
sulfone 4t in 66% yield. Different types of aryl and heteroaryl
sulfonyl chlorides containing 2-naphthyl (4v-4x), biphenyl (4s),
thiophenyl (4m
& 4u) and pyridinyl (4n) were successfully
employed and reacted with various aliphtic halides to produce
the corresponding aliphatic sulfones in good to excellent yields.
Scheme 3. Sulfonylating of iodoarenes
In case when a magnesium metal sensitive group, e.g., Br (4f
&
4r) and nitro (4g & 4l), were presented on the ring of aryl
Aryl methyl sulfone moiety was found as an key structural
motif in many drugs, e.g., in the antibacterial Laropiprant.20 In
order to examine the efficiency of our protocol in practical
methyl sulfone synthesis, a 50 mmol scale synthesis of 4-
sulfonyl chloride, reduction of sulfonyl chlorides were better
conducted by employing an equimolar combination of
magnesium metal and zinc chloride.
Aliphatic sulfonyl chlorides could also participate in this
type of reactions. Benzyl sulfones have significant functions in
organic synthesis16 and biochemistry.17 These compounds are
normally synthesized from the corresponding benzyl chloride
via sulfinate salts18 or oxidation of sulfide in multiple steps. In
our protocol, benzylic sulfones could be readily prepared from
benzylsulfonyl chlorides too. Thus, treatment of in situ formed
benzylsulfinate salts with MeI or ethyl 2-chloroacetate
fluorophenyl methyl sulfone
7 was carried out (Scheme 5).
Thus 4-fluorobenzenesufonyl chloride 2c (9.73g, 50 mmol) was
first reduced by Mg (1.44g, 60 mmol) into corresponding
magnesium sulfinate salt and was then submitted to react with
MeI (10.64g, 75 mmol) to afford 4-fluorophenyl methyl sulfone
7
in 82% isolated yield (Scheme 4).
produced the desired benzyl sulfones (5a
& 5b) in moderate
yields.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 4 of 5
View Article Online
DOI: 10.1039/C7OB00251C
ARTICLE
Journal Name
pESI m/z: calcd for C7H8ClMgO2S [M+H]+ 214.9784; found
214.9815.
General procedure for preparation of sulfones via Mg mediated
coupling reaction of sulfonyl chlorides and alkyl halides
Scheme 4. Large scale synthesis of 4-fluorophenyl methyl
To a dry and argon-flushed Schlenk tube, sulfonyl chlorides (1
mmol), magnesium turnings (29 mg, 1.2 mmol), and 3 mL of
THF were charged. The tube was then immersed in an
ultrasound cleaning bath and was ultrasonicated at room
temperature for one hour. NaI (30 mg, 0.2 mmol), alkyl halides
(1.2 mmol) and DMSO (1 mL) was then added and the reaction
sulfone.
3. Conclusions
In summary, we have developed an easy and practical
magnesium metal mediated cross-coupling reaction of sulfonyl
chlorides with organic halides whereby different types of
sulfones could be produced in moderate to excellent yields. By
this method, anhydrous sulfinate salt could be readily prepared
from corresponding sulfonyl chlorides in excellent yield. With
catalytic amount of NaI, alkyl chlorides can be employed as
alkylating agents to furnish the aliphatic sulfones in high yields.
This protocol provides a direct and operationally simple
synthetic method for a wide range of aliphatic sulfones in good
to excellent yields.
o
mixture was sonicated for one hour at 60 C (for alkyl chlorides,
4 hours). After usual work-up, the sulfone products were
obtained by column chromatography on silica gel using
petroleum ether/ethyl acetate as an eluent.
1
n-Hexyl p-tolyl sulfone 3r.21 Colorless oil. H NMR (600 MHz,
CDCl3) δ (ppm): 7.78 (d, J = 7.8 Hz, 2H), 7.35 (d, J = 7.8 Hz, 2H),
3.05 (t, J = 7.8 Hz, 2H), 2.45 (s, 3H), 1.72-1.66 (m, 2H), 1.36-
1.32 (m, 2H), 1.28-1.22 (m, 4H), 0.85 (t, J = 6.6 Hz, 3H). 13C
NMR (150 MHz, CDCl3) δ (ppm): 144.5, 136.3, 129.8, 128.0,
56.4, 31.1, 27.9, 22.7, 22.3, 21.6, 13.9.
4. Experimental
Allyl 4-nitrophenyl sulfone 4f.22 White solid, mp 140-141 oC. 1H
NMR (600 MHz, CDCl3) δ (ppm): 8.40 (d, J = 9.0 Hz, 2H), 8.08 (d,
J = 8.4 Hz, 2H), 5.85-5.77 (m, 1H), 5.38 (d, J = 10.2 Hz, 1H), 5.16
(dd, J = 16.8, 0.6 Hz, 1H), 3.87 (d, J = 7.2 Hz, 2H). 13C NMR (150
MHz, CDCl3) δ (ppm): 137.2, 132.4, 130.1, 129.1, 125.1, 124.4,
60.8.
General experimental information. All the reactions were carried
out under argon or nitrogen atmosphere. Sonochemical
reactions were carried out in
a commercially available
ultrasound cleaning bath (40 kHz, 600 W) equipped with an
automatic constant temperature heating-cooling circulatory
1
system. H NMR (400 and 600 MHz), and 13C NMR (100 and
Benzyl methyl sulfone 5a.23 White solid, mp 124-126 oC. 1H
NMR (400 MHz, CDCl3) δ (ppm): 7.42 (s, 5H), 4.26 (s, 2H), 2.76
(s, 3H). 13C NMR (100 MHz, CDCl3) δ (ppm): 130.5, 129.1, 128.3,
61.3, 39.0.
150 MHz) were recorded on Bruker AV400 or 600 NMR
1
spectrometer with CDCl3 as solvent. Chemical shifts of H and
13C NMR spectra are reported in parts per million (ppm) with
TMS as an internal standard. Column chromatography was
performed on silica gel 300-400 mesh. Analytical thin layer
chromatography (TLC) was performed on pre-coated, glass-
backed silica gel plates. Visualization of the developed
chromatogram was performed by UV absorbance (254 nm).
Allyl n-octyl sulfone 5f.24 Colorless oil. 1H NMR (600 MHz,
CDCl3) δ (ppm): 5.97-5.92 (m, 2H), 5.48 (dd, J = 10.2, 0.6 Hz,
1H), 5.44 (dd, J = 16.8, 0.6 Hz, 1H), 3.69 (d, J = 7.8 Hz, 2H), 2.94
(t, J = 7.8 Hz, 2H), 1.85-1.79 (m, 2H), 1.44-1.41 (m, 2H), 1.33-
1.25 (m, 10H), 0.88 (t, J = 7.2 Hz, 3H). 13C NMR (150 MHz, CDCl3)
δ (ppm): 125.3, 124.4, 57.6, 51.3, 31.7, 29.0, 28.9, 28.4, 22.6,
21.8, 14.0.
Preparation of anhydrous p-tolylsulfinate magnesium salt
A dry and argon-flushed Schlenk flask containing p-tosyl
chloride (1.90g, 10 mmol), magnesium turnings (0.24 g, 12
mmol) and 30 mL of THF was immersed in an ultrasound
cleaning bath at room temperature for 1 h. Dry ether (50 mL)
was added and the magnesium sulfinate salt suspensions but
the small magnesium residues precipitated at the bottom of
the flask was carefully transferred into a filter and the filter
cake was washed with ether (20 mL) for 3 times. The cake was
then transferred into a round-bottled flask and was evacuated
under reduced pressure at room temperature for 3 h to
remove any remaining solvent. The sulfinate salt powder thus
prepared was determined to be magnesium p-tolylsulfinate
chloride. 1.79g, 92% yield. 1H NMR (600 MHz, DMSO-d6) δ
(ppm): 7.45 (d, J = 7.8 Hz, 2H), 7.19 (d, J = 7.8 Hz, 2H), 2.48 (s,
3H).13C NMR (150 MHz, DMSO-d6) δ (ppm): 146.1, 138.1, 128.5,
126.0, 21.2. IR (KBr) ν (cm-1): 1653, 1398, 1190, 1029. FTMS +
General procedure for the synthesis of diarylsulfones via Mg
mediated coupling of arylsulfonyl chlorides with aryl halides (6a-6f)
A dry and argon-flushed Schlenk tube equipped with a
magnetic stirrer and a septum was charged with sulfonyl
chlorides (1 mmol), magnesium turnings (29 mg, 1.2 mmol)
and 3 mL of THF. After sonication of the reaction mixture at
room temperature for one hour, THF was removed under
reduced pressure. CuI (0.29g, 1.5 mmol), aryl iodides (1 mmol)
and DMF (3 mL) was added. The reaction mixture was heated
to 110 oC and stirred for 12 hour under argon. After cooling, 10
mL of aqueous NH4Cl and 10 mL of ethyl acetate was added
and the organic phase was separated, washed with 10 mL of
water and then with 10 mL of brine. The water phase was
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 5 of 5
View Article Online
DOI: 10.1039/C7OB00251C
Journal Name
ARTICLE
extracted with ethyl acetate (2×10 mL). The organic phase
14 Known synthetic procedures for sulfinate dihydrate salts, see:
(a) L. Liu, Y. Chi, K. Jen, J. Org. Chem., 1980, 45, 406; (b) F.
O’Hara, R. D. Baxter, A. G. O’Brien, M. R. Collins, J. A. Dixon, Y.
was combined, dried (Na2SO4) and concentrated under
reduced pressure. The diarylsulfone products were obtained by
column chromatography on silica gel using petroleum/ethyl
acetate as an eluent.
Fujiwara, Y. Ishihara, P. S. Baran, Nat. Protoc., 2013,
(c) F. C. Whitmore, F. H. Hamilton, Org. Syn., 1922,
8
, 1042;
2
, 89; (d)
N. Chumachenko, P. Sampson, Tetrahedron, 2006, 62, 4540;
(e) B. Skillinghaug, J. Rydfjord, L. R. Odell, Tetrahedron Lett.,
2016, 57, 533.
Phenyl p-tolyl sulfone 6a.25 White solid, mp 121-123 oC. 1H
NMR (400 MHz, CDCl3) δ (ppm): 7.93 (ddd, J = 8.0, 2.4, 1.6 Hz,
2H), 7.83 (d, J = 8.4 Hz, 2H), 7.55 (tdd, J = 7.2, 2.4, 1.2 Hz, 1H),
7.49 (tdd, J = 7.2, 2.4, 0.8 Hz, 2H), 7.29 (d, J = 8.8 Hz, 2H), 2.40
(s, 3H). 13C NMR (100 MHz, CDCl3) δ (ppm): 144.2, 141.9, 138.6,
133.0, 129.9, 129.2, 127.7, 127.5, 21.6.
15 P. K. Shyam, H.-Y. Jang, J . Org. Chem., 2017, 82, 1761.
16 (a) T. Niwa, H. Yorimitsu, K. Oshima, Tetrahedron, 2009, 65
1971; (b) M. Nambo, E. C. Keske, J. P. G. Rygus, J. C.-H. Yim, C.
M. Crudden, ACS Catal., 2017, , 1108.
17 M. Lu, S. Merali, R. Gordon, J. Jiang, Y. Li, J. Mandeli, X. Duan,
J. Fallon and J. F. Holland, Genes Cancer, 2011, , 985.
,
7
2
Error! Bookmark not defined.
18 F. W. Lewis, T. C. McCabe and D. H. Grayson, Tetrahedron,
2011, 67, 7517.
4-Bromodiphenyl sulfone 6f.
White solid,
mp 102-104 oC. 1H NMR (CDCl3) δ (ppm): 7.52 (tt, J = 7.6, 1.2 Hz,
2H), 7.59 (tt, J = 7.6, 1.2 Hz, 1H), 7.65 (dt, J = 8.4, 2.0 Hz, 2H),
7.80 (dt, J = 8.8, 2.0 Hz, 2H), 7.91-7.95 (m, 2H). 13C NMR (CDCl3)
δ (ppm): 127.6, 128.4, 129.2, 129.4, 132.6, 133.4, 140.6, 141.1.
19 H. Suzuki, H. Abe, Tetrahedron Lett., 1995, 36, 6239.
20 C. F. Sturino, G. O’Neill, N. Lachance, M. Boyd, C. Berthelette,
M. Labelle, L. Li, B. Roy, J. Scheigetz, N. Tsou, Y. Aubin, K. P.
Bateman, N. Chauret, S. H. Day, J.-F. Lévesque, C. Seto, J. H.
Silva, L. A. Trimble, M.-C. Carriere, D. Denis, G. Greig, S.
Kargman, S. Lamontagne, M.-C. Mathieu, N. Sawyer, D.
Slipetz, W. M. Abraham, T. Jones, M. McAuliffe, H. Piechuta,
D. A. Nicoll-Griffith, Z. Wang, R. Zamboni, R. N. Young, K. M.
Metters, J. Med. Chem., 2007, 50, 794.
Acknowledgements
The authors are grateful for financial support from the National
Natural Science Foundation of China (No. 21262030,
20962017).
21 R. Ballini, E. Marcantoni, M. Petrini, Tetrahedron, 1989, 45
6791.
,
22 D. J. Pasto, F. Cottard, C. Picconatto, J. Org. Chem., 1994, 59
7172.
23 Y. Ju, D. Kumar, R. S. Varma, J. Org. Chem., 2006, 71, 6697.
,
24 H.-S. Dang, B. P. Roberts, J. Chem. Soc., Perkin Trans. 1, 1996,
1493.
Notes and references
25 B. P. Bandgar, S. V. Bettigeri, J. Phopase, Org. Lett., 2004, 6,
2105.
1
2
(a) G. Wozel, Int. J. Dermatol., 1989, 28, 17; (b) D. Wcisło-
Dziadecka, M. Zbiciak, L. Brzezińska-Wcisło.Dermatologia
Kliniczna, 2014, 16, 35.
(a) W.-M. Xu, F.-F. Han, M. He, D.-Y. Hu, J. He, S. Yang, B.-
A.Song, J. Agric. Food Chem., 2012, 60, 1036; (b) Y. Noutoshi,
M. Ikeda, T. Saito, H. Osada, K. Shirasu, Front. Plant Sci. 2012,
3, 245.
3
4
5
M. A. Hickner, H. Ghassemi, Y. S. Kim, B. R. Einsla, J. E.
McGrath, Chem. Rev., 2004, 104, 4587.
N. S. Simpkins, Sulfones in Organic Synthesis, Pergamon Press,
Oxford, 1993.
(a) Y. Fu, X. Zhao, B. Hou, Chin. J. Org. Chem., 2016, 36, 1184;
(b) Y. Fang, Z. Luo, X. Xu, RSC Adv., 2016, 6, 59661; (c) C. Shen,
P. Zhang, Q. Sun, S. Bai, T. S. Andy Hor, X. Liu, Chem. Soc. Rev.,
2015, 44, 291.
6
(a) J. Wei, J. Jiang, X. Xiao, D. Lin, Y. Deng, Z. Ke, H. Jiang, W.
Zeng, J. Org. Chem., 2016, 81, 946; (b) H.-W. Liang, K. Jiang, W.
Ding, Y. Yuan, L. Shuai, Y.-C. Chen, Y. Wei, Chem. Commun.,
2015, 51, 16928.
7
8
(a) B. P. Bandgar, S. V. Bettigeri, J. Phopase, Org. Lett., 2004,
2105; (b) F. Hu, X. Lei, ChemCatChem, 2015, , 1539.
(a) Y. Fu, W. Zhu, X. Zhao, H. Hügel, Z. Wu, Y. Su, Z. Du, D.
Huang, Y. Hu, Org. Biomol. Chem., 2014, 12, 4295; (b) P. Sun,
L. Wang, Y. Zhang, Tetrahedron Lett., 1997, 38, 5549; (c) S. S.
Labadie, J. Org. Chem., 1989, 54, 2496.
6
,
7
9
X. Sun , L. Wang, Y. Zhang, Synth. Commun., 1998, 28, 1785.
10 P. Saikia, D. D. Laskar, D. Prajapati, J. S. Sandhu, Chem. Lett.,
2001, 512.
11 Y. Ye, Q. Zhou, R. Zheng, H. Jiang, R. Chen, Y. Zhang, Appl.
Organometal. Chem., 2011, 25, 331.
12 H. Suzuki, Y. Nishioka, S. I. Padmanabhan, T. Ogawa, Chem.
Lett., 1988, 727.
13 Y. Fu, Y. Su, Q.-S. Xu, Z. Du, Y. Hu, K.-H. Wang, D. Huang, RSC
Adv., 2017, 7, 6018.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins