Controllable Sulfoxidation and Sulfenylation with Organic Thiosulfate Salts via Dual Electron- and Energy-Transfer Photocatalysis

Article abstract of DOI:10.1021/acscatal.7b02735

Sulfoxides and sulfides are two important functional groups in organic molecules, containing different valence states of sulfur. Both sulfoxidation and sulfenylation with common sulfurating reagents were successfully tuned via a facile variation of the atmosphere under photocatalyzed conditions. The sulfoxidation and sulfenylation transformations involved tandem electron-/energy-transfer and single-electron-transfer processes, respectively. Late-stage sulfoxidation for pharmaceuticals and sugar derivatives was established to be highly compatible. Divergent formal syntheses of sulfoxide/sulfide-containing marketed pharmaceuticals were switchably implemented. Gram-scale operations further demonstrated the practicability of the protocol.

Full text of DOI:10.1021/acscatal.7b02735

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Letter
Controllable Sulfoxidation and Sulfenylation with Organic Thiosul-
fate Salts via Dual Electron- and Energy-Transfer Photocatalysis
Yiming Li, Ming Wang, and Xuefeng Jiang
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.7b02735 • Publication Date (Web): 03 Oct 2017
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ACS Catalysis
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Controllable Sulfoxidation and Sulfenylation with Organic Thiosul-
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† ‡
† ‡
Yiming Li , Ming Wang , Xuefeng Jiang *,†,§, #
†Shanghai Key Laboratory of Green Chemistry and Chemical Process, East China Normal University, 3663 North
Zhongshan Rd., Shanghai 200062, P. R. China.
§State Key Laboratory of Elemento-organic Chemistry, Nankai University, Tianjin 300071, P. R. China.
#State Key Laboratory of Organometallic Chemistry, Shanghai, Institute of Organic Chemistry, Chinese Academy of Scienc-
es, Shanghai 200032, P. R. China.
ABSTRACT: Sulfoxides and sulfides are two important functional groups in organic molecules, containing different valence states
of sulfur. Both sulfoxidation and sulfenylation with common sulfurating reagents were successfully tuned via a facile variation of
the atmosphere under photocatalyzed conditions. The sulfoxidation and sulfenylation transformations involved tandem electron-
/energy-transfer and single electron-transfer processes, respectively. Late-stage sulfoxidation for pharmaceuticals and sugar deriva-
tives was established to be highly compatible. Divergent formal syntheses of sulfoxide/sulfide-containing marketed pharmaceuti-
cals were switchably implemented. Gram-scale operations further demonstrated the practicability of the protocol.
KEYWORDS. Sulfoxidation, Sulfenylation, Electron Transfer, Energy Transfer, Photocatalysis
Various organosulfur molecules widely exist in nature.1 In
addition, synthetic sulfur-containing compounds are also
abundant with miscellaneous functions especially for pharma-
ceuticals.2 Sulfide and sulfoxide are usually studied with each
other in drug discovery, due to their mutual transformations
assisted by enzymes in vivo.3 Similar molecular backbones
with different oxidation states of sulfur in pharmaceuticals
have afforded a diversity of drug activities (Scheme 1a). Sul-
fide-containing albendazole,4 an oral medication for the treat-
ment of intestinal parasites in humans, is a vital drug on the
list of essential medicines from the World Health Organization
(WHO).5 The corresponding sulfoxide-containing rico-
bendazole is commonly applied as an antihelminthic agent
against lungworms and roundworms in ruminants.6 Sulfide-
containing arbidol (umifenovir) is an antiviral pharmaceutical
for prophylaxis and treatment of infections with influenza A
and B viruses in Russia and China,7 while its sulfoxide deriva-
tive ARB-IIIf has been found to be an exclusive inhibitor of
chikungunya virus (a mosquito-borne arthrogenic alpha-
virus).8 Sulfide-containing sulprofos is applied to control
worms on cotton and tobacco,9 while the similar sulfoxide-
containing fensulfothion10 is an insecticide for corn and sugar
cane. Considering the accompanying and complementary
characteristics between sulfides11 and sulfoxides,12,13 a diver-
gent construction strategy with a common precursor is in ur-
gent demand. However, contradictions11,14 between sulfenyla-
tion and oxygenation in transition-metal-catalyzed coupling
have brought challenges toward this goal. A mild photocata-
lyzed15 system with different kinds of catalytic modes (single
electron transfer and energy transfer)16 provides an opportuni-
ty for both sulfenylation17 and oxygenation,18 despite the poor
compatibility among the sulfur species, aryl radical, and active
oxygen (Scheme 1b). Our masked strategy,19 in which stabili-
zation of a sulfur radical was realized through an electronic
conjugation and steric hindrance effect, could impede the
highly active undesired processes, such as homocoupling and
over oxidation. (Scheme 1c).
Scheme 1. Selective Sulfoxidation and Sulfenylation.
and
Sulfide
Sulfoxide:
a)
Br
O
S
Me
S
OMe
Me
nPr
N
OH
Me
N
S
P
SnPr
N
NH
S
O
N
H
OEt
CO2Et
Arbidol
Influenza A
Me
Albendazole
Intestinal Parasites in Human
Sulprofos
and
on
and
B
Worms
Cotton
Tobacco
OH
O
O
S
Me
O
NH
O
N
CF3
S
OMe
nPr
Me
N
S
S
OEt
OEt
P
N
H
CO2tBu
ARB-IIIf
O
Ricobendazole
in Ruminants
Fensulfothion
on
and
Chikungunya Virus
Insects
Corn
Cane
Lungworms
Sugar
Our Concept:
S
b)
O
+
+
O
Ar
R
S
[
]
R
Ar
S
Ar
R
Challenges
S
R
Ar Ar
Ar OH
R
S
This Work:
S
c)
O
S
EY hv
EY hv
,
,
S
+
Ar2IBF4
Mask
Ar/Alkyl
Ar
Ar/Alkyl
N2
Air
Ar
Ar/Alkyl
=
Mask SO3Na
We commenced this study using n-pentyl thiosulfate salt
and diphenyl iodonium in air under photocatalyzed conditions.
Unfortunately, no sulfoxide was detected when catalyzed by
tris(bipyridine)ruthenium(II) chloride with potassium car-
bonate in a mixture of dimethyl sulfoxide and water.19f When
subjected to the dye eosin Y (EY) in methanol, pen-
tyl(phenyl)sulfoxide 3a was delightedly obtained in 20% yield
(Table 1, entry 1). Other solvents, such as dimethyl sulfoxide,
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N,N-dimethylformamide, and water, did not deliver 3a (Table ides (3j and 3k) were also achieved. Various thiosulfate salts
1
2
3
4
5
6
7
8
1, entries 2-4). Different bases were also checked (Table 1,
entries 5-7), in which Hünig’s base, diisopropylethylamine,
improved the yield to 31%. Zinc acetate, which is known to
improve the selectivity during oxidation,20 elevated the yield
to 53% (Table 1, entry 8). Other Lewis acids and Brønsted
acids did not elevate the efficiency (Table 1, entries 9 and 10).
A higher concentration afforded a better result with 65% yield
(Table 1, entry 11). The solvent combination of methanol and
acetonitrile, adjusting the solubility of starting materials,
yielded 77% sulfoxide (Table 1, entry 12). A green LED (λ =
530 nm), which matches the maximum absorption wavelength
of eosin Y (520 nm), afforded 3a in 82% isolated yield (Table
1, entry 13). Conveniently, by only altering the atmosphere to
nitrogen, pentyl(phenyl)sulfane 4a was efficiently obtained in
84% isolated yield (Table 1, entries 14 and 15).
substituted with benzyl (3l), ether (3m and 3n), cyano (3o),
and ester (3p) groups were successfully converted. It is note-
worthy that a functional group with an active hydrogen hy-
droxyl (3q) was well retained. In addition to aryl alkyl sulfox-
ides, diaryl ones were delightedly afforded, which can be
hardly achieved under mild visible-light-promoted oxygena-
tion of sulfides.12c,18 Electron-neutral 3r and 3s were acquired
in good yields. Chloro and bromo substituents were compati-
ble (3s-3u). Sulfoxide 3u was further confirmed by X-ray dif-
fraction.21 Impressively, diarylsulfoxides with electron-
deficient groups, such as fluoro (3v) and ester (3w) groups,
were also synthesized. Late-stage sulfoxidation of the func-
tional molecules furanose (3x) and pyranose (3y) were imple-
mented from side-chain-derivatised thiosulfates. Moreover,
nitro-containing metronidazole was sulfoxidized in 50% yield
(3z). On the other hand, aryl alkyl sulfides were obtained in
good to excellent yields with a variety of functional substitu-
ents, such as bromo (4b), hydroxyl (4d), nitrile (4e), benzyl
(4f and 4g), and propargyl (4h) groups. Particularly, this
method showed great potential for constructing diaryl sulfides,
wherein the electronic effects of substituents on both the diaryl
iodonium salts and thiosulfate salts did not affect the efficien-
cy (4i-4s). The steric effects were illuminated through the syn-
thesis of 2-methyl- and 2,4,6-trimethyl-substituted sulfides 4m
and 4n. Gram-scale operation further demonstrated the utility,
in which 3a and 4i were synthesized on a 10 mmol scale under
these mild and easily handled conditions. With these tunable
systems in hand, the controllable formal synthesis of albend-
azole,22 ricobendazole,22 ARB-IIIf,8 and fensulfothion23 was
conducted, as discussed below (Scheme 2).
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
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42
43
44
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Table 1. Selectivity Establishmenta
BF4
O
S
I
Sulfoxidation
Sulfidation
S
nPent
Ph Ph
Ph
1a
nPent
Ph
+
4a
NaO3S2 nPent
3a
2a
yield/3ab
20
yield/4ab
-
entry
base
additive
solvent
-
-
-
K
2CO3
K
2CO3
K
2CO3
1
2
3
MeOH
DMSO
DMF
-
-
trace
trace
-
-
-
-
-
-
-
-
K
H
2O
2CO3
4
5
6
7
trace
15
KOH
MeOH
MeOH
MeOH
Further control experiments were pursued to gain insight in-
to the mechanism. First, UV-Vis absorption experiments
showed that only eosin Y possessed obvious absorption in the
visible-light region (SI, Figure S1). Stern–Volmer fluorescent
quenching experiments demonstrated that diaryl iodonium,
instead of the thiosulfate salt, quenched the excited catalyst
EY* efficiently (SI, Figure S2). Moreover, radical quenching
experiments with 2,2,6,6-tetramethylpiperidinooxy (TEMPO)
completely suppressed both the sulfoxidation and sulfenyla-
tion pathways (SI, Tables S1 and S2). The results above indi-
cate that the current reactions started with a single electron
transfer between EY* and the aryliodonium salt. Second, a
control experiment with sulfide 4a was carried out under
standard conditions for sulfoxidation (Table 3, entry 1),
providing an almost quantitative transformation to the related
sulfoxide 3a, which indicated that the sulfoxidation operated
by cascade sulfenylation and oxygenation processes. The fluo-
rescence of Eosin Y was not quenched by a sulfide, which
demonstrated that there is no direct interaction of the sulfide
KOtBu
DIPEA
DIPEA
DIPEA
12
31
53
30
-
-
8
9
MeOH
Zn(OAc)2
3.OEt2
BF
MeOH
MeOH
MeOHc
-
-
10
11
DIPEA
DIPEA
HOAc
22
65
Zn(OAc)2
-
MeOH/MeCNd
MeOHd
12
13
DIPEA
DIPEA
DIPEA
77
Zn(OAc)2
Zn(OAc)2
Zn(OAc)2
-
85(82)e
-
14g
68
MeOHd
.2H2Of
Zn(OAc)2
-
MeOHc
15g
DIPEA
86(84)
aStandard conditions: 1a (0.2 mmol), 2a (0.6 mmol), catalyst
(2 mol%), additive (0.4 mmol), base (2 equiv.), and solvent
(1.0 mL) were added and stirred for 24 h under the irradiation
of a 23 W CFL. b1H NMR yields (%). Isolated yields (%) are
-.
with EY* (SI, Figure S2). The oxygen radical anion (O2 )
c
d
e
f
in parentheses. 0.5 mL. 0.3/0.1 mL. 18 W green LED. 10
quencher 1,4-benzoquinone (BQ)18d had no effect on the oxy-
genation reaction (Table 3, entry 2). However, the singlet oxy-
gen (1O2) quencher cobaltic acetylacetonate, [Co(acac)3],18g
dramatically decreased the yield with a recovery of 85% sul-
fide (Table 3, entry 3). Additional fluorescent quenching ex-
periments revealed that neither BQ nor Co(acac)3 quenched
EY* (Figure 1, for details, see Figure S3), which showed that
1O2 is the key active oxygen species generated through energy
mol%. gNitrogen atmosphere was applied instead of air.
With this tunable protocol in hand, the sulfoxide library was
first established (Table 2). Diaryliodonium salts with electron-
donating (3b) and electron-withdrawing groups in different
positions (3c and 3g) delivered the corresponding sulfoxides
smoothly. Fluoro, chloro, and bromo substituents were well
tolerated (3d-f), which could be further modified with cross
coupling reactions. Sterically hindered substrates with 2-
methyl and 2,4,6-trimethyl groups still efficiently underwent
the reaction (3h and 3i). Fused- and hetero-aromatic sulfox-
transfer
between
EY*
and
3O2.
Over
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Table 2: Substrate Scopes of Sulfoxidesa and Sulfidesb
1
2
3
4
O
S
Sulfoxidation
Sulfidation
BF4
I
S
4
+
R
Na
S2O3
Ar
R
Ar
R
Ar Ar
3
1
2
5
6
7
8
O
S
O
S
O
S
S
S
OH
6
nPent
Me
nPent
S
nPent
nPent
R
R
R
c
90%h
=
=
=
R
3-CF3
2-Me
=
3a 82%
R
H
3d 64% R
3e 70%
F
Cl
Br
3g 87%
3h 57%
4a 84% R
4b 87%
H
4c
4d 50%
9
tBu
3j 81%
3b 88%
Br
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
3c 67% CF3 3f 83%
3i
50% 2,4,6-Me
R
O
S
Ph
O
O
S
CN
S
S
R
S
S
nPent
S
R
68%d
65%d
=
=
=
R
tBu
3l 57%
R
Ph 3o 62% R
CN 3r
Me
3s
=
4e 60%
4f 73%
4g 60%
H
4h 46%
R
Me
Cl
(CH2)2
CO2
CH2OEt
O
3k 50%
3m
3p 74%
(CH2)2
63%
OH
3n 60%
3q
77%
(CH2)5
O
Me
Me
S
O
S
S
S
S
R
Me
Me
R
OMe
84%
R
OMe
OMe
OMe
i
70%d
72%d
Cl
Br
62%e
55%e CO2
=
=
Br 4m 68%
3t
3u
=
4i 77% R H 4k
R
4n 42%
R
3v
=
F
R
CF3
4j 65%
F 4l 71%
Et
3w
3u
Late Stage Sulfoxidation
Ph
Me
S
S
S
O
S
Me
O
O
O
NO2
N
3
S
OBz
O
O
O
BzO
O
N
O
O
Ph
S
R
OMe
CF3
4o 73%
OMe
O
Me
Me
O
=
4q 83% R Me
O
3z 50%f
4p 53%
84%f,g
61%f,g
3x
3y
4r 75%
4s 79%
Cl
CF3
Me
OBzOMe
aStandard conditions for sulfoxidation: diaryl iodonium salt (0.2 mmol), thiosulfate salt (0.6 mmol), eosin Y (0.004 mmol), DIPEA (0.4
mmol), Zn(OAc)2 (0.4 mmol), MeOH/MeCN = 0.3/0.1 mL, air, 18 W green LED, 24 h. bStandard conditions for sulfenylation: diaryl io-
.
donium salt (0.2 mmol), thiosulfate salt (0.6 mmol), eosin Y (0.004 mmol), DIPEA (0.4 mmol), Zn(OAc)2 2H2O (0.02 mmol), MeOH =
0.5 mL, N2, 23 W CFL, 24 h. c76%, 10 mmol scale. Air, 12 h, then O2, 24 h. eAir, 12 h, then O2, 48 h. f23 W CFL, CH3CN (0.4 mL).
d
g
hMethyl thiosulfate salt (5 equiv.). i63%, 10 mmol scale.
Scheme 2: Formal Synthesis of Albendazole, Rico-
bendazole, ARB-IIIf, and Fensulfothiona,b
8 and EY+. produced the sulfide and regenerated the low-
energy EY. An energy-transfer process was involved between
3O2 and EY*, generating 1O2. The persulfoxide 9,12c,18b,g which
was obtained via the combination of the sulfide and 1O2, stabi-
lized by zinc acetate18c and finally delivered the sulfoxide with
another sulfide.
BF4
NO2
S
nPr
Eosin Y
N2
I
+
R
NaO3S2
2
Ar Ar'
NHAc
1
6a 76%[c]
Albendazole
Eosin Y Air
Table 3: Control Experiments
standard conditions
for sulfoxidation
O
S
S
O
O
S
Me
Ph
nPent
O
S
Et
CO2
CF3
N
Ph
nPent
S
NO2
20 h
nPr
Me
O
4a
3a
OEt
P
tBu
CO2
O
NHAc
5a 75%[c]
Ricobendazole
OEt
entry
alteration
conditions
of
-
yield
99%
5b 50%
ARB-IIIf
5c 50%[c]
Fensulfothion
1
2
3
aStandard conditions for sulfoxidation. Standard conditions for
b
+
mol%)
97%
BQ
(6
sulfenylation. cAr’ = 2,4,6-trisopropylphenyl.
+
+
11% 85% 4a
mol%)
Co(acac)3 (6
all, a proposed mechanism was depicted, as show in Scheme 3
below: EY* was generated from EY under visible-light irradia-
tion, which subsequently interacted with diaryliodonium salt 1
through a single electron-transfer process. The newly formed
aryl radical 7 coupled with the thiosulfate salt to produce sul-
fide radical 8. The following electron-transfer process between
In conclusion, a selective construction of organic sulfurs in
different valence states from common thiosulfate salts was
developed under visible-light-catalyzed conditions via easily
tuning the reaction atmosphere. Late-stage sulfoxidation,
switchable synthesis of pharmaceuticals, and gram-scale oper-
ations were systematically established. Mechanistic studies
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Scholar) at Shanghai Institutions of Higher Learning, and Nation-
al Program for Support of Top-Notch Young Professionals.
1
2
3
REFERENCES
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Figure 1: Stern–Volmer Fluorescent Quenching Experi-
ments
Scheme 3: Proposed Mechanism
O
S
Ar
S
Zn(OAc)2
O
Ar
R
S
Ar
R
R
S
8
Ar
R
3O2
OAc
O
R
EY
Zn
S
Ar
OAc
SO3Na
10
EY+
ELECTRON
TRANSFER
ENERGY
TRANSFER
hv
Zn(OAc)2
O
R
O
EY*
1O2
(10) (a) The Pesticide Action Network (PAN) Pesticide Database.
http://www.pesticideinfo.org/. (b) Kerven, G. L.; Dwyer, W.; Duri-
yaprapan, S.; Britten, E. J. J. Agric. Food. Chem. 1980, 28, 164-167.
(11) For representative reviews: (a) Thuillier, A.; Metzner, P. Sulfur
Reagents in Organic Synthesis; Academic Press: New York, 1994. (b)
Kondo, T.; Mitsudo, T. A. Chem. Rev. 2000, 100, 3205-3220. (c)
S
9
S
Ar
NaO3S
R
BF4
I
1
2
Ar
7
+
S
Ar
R
Ar
Ar
+
BF4
ArI
indicated that the sulfoxidation might involve cascade elec-
tron- and energy-transfer processes, whereas a single electron
transfer might dominate in the sulfenylation pathway. A sul-
foxide-containing pharmaceutical library is being constructed
in our group.
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ASSOCIATED CONTENT
Supporting Information.
The supporting Information is available free of charge via the
Internet at http://pubs.acs.org.
Detailed mechanistic studies, experimental procedures, character-
ization data, X-ray analyses of compound 3u, and NMR spectra
for the compounds (PDF).
AUTHOR INFORMATION
Corresponding Author
*E-mail: xfjiang@chem.ecnu.edu.cn.
ORCID
Xuefeng Jiang: 0000-0002-1849-6572
(14) Wang, H.; Lu, Q.; Qian, C.; Liu, C.; Liu, W.; Chen, K.; Lei. A.
Angew. Chem. Int. Ed. 2016, 55, 1094-1097.
Author Contributions
‡These authors contributed equally.
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ACKNOWLEDGMENT
Financial support was provided by NSFC (21672069, 21472050),
DFMEC (20130076110023), Fok Ying Tung Education Founda-
tion (141011), the Program for Shanghai Rising Star
(15QA1401800), Professor of Special Appointment (Eastern
ACS Paragon Plus Environment

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(21) CCDC-1541117 (3u): C13H11BrO2S, MW = 311.19, Triclinic,
space group P21/n, final R indices [I > 2σ(I)], R1 = 0.0321, wR2
0.0855, R indices (all data), R1 = 0.0375, wR2 = 0.0893, a,
=
=
6.6244(3) Å , , b = 9.5477(5) Å, c = 11.0255(5) Å, α = 69.7280(10) o,
β = 77.3960(10)o , , γ = 74.1380(10)o, V = 623.31(5) Å3, Z = 2, Reflec-
tions collected/unique: 7271/2171 (R(int) = 0.0212). These data can be
obtained free of charge from Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/ci.
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EY hv
N2
EY hv
,
,
O
S
Air
S
S
+
Ar2IBF4
Mask
Ar/Alkyl
Ar
Ar/Alkyl
Ar
Ar/Alkyl
SET
SET ET
=
Mask SO3Na
6
7
•
•
and
Selective Sulfoxidation
Sulfidation
Late-Stage Sulfoxidation
8
•
•
Mild
and
Cascade Electron
Energy Transfer
Diarylsulfoxide Synthesis
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