Odorless, Regioselective Synthesis of Diaryl Sulfides and α-Thioaryl Carbonyls from Sodium Arylsulfinates via a Metal- Free Radical Strategy in Water

Article abstract of DOI:10.1002/adsc.201600846

Regioselective arylthiolations of aromatic amines, arenols and ketones via C–H bond functionalization have been achieved with I₂and PPh₃in an aqueous system, whereby arylsulfenyl radicals are in situ generated from odorless sodium arylsulfinates. The arylsulfenyl radicals can react with free anilines containing electron-withdrawing groups and complex substrates (estrone and progesterone). Further experiments and quantum chemical calculations were also performed to deduce a mechanism for the formation of arylsulfenyl radicals. (Figure presented.).

Full text of DOI:10.1002/adsc.201600846

FULL PAPERS
DOI: 10.1002/adsc.201600846
Odorless, Regioselective Synthesis of Diaryl Sulfides and
a-Thioaryl Carbonyls from Sodium Arylsulfinates via a Metal-
Free Radical Strategy in Water
Ya-mei Lin,a Guo-ping Lu,a,* Gui-xiang Wang,a and Wen-bin Yia,*
a
Chemical Engineering College, Nanjing University of Science and Technology, Nanjing 210094, Peopleꢀs Republic of
China
Fax : (+86)-25-8431-5030; phone: (+86)-25-8431-5514; e-mail: glu@njust.edu.cn or yiwenbin@njust.edu.cn
Received: July 30, 2016; Revised: October 15, 2016; Published online: && &&, 0000
Supporting information for this article can be found under: http://dx.doi.org/10.1002/adsc.201600846.
Abstract: Regioselective arylthiolations of aromatic substrates (estrone and progesterone). Further ex-
amines, arenols and ketones via C–H bond function- periments and quantum chemical calculations were
alization have been achieved with I2 and PPh3 in an also performed to deduce a mechanism for the for-
aqueous system, whereby arylsulfenyl radicals are in mation of arylsulfenyl radicals.
situ generated from odorless sodium arylsulfinates.
The arylsulfenyl radicals can react with free anilines Keywords: arylthiolation; diaryl sulfides; radical re-
containing electron-withdrawing groups and complex action; sodium arylsulfinates; a-thioaryl carbonyls
Introduction
enolates with various sulfanylating agents using strong
bases;[8] (ii) the nucleophilic substitution of a-halogen-
Both diaryl sulfides[1] and a-thioaryl carbonyl com- ated ketones with benzenethiols or disulfides;[9] and
pounds[2] are important and useful intermediates in (iii) metal-catalyzed reactions for the construction of
organic synthesis as well as being ubiquitous in natu- C–S bonds.[10] To eliminate the use of strong bases
ral products, pharmacologically active compounds and and metals, several metal-free strategies were devel-
organic materials. Traditionally, there are two main oped for the synthesis of such compounds via nucleo-
approaches for the preparation of diaryl sulfides. One philic a-sulfanylation of ketones, but thiols (or sulfur
is the transition metal-catalyzed cross-coupling of di- reagents pre-prepared from thiols) and organic sol-
sulfides or thiols with aryl halides or pseudohalides.[3] vents are the norm.[11] Based on these results, the
Another method typically relies on the coupling of quest for an efficient protocol using odorless sulfur
electrophilic sulfur reagents with organozinc or reagents in green solvents is still ongoing.
Grignard reagents.[4] In recent years, a series of regio-
With our interest in exploring new approaches for
selective methods for the direct C–H arylthiolation of the construction of C–S bonds in water,[12] we disclose
arenes[5] or cyclohexanone[6] via electrophilic substitu- a metal-free radical route for the synthesis of diaryl
tion routes to afford diaryl sulfides has been reported. sulfides and a-thioaryl carbonyl compounds using
Although the arylthiolations of various electron-rich odorless and easy-to-handle sodium arylsulfinates as
arenes proceeded smoothly in these approaches, other the sulfur source in an aqueous I2/PPh3 system. To the
arenes such as free anilines failed to yield the desired best of our knowledge,[13] this is the first example of
products.
the arylsulfanylation of free anilines and ketones
Therefore, a metal-free protocol for the arylsulfura- using sodium arylsulfinates by a metal-free radical
tion of aromatic amines (especially free anilines) via process in water. Further control experiments and
direct aryl C–H bond functionalization appears desir- quantum chemical calculations were also performed
able and synthetically attractive. Arylsulfenyl radicals to gain insights into the generation mechanism of ar-
seem to be an ideal species to achieve this goal since ylsulfenyl radicals in this system.
they are less electrophilic but more stable than the
corresponding sulfenyl cations.[7] On the other hand,
the classical methods for the formation of a-thioaryl
carbonyl compounds include (i) the sulfanylation of
Adv. Synth. Catal. 0000, 000, 0 – 0
1
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

FULL PAPERS
asc.wiley-vch.de
Results and Discussion
Initially, the coupling of 2,6-dimethylaniline 1a with
sodium p-tolylsulfinate 2a was selected as the model
reaction to optimize the reaction conditions (Table 1).
After screening different solvents, water proved to be
the best option (entry 8). Both I2 and PPh3 are neces-
sary for the reaction. Diethyl phosphite in place of
PPh3 resulted in a lower yield of 3a (entry 9). DMSO
was also employed to reduce the amount of I2,[14] but
the results were unsatisfac tory (entry 10). Other
sulfur sources including p-tolylthiol and 1,2-bis(4-tol-
yl)disulfane failed to yield the desired products in this
system.
With the optimized conditions in hand, various
amines and sodium arylsulfinates were chosen to es-
tablish the scope and generality of this protocol
(Scheme 1). A series of electron-rich free anilines was
subjected to the reaction conditions to produce the
desired products (3a, 3b, 3e, 3f, 3l). To our delight,
moderate to good yields were afforded in the cases of
free anilines with electron-withdrawing groups (3c,
3d, 3h–3k), which failed to yield the desired products
in the nucleophilic approaches. The reactions pro-
ceeded smoothly using N-substituted arylamines as
Table 1. Optimization of the reaction conditions.[a]
Entry
Solvent
Yield [%][b]
1
2
toluene
THF
45
13
3
4
5
6
7
8
9
10
11
12
dioxane
DMSO
DMF
EtOH
MeCN
H2O
H2O
H2O
H2O
H2O
30
trace
54
Scheme 1. The reaction of arylamines with sodium arylsulfi-
nates in water. PT=p-tolyl. Conditions: amine (0.25 mmol),
sodium arylsulfinate (0.30 mmol), I2 (0.25 mmol), PPh3
(0.6 mmol), H2O (1.0 mL), 1008C, 12 h. Isolated yields are
reported.
29
trace
92, 0,[c] 0[d]
38[e]
26[f]
trace[g]
trace[h]
the starting materials (3m–3q). Generally, the para-
Conditions: 1a (0.25 mmol), 2a (0.30 mmol), I2 sulfanylarylamines were the main products, and traces
[a]
(0.25 mmol), PPh3 (0.60 mmol), H2O (1.0 mL), 1008C,
12 h.
Isolated yields.
Without I2.
of the disulfanyl products were obtained (3b, 3n, 3p)
in some cases. For the para-substituted aromatic
amines, ortho-sulfanyl products were obtained as the
final products.
The reactions of quinolin-8-amine or N-methylani-
line with sodium p-tolylsulfinate resulted in 2,4-disul-
fanylarylamines as the main products (3l, 3m). Sur-
prisingly, an aromatization product (3o) was derived
when using 1,2,3,4-tetra-hydroquinoline as the sub-
strate. A 2,6-disulfanyl product (3r) was afforded
[b]
[c]
[d]
[e]
[f]
Without PPh3.
Diethyl phosphite in place of PPh3.
DMSO (3 equiv.) and I2 (20 mol%) in place of I2
(1 equiv.).
p-Tolylthiol in place of sodium p-tolylsulfinate was used.
1,2-Bis(4-tolyl)disulfane in place of sodium p-tolylsulfi-
nate was used.
[g]
[h]
Adv. Synth. Catal. 0000, 000, 0 – 0
2
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

FULL PAPERS
asc.wiley-vch.de
when 1-phenyl-1H-pyrrole was used as the substrate.
Sodium methanesulfinate was also applied in the re-
action to gain a poor yield of the desired product
(3g).
In the view of the similar reactivity of arenols with
aromatic amines, we next sought to study the sulfany-
lation of arenols (Scheme 2). Generally, the electron-
rich phenols should undergo the sulfanylation to fur-
nish the products (4a–4i) in moderate to good yields.
However, no reaction took place in the cases of the
phenols with electron-withdrawing groups (such as
nitro and trifluoromethyl groups). An excellent para-
selectivity of the sulfanylation was observed (4c–4f),
meanwhile only ortho-substituted products were pro-
vided when arenols bearing para groups were used
(4a, 4b, 4h, 4i, 4k). In the cases of benzene-1,3,5-triol
and 1H-indol-5-ol, disulfanyl (4g) and trisulfanyl
products (4j) were yielded, respectively. A complex
phenol (estrone) was also applied in the protocol to
afford the desired product (4k).
With the successful development of the sulfanyla-
tion of arenes, further investigations were made to re-
alize the sulfanylation of ketones with sodium arylsul-
Scheme 3. The reactions of sodium arylsulfinates with ke-
tones. PT=p-tolyl. Conditions: sodium arylsulfinate
(0.30 mmol), ketone (0.25 mmol), I2 (0.25 mmol), PPh3
(0.60 mmol), H2O (1.0 mL), 1008C, 12 h. Isolated yields are
reported.
finates via C–H functionalization (Scheme 3). Linear
ketones could react with sodium arylsulfinates to
form a-arylthio ketones (5a–5d) in low to moderate
yields. Cyclic ketones exhibit better reactivity than
linear ones (5e–5h, 5j–5l). It should be noted that un-
expected a-sulfanyl enones (5f–5h) and 2-sulfanylare-
nols (5j–5l) were generated under the optimized con-
ditions, presumably owing to the iodine-induced oxy-
dehydrogenations.[6] The scope was also extended to
other cyclic carbonyl compounds, such as isochroman-
3-one and 4-hydroxycoumarin (5i, 5m). Encouraged
by the broad generality of this protocol, we sought to
demonstrate its applicability in more complex ke-
tones. To our delight, a disulfanyl product (5n) was
obtained when progesterone was subjected to the
identical conditions. Interestingly, a sulfanylfuran (5o)
was obtained from cyclopropyl(phenyl)methanone
with sodium p-tolylsulfinates through a ring-opening
and recyclization route (Scheme 4).
Scheme 2. The sulfanylation of arenols with sodium arylsul-
finates. PT=p-tolyl. Conditions: sodium arylsulfinate
(0.30 mmol), arenol (0.25 mmol), I2 (0.25 mmol), PPh3
(0.60 mmol), H2O (1.0 mL), 1008C, 12 h. Isolated yields are
reported.
Adv. Synth. Catal. 0000, 000, 0 – 0
3
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

FULL PAPERS
asc.wiley-vch.de
Scheme 4. The reaction of cyclopropyl(phenyl)methanone
with sodium p-tolylsulfinates in water.
To probe the mechanism, radical trapping experi-
ments were designed and investigated (Figure 1). All
the reactions were inhibited in the presence of the
radical trap TEMPO. Radical trapping product 6 was
observed by GC-MS, separated and further identified
Figure 2. EPR results in the system of I2/PPh3.
by 1H and 13C NMR spectra suggesting that these
transformations may involve radical processes. To fur-
ther certify the radical process in the system, electron
paramagnetic resonance (EPR) experiments were
also performed. The TEMPO signals disappeared
when both I2 and PPh3 were employed in aqueous sys-
tems (Figure 2, a vs. b). Weak radical signals were de-
tected in the system of I2/PPh3 when DMF was added
(c vs. d), so DMF may play a role as the radical stabil-
izer in this system.
Based on these results, it can be concluded that
free radicals are generated in the system of I2/PPh3.
Further control experiments were carried out to con-
firm whether S-phenyl benzene sulfonothioate, 1,2-di-
p-tolyl disulfane or 4-methylbenzenethiol were the in-
termediates in this system (Table 2). It was found that
no or poor yields of the final products were afforded
in most cases. Although the desired products could be
Figure 1. The radical trapping experiments. Conditions: 1a
(0.30 mmol), aniline, phenol or cyclopropyl(phenyl)metha-
none (0.25 mmol), I2 (0.25 mmol), PPh3 (0.60 mmol), H2O
(1 mL), 1008C, 12 h. Isolated yields are reported.
Table 2. Control experiments for the probable reaction intermediates.[a]
Entry
Intermediate
Substrate
Yield [%][b]
Yield [%][b,c]
1
2
3
4
5
6
7
8
9
acetophenone
phenol
aniline
acetophenone
phenol
aniline
acetophenone
phenol
aniline
nr
10
61
nr
nr
nr
nr
nr
nr
–
trace
63
–
–
–
–
–
–
1,2-bis(4-chlorophenyl)disulfane
[a]
The reaction conditions were the optimized conditions except that sodium p-tolylsulfinate was used instead of the inter-
mediates.
[b]
[c]
The yields were determined by GC-MS.
3 equiv. TEMPO were used in these reactions.
Adv. Synth. Catal. 0000, 000, 0 – 0
4
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

FULL PAPERS
asc.wiley-vch.de
Table 3. The calculated values of the BDEs of some possible
intermediates based on quantum calculations.
Compound
Dissociation bond
BDE [kJ/mol]
Ph–S–I
I2
PhS–SPh
Br2
S–I
I–I
S–S
Br–Br
190.35
171.02 (151)[a]
228.14
190.09 (192)[a]
[a]
Actual measured value.
Figure 4. A tentative pathway for the arylthiolation of
arenes with sodium arylsulfinates in the I2/PPh3 system.
obtained with moderate yields in the reaction of ani-
line with S-phenyl benzenesulfonothioate, the reac-
tion did not involve a radical route. Thus, all of them
proved to be not the intermediates in the system.
According to the calculation results of the bond dis- Conclusions
sociation energies (BDEs) (Table 3), it can be con-
cluded that both homolyses of I2 and PhSI are likely In summary, we have introduced an efficient aqueous
to occur to form phenylthio radicals in the I2/PPh3 sys- system for the regioselective synthesis of diaryl sul-
tem.[12a,15] On the basis of the results above and previ- fides and a-thioaryl carbonyls from sodium arylsulfi-
ous literature reports, a mechanism was proposed for nates, in which no metal, organic solvent or evil smell-
the formation of arylsulfenyl radicals in the I2/PPh3 ing thiol is required. Electron-deficient free anilines
system and is illustrated in Figure 3. At first, reduc- and complex subtrates (estrone and progesterone)
tion of sodium arylsulfinate mediated by a combina- can be applied in the protocol owing to the high reac-
tion of I2 and PPh3 results in ArSI.[16] Then, arylsul- tivity of the in situ generated arylsulfenyl radicals.
fenyl radicals are formed via the homolysises of I2 or The experiments and quantum calculations were also
ArSI in the I2/PPh3 system. Meanwhile, polar process- performed to gain insights into the generation mecha-
es may also exist in these transformations as the nism of arylsulfenyl radicals. Moreover, this sulfura-
minor pathways.
tion chemistry has the potential to promote the dis-
Although the detailed mechanisms of these reac- covery of other new radical sulfuration reactions for
tions remain to be elucidated, a tentative pathway for the construction of organosulfur compounds.
C–H arylthiolation of arenes is proposed (Figure 4).
Firstly, an arylsulfenyl radical adds to the arene to
produce radical intermidate 7 (o-substituted) or 8 (p- Experimental Section
substituted). Then, the o-substituted product (or p-
substituted product) is formed by the reaction of General Procedure for the Synthesis of 3 and 4
ArSI and 7 (or 8) following the formation of an aryl-
A mixture of sodium arylsulfinate (0.30 mmol), phenol or
aromatic amine (0.25 mmol), I2 (0.25 mmol) and PPh3
sulfenyl radical and HI.[5,12a]
(0.60 mmol) in water (1.0 mL) was stirred at 1008C for 12 h.
Upon completion, the reaction mixture was diluted with
EtOAc (4.0 mL), filtered through a bed of silica gel layered
over Celite. The volatiles were removed under vacuum to
afford the crude product. Further column chromatography
on silica gel (EtOAc/petroleum ether) was needed to afford
the pure desired product 3 or 4.
General Procedure for the Synthesis of 5
A mixture of sodium arylsulfinate (0.30 mmol), ketone
(0.25 mmol), I2 (0.25 mmol) and PPh3 (0.60 mmol) in water
(1.0 mL) was stirred at 1008C for 12 h. Upon completion,
the reaction mixture was diluted with EtOAc (4.0 mL), fil-
tered through a bed of silica gel layered over Celite. The
volatiles were removed under vacuum to afford the crude
Figure 3. The proposed mechanism of formation of arylsul-
fenyl radicals from sodium arylsulfinates in the I2/PPh3
system.
product. Further column chromatography on silica gel
(EtOAc/petroleum ether) was needed to afford the pure de-
sired product 5.
Adv. Synth. Catal. 0000, 000, 0 – 0
5
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

FULL PAPERS
asc.wiley-vch.de
3098; f) Q. Wu, D. Zhao, X. Qin, J. Lan, J. You, Chem.
Commun. 2011, 47, 9188–9190; g) D. Wang, R. Zhang,
S. Lin, Z. Yan, S. Guo, RSC Adv. 2015, 5, 108030–
108033.
Acknowledgements
We gratefully acknowledge the Natural Science Foundation
of China (21402093, 21476116) and Jiangsu (BK20140776,
BK20141394), Chinese Postdoctoral Science Foundation
(2016T90465, 2015M571761), the Center for Advanced Mate-
rials and Technology in Nanjing University of Science and
Technologyand Priority Academic Program Development of
Jiangsu Higher Education Institutions for financial support.
[6] a) Y. Liao, P. Jiang, S. Chen, H. Qi, G.-J. Deng, Green
Chem. 2013, 15, 3302–3306; b) Y. Chen, F. Xiao, H.
Chen, S. Liu, G.-J. Deng, RSC Adv. 2014, 4, 44621–
44628; c) W. Ge, X. Zhu, Y. Wei, Adv. Synth. Catal.
2013, 355, 3014–3021.
[7] a) X.-Q. Pan, J.-P. Zou, W.-B. Yi, W. Zhang, Tetrahe-
dron 2015, 71, 7481–7529; b) A. Studer, D. P. Curran,
Angew. Chem. 2016, 128, 58–106; Angew. Chem. Int.
Ed. 2016, 55, 58–102; c) F. Denes, M. Pichowicz, G.
Povie, P. Renaud, Chem. Rev. 2014, 114, 2587–2693.
[8] a) B. M. Trost, T. N. Salzmann, K. Hiroi, J. Am. Chem.
Soc. 1976, 98, 4887–4902; b) P. Groenewegen, H. Kal-
lenberg, A. van der Gen, Tetrahedron Lett. 1979, 20,
2817–2820; c) K. Deng, J. Chalker, A. Yang, T. Cohen,
Org. Lett. 2005, 7, 3637–3640.
[9] a) C. Peppe, L. Borges de Castro, Can. J. Chem. 2009,
87, 678–683; b) B. C. Ranu, R. Jana, Adv. Synth. Catal.
2005, 347, 1811–1818; c) B. C. Ranu, T. Mandal, J. Org.
Chem. 2004, 69, 5793–5795.
[10] a) M. A. McKervey, P. Ratananukul, Tetrahedron Lett.
1982, 23, 2509–2512; b) S. Sengupta, S. Mondal, Tetra-
hedron Lett. 1999, 40, 8685–8688.
[11] a) W. Wang, H. Li, J. Wang, L. Liao, Tetrahedron Lett.
2004, 45, 8229–8231; b) J. S. Yadav, B. V. Subba Reddy,
R. Jain, G. Baishya, Tetrahedron Lett. 2008, 49, 3015–
3018; c) A. F. Vaquer, A. Frongia, F. Secci, E. Tuveri,
RSC Adv. 2015, 5, 96695–96704.
[12] a) Y.-m. Lin, G.-p. Lu, C. Cai, W.-b. Yi, Org. Lett. 2015,
17, 3310–3313; b) Y.-m. Lin, W.-b. Yi, W.-z. Shen, G.-p.
Lu, Org. Lett. 2016, 18, 592–595; c) G.-p. Lu, C. Cai, F.
Chen, R.-l. Ye, B.-j. Zhou, ACS Sustain. Chem. Eng.
2016, 4, 1804–1809; d) G.-p. Lu, C. Cai, Adv. Synth.
Catal. 2013, 355, 1271–1276; e) G.-p. Lu, C. Cai, RSC
Adv. 2014, 4, 59990–59996.
[13] Only some examples on the arylthiation of substituted
anilines or anisoles from thiols through metal-free radi-
cal routes have been reported. a) D. Yang, K. Yan, W.
Wei, J. Zhao, M. Zhang, X. Sheng, G. Li, S. Lu, H.
Wang, J. Org. Chem. 2015, 80, 6083–6092; b) Z. Huang,
D. Zhang, X. Qi, Z. Yan, M. Wang, H. Yan, A. Lei,
Org. Lett. 2016, 18, 2351–2354.
References
[1] a) A. Gangjee, Y. Zeng, T. Talreja, J. J. McGuire, R. L.
Kisliuk, S. F. Queener, J. Med. Chem. 2007, 50, 3046–
3053; b) K. Takimiya, S. Shinamura, I. Osaka, E. Miya-
zaki, Adv. Mater. 2011, 23, 4347–4370; c) Y. Zhou, W.-J.
Liu, Y. Ma, H. Wang, L. Qi, Y. Cao, J. Wang, J. Pei, J.
Am. Chem. Soc. 2007, 129, 12386–12387; d) T. Mori, T.
Nishimura, T. Yamamoto, I. Doi, E. Miyazaki, I.
Osaka, K. Takimiya, J. Am. Chem. Soc. 2013, 135,
13900–13913; e) I. P. Beletskaya, V. P. Ananikov, Chem.
Rev. 2011, 111, 1596–1636.
[2] a) B. M. Trost, Acc. Chem. Res. 1978, 11, 453–461;
b) B. M. Trost, Chem. Rev. 1978, 78, 363–382; c) Q. Lu,
H. Wang, P. Peng, C. Liu, Z. Huang, Y. Luo, A. Lei,
Org. Chem. Front. 2015, 2, 908–912.
[3] a) T. Kondo, T.-a. Mitsudo, Chem. Rev. 2000, 100,
3205–3220; b) D. Ma, Q. Cai, Acc. Chem. Res. 2008, 41,
1450–1460; c) T. Ramana, P. Saha, M. Das, T. Punniya-
murthy, Org. Lett. 2010, 12, 84–87; d) Z. Jiang, J. She,
X. Lin, Adv. Synth. Catal. 2009, 351, 2558–2562; e) C.-
K. Chen, Y.-W. Chen, C.-H. Lin, H.-P. Lin, C.-F. Lee,
Chem. Commun. 2010, 46, 282–284.
[4] a) J.-H. Cheng, C. Ramesh, H.-L. Kao, Y.-J. Wang, C.-
C. Chan, C.-F. Lee, J. Org. Chem. 2012, 77, 10369–
10374; b) J. T. Reeves, K. Camara, Z. S. Han, Y. Xu, H.
Lee, C. A. Busacca, C. H. Senanayake, Org. Lett. 2014,
16, 1196–1199; c) I. M. Yonova, C. A. Osborne, N. S.
Morrissette, E. R. Jarvo, J. Org. Chem. 2014, 79, 1947–
1953.
[5] All the reactions in the article are C–H arylthiolations
of arenes, which should be C–H functionalizations, al-
though no direct H-abstraction process exists during
these reactions. For selected monographs on the direct
C–H arylthiolation of arenes by electrophilic substitu-
tion routes, see: a) T. Hostier, V. Ferey, G. Ricci, D.
Gomez Pardo, J. Cossy, Org. Lett. 2015, 17, 3898–3901;
b) S. K. R. Parumala, R. K. Peddinti, Green Chem.
2015, 17, 4068–4072; c) F. Xiao, S. Chen, J. Tian, H.
Huang, Y. Liu, G.-J. Deng, Green Chem. 2016, 18,
1538–1546; d) X. Zhao, T. Li, L. Zhang, K. Lu, Org.
Biomol. Chem. 2016, 14, 1131–1137; e) S. Saba, J. Rafi-
que, A. L. Braga, Catal. Sci. Technol. 2016, 6, 3087–
[14] F. Xiao, H. Xie, S. Liu, G.-J. Deng, Adv. Synth. Catal.
2014, 356, 364–368.
[15] a) Y. Zheng, Y. He, G. Rong, X. Zhang, Y. Weng, K.
Dong, X. Xu, J. Mao, Org. Lett. 2015, 17, 5444; b) F.-X.
Wang, S.-K. Tian, J. Org. Chem. 2015, 80, 12697.
[16] a) P. Katrun, S. Hongthong, S. Hlekhlai, M. Pohmakotr,
V. Reutrakul, D. Soorukram, T. Jaipetch, C. Kuhakarn,
RSC Adv. 2014, 4, 18933; b) K. Takai, K. Oshima, H.
Nozaki, Bull. Chem. Soc. Jpn. 1983, 56, 3791.
Adv. Synth. Catal. 0000, 000, 0 – 0
6
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

FULL PAPERS
Odorless, Regioselective Synthesis of Diaryl Sulfides and a-
Thioaryl Carbonyls from Sodium Arylsulfinates via a Metal-
Free Radical Strategy in Water
7
Adv. Synth. Catal. 2016, 358, 1 – 7
Ya-mei Lin, Guo-ping Lu,* Gui-xiang Wang, Wen-bin Yi*
Adv. Synth. Catal. 0000, 000, 0 – 0
7
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!