Trifluoromethylation of thiophenols and thiols with sodium trifluoromethanesulfinate and iodine pentoxide

Article abstract of DOI:10.1039/c5cy01561h

A selective and facile trifluoromethylation process for a wide range of thiophenols and thiols under metal free conditions has been developed using two simple and safe solids, sodium trifluoro-methanesulfinate and iodine pentoxide, via the radical process.

Full text of DOI:10.1039/c5cy01561h

View Article Online
View Journal
Catalysis
Science &
Technology
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: J. Ma, W. Yi, G. Lu
and C. Cai, Catal. Sci. Technol., 2015, DOI: 10.1039/C5CY01561H.
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
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
Information for Authors.
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 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.
www.rsc.org/catalysis

Please do not adjust margins
Catalysis Science & Technology
Page 1 of 5
View Article Online
DOI: 10.1039/C5CY01561H
Journal Name
COMMUNICATION
Trifluoromethylation of Thiophenols and Thiols with Sodium
Trifluoromethanesulfinate and Iodine Pentoxide
Jing-Jing Maa, Wen-Bin Yia*, Guo-Ping Lua and Chun Caia
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
containing compounds were generated as the trifluoromethyl
group attached to sulfur atoms instead of carbon atoms, which
displayed rather different properties, compared to the SCH3
group.3 The linkage of a strong electron-withdrawing, and
metabolically stable CF3 group with a highly polarizable and
bio-friendly sulfur atom, which makes SCF3 showed extremely
I2O5
DM
CF3SO2Na
I2O5
R
SCF3
R
SH
+
SO
R= Aryl or Alkyl
peroxide free
transition-metal free
broad substrate scope
SET
I2
(R-S)2
or
п
=1.44)4 for small molecules to cross lipid
CF3
high lipophilicity (
membranes and influences intracellular targets.5 Therefore,
numerous efforts have been devoted to the development of
new methodologies for the preparation of these SCF3-
containing molecules.
S
Trifluoromethylation via radical pathway
HI
R
I
A selective and operationally easy trifluoromethylation of a wide
range of thiophenols and thiols under metal free conditions by
using two simple and safe solids, sodium trifluoro-
methanesulfinate and iodine pentoxide, via the radical process
has been developed.
Direct
R
X
SCF3 reagents
X = H, halos, carboxyl, etc.
H
R
SCF3
SCF3
O
N
O
H
N
N
SCF3
N
SCF3
S
Me
Et
Et
R
+
Y
N
O
Me
H
Indirect
O
or
sulfur souce
OMe
Me
ToltrazurII1b
RZ
1c
1a
CF3 reagents
Tiforex
Adrenergicagent
Y = H, cyanates, metal, etc.
Z = H etc.
Figure 2. Two major strategies for the preparation of SCF3-containing
Cl
SCF3
OH
HOOC
SCF3
compounds.
N
SCF3
O
NH
NH2
OH OH
N
SO2CH3
Accordingly, two major strategies have been developed for
the formation of SCF3 over years (Figure 2). One is the direct
trifluoromethylthiolation with SCF3 reagents.6 This strategy is a
straightforward protocol for the preparation of SCF3
compounds, which does not require specific skills and use of
protective clothing and equipment.7 Many researches are
focused on typical novel trifluoromethylthiolated reagents,
such as MSCF3 (M= Cu, Ag, Cs),8 (Me4N)SCF3,9 N-SCF3 reagents10,
O-SCF3 reagents11 and hypervalent iodine SCF3 reagents,12
which have replaced the hazardous reagents that were most
available in the gaseous form or relatively ineffective
reagents.13 Nevertheless, some of these SCF3 reagents still
existed drawbacks, such as high cost or the pre-preparation
process which involved lengthy reactions or harsh conditions.
1d
1e
1f
Pesticideanalogue
Methionineanalogue
-RIbosyl-homocysteineanalogue
S
Figure 1. Examples of SCF3-containing biologically active compounds.
Trifluromethylthio group (SCF3) has received increasing
attention as an enhanced version of CF3 in bioactive
molecules,1 which is a highly privileged functionality for
pharmaceutical and agrochemical agents (Figure 1).2 SCF3-
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
Catalysis Science & Technology
Page 2 of 5
View Article Online
DOI: 10.1039/C5CY01561H
COMMUNICATION
Journal Name
The other was the indirect formation focused on trifluoro- I2O5 using DCE/H2O as solvent, giving p- tolyl(trifluoromethyl)-
methylating of different sulphur sources. Great attention has
sulfane (2b) in 43 % yield (entry 6). Contrasted to aqueous
concentrated on this field since a variety of sulphur sources,
15
Table 1. Optimization of the reaction conditions.a
such as thiolates,14 S8,
thiocyanates,16 Na2S2O3,17
sulfocyanate,18 disulfides19 and thiols20 have been effectively
combined with relatively inexpensive trifluoromethylated
reagents. For example, pioneering by Umemoto, thiolates
were found to be efficient sulphur sources with Se-
(trifluoromethyl)dibenzoselenophenium for the synthesis of
SCF3.14a S8 was an effective example which could be connected
with FSO2CF2CO2Me and CF3SiMe3, as well as CF3SO2Na to
afford SCF3 moieties.15a-b,15f Goossen and co-workers employed
thiocyanate to prepare the corresponding aryl trifluoromethyl
with arenediazonium salts.16a Liu et al. reported an effective
trifluoromethylthiolation using Na2S2O3 as sulphur source.17
The Langlois group developed a photocatalytic trifluoro-
methylation method in the presence of disulfides.19c,19d Boiko
and Yagupolskii demonstrated a series of trifluoromethylation
of thiols in liquid ammonia and UV initiation.20a,20b Although
these approaches provided convenience for the SCF3-
containing compounds, several issues of these approaches
should be addressed: (1) the limited starting substrates, such
as aryl halogens, aryl boronic acids, terminal alkynes; (2)
excess sulphur sources were utilized; (3) high volatile
trifluoromethylated reagents were often used under radical
process.
Entry
Oxidant (equiv.)
CF3SO2Na
(equiv.)
3.0
Solventb
T (oC)
Yield
(%)c
1
2
I2 (2.0)
PhIO (2.0)
PhI(OAc)2 (2.0)
NaIO3 (2.0)
HIO3 (2.0)
I2O5 (2.0)
I2O5 (2.0)
I2O5 (2.0)
I2O5 (2.0)
I2O5 (2.0)
I2O5 (2.0)
I2O5 (1.0)
I2O5 (3.0)
I2O5 (4.0)
I2O5 (2.0)
I2O5 (2.0)
I2O5 (2.0)
I2O5 (2.0)
-
DCE/H2O
DCE/H2O
DCE/H2O
DCE/H2O
DCE/H2O
DCE/H2O
DCE/H2O
DMSO
110
110
110
110
110
110
110
110
110
110
110
110
110
110
90
N. D
N. D
N. D
N. D
N. D
43
.
.
.
.
.
3.0
3
3.0
4
3.0
5
3.0
6
7d
3.0
3.0
63
8
3.0
92
9
1.0
DMSO
31
10
11
12
13
14
15
16
17
18
19e
20f
21g
2.0
DMSO
59
4.0
DMSO
88
3.0
DMSO
39
3.0
DMSO
89
3.0
DMSO
81
3.0
DMSO
79
3.0
DMSO
70
24
3.0
DMSO
50
trace
trace
N. D.
N. D.
92
3.0
DMSO
R.T.
110
110
110
In 1989, Langlois and his co-workers described a TBHP-
initiated trifluoromethylation of disulfides using CF3SO2Na as
trifluoromethylated reagent.21a Although this method utilized
stable and inexpensive trifluoromethylated source, almost half
disulfides were oxidized by excess peroxide with low yield.21b-d
Among these indirect cases, trifluoromethylation of thiols
under radical process was an efficient protocol to obtain SCF3
and several researches have been reported. Hard-handling and
poor user-friendliness reagents, such as CF3Br,22 CF3I23 were
used during the original research. Another type of
trifluoromethylation reagent used in radical reactions was N-
3.0
DMSO
I2O5 (2.0)
I2O5 (2.0)
-
DMSO
3.0
DMSO
a
Unless otherwise stated, all reactions were carried out with 1b (0.2 mmol),
b
solvent 2.0 mL, 24 h, GC yield. DCE/H2O (v/v= 3/1, 4.5 mL); DCE = 1,2-
c
d
dichloroethane. N.D.: not detected by GC-MS. DMSO (1.0 mL) was added;
DMSO = (methylsulfonyl)methane. Without I2O5. f Without CF3SO2Na. g Under
e
argon atmosphere.
solvents, DMSO was more suitable for this reaction (entry 6 vs
entry 8). Additionally, 3.0 equiv. CF3SO2Na was necessary for
the depletion of the thiols after screening (entries 8-11). The
content of I2O5 was also screening, the result indicated that 2.0
equiv. I2O5 was enough for this reaction and the overloading of
I2O5 might bring the decreasing yield (entries 12-14). Only
trace product was found at room temperature, indicating that
it is a temperature-dependent reaction (entries 15-18). Both
I2O5 and CF3SO2Na were important for smooth transformation
of this reaction (entries 19-20). Almost no difference was
found when reacted under the argon atmosphere (entry 21).
Under the optimized reaction conditions, the trifluoro-
methylation of various thiophenols and thiols were tested to
examine the scope of this reaction (Table 2). The reaction
proved to be general and amenable to a range of structurally
trifluoromethyla-N-nitrososulfon
amide,24 but
difficult
preparation process with low yield limited its application. Thus,
the radical trifluoromethylation of thiols has not been well-
studied.
Very recently, Liu and his co-workers reported a novel
method to generate the corresponding CF3 radical from
sodium trifluoromethanesulfinate, using iodine pentoxide as a
low-cost, green and stable inorganic oxidant.25 Inspired by
their work, and as part of our efforts in the field of
organofluorine chemistry,26 we herein endeavoured to
develop a simple and atom economic trifluoromethylation
method of a wide range of thiophenols and thiols in the
presence of iodine pentoxide using CF3SO2Na as CF3 source.
This method allows for smooth transformation to various SCF3
without transition metal catalysts and takes advantage of
sulphur sources as much as possible.
diverse substrates, and the desired products (2a-2w) were
achieved in good yields. In general, both electron-rich and
electron-deficient substrates reacted well and a wide variety of
functional groups were covered, including methyl (2b), tert-
We initially chose the trifluoromethylation of 4-
methylbenzenethiol (1b) as the model reaction to optimize
reaction conditions (Table 1). After screening several oxidants
(entries 1-6), the best result was achieved in the presence of
butyl (2c), methoxyl (2d), halos (2e
-2g), amino (2h, 2i), nitro
(
2k-2m), carboxyl (2n). A slight difference in the yield about
substituents (such as –NO2) on the aromatic ring at any
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
Catalysis Science & Technology
Page 3 of 5
View Article Online
DOI: 10.1039/C5CY01561H
Journal Name
COMMUNICATION
position (para-, meta-, ortho-) was found (2k-2m). In addition, diphenylethylene (3.0 equiv.) as radical scavengers (equ. 5 and
benzeneselenol was obtained in 74% yield (2o). Furthermore, 6), which points toward a radical mechanism.
the aromatic rings with nathphyl, thiazole, pyridine, pyrimidine
Although the precise reaction mechanism remains to be
clarified, we prefer a plausible mechanism in Scheme 2.25,28
Table 2. Trifluoromethylation of thiophenols and thiols. a
a
Scheme 1. Control experiments. CF3SO2Na (3.0 equiv.), I2O5 (2.0 equiv.) and
DMSO 2.0 mL, 110
℃
for 24 h. b 0.1 mmol disulphide
High temperature leaded to rapid reacting of iodine pentoxide
and CF3SO2Na. As a result, I2 was released and generated the
CF3 radical via single electron transfer. I2 then reacted with
thiols or thiophenols to form
4 28c,28d
Finally, the CF3 radical coordinated to
desired products.
3
and further reacted to form
.
3
or 4, giving the
a
Reaction condition: 1 (0.2 mmol), CF3SO2Na (3.0 equiv.), I2O5 (2.0 equiv.) and
b
c
DMSO 2.0 mL, 110 ℃ for 24 h, isolated yield. GC yield (due to high volatility).
Used DL-thioctic acid as 1w.
were viable substrates under the current reaction, giving the
corresponding products (2p 2s) in satisfactory yields. Thiols,
-
such as benzylthiol, 2-mercaptoethanol and 3-mercapto-
propanoic acid, were also smooth transformation for the
products (2t
sulfur 2w
substrate.27
-
2v). Selective trifluoromethylation with branched
(
)
was found when DL-thioctic acid used as
Scheme 2. Proposed reaction mechanisms.
In the initial stage of the reaction, disulfides
gradually reduced as the extension of the reaction time. This
might indicated that was an intermediate. Using disulfide to
3 was found and
In conclusion, we developed a convenient trifluoromethylation
reaction of various thiophenols and thiols by using sodium
trifluoromethanesulfinate and iodine pentoxide. The
advantages such as good yields, excellent functional group
tolerance made this transition-metal-free trifluoromethylation
strategy for useful and practical formation of SCF3-containing
compounds. Mechanistic investigation revealed that this
reaction proceeded via a radical pathway.
3
replace thiol and afforded almost the same result (Scheme 1,
equ. 1). According to the contrast experiments, CF3SO2Na, as
well as I2O5 was failed to promote the formation of disulfides 3,
Iodine, which was the residue of CF3SO2Na and I2O5, could be
achieved (equ. 2-4). DMSO was also tested but failed, which
were not shown in Scheme 1. To better understand the
mechanism of this transformation, radical trapping
experiments were carried out. No desired product was
detected in the reaction in the presence of TEMPO (2,2,6, 6-
Acknowledgements
tetramethyl-1-piperidinyloxy)
(3.0
equiv.)
and
1,1-
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
Catalysis Science & Technology
Page 4 of 5
View Article Online
DOI: 10.1039/C5CY01561H
COMMUNICATION
Journal Name
We thank the Fundamental Research Funds for the Central Universities
(30920130111002), National Natural Science Foundation of China (21476116),
Natural Science Foundation of Jiangsu (BK20141394). We also thank the Center for
Advanced Materials and Technology for financial support.
Chem. Soc. 2015, 137, 4164−4172; (d) G.-Y. Yin, I. Kalvet and
F. Schoenebeck, Angew. Chem. Int. Ed. 2015, 54, 6809-6813.
10 (a) F. Baert, J. Colomb, T. Billard, Angew. Chem. Int. Ed. 2012,
51, 10382-10385; (b) T. Bootwicha, X.-G. Liu and M. Rueping,
Angew. Chem. Int. Ed. 2013, 52, 12856-12859; (c) J.-B. Liu, L.-
L. Chu and F.-L. Qing, Org. Lett. 2013, 15, 894-897; (d) C.-F.
Notes and references
Xu, B.-Q. Ma and Q.-L. Shen, Angew. Chem. Int. Ed. 2014, 53
9316-9320; (e) C.-F. Xu and Q.-L. Shen, Org. Lett. 2014, 16
,
,
1
B. Bayarmagnai, C. Matheis, K. Jouvin and L. J. Goossen,
Angew. Chem. Int. Ed. 2015, 54, 5753-5756.
2046−2049; (f) K. Kang, C.-F. Xu and Q.-L. Shen, Org. Chem.
Front. 2014, , 294–297; (g) R. Pluta and M. Rueping, Chem.
1
2
(a) W. C. Holz, J. P. Hieble and R. G. Pendleton,
Psychopharmacology, 1982, 77, 259-267; (b) P. Laczay, G.
Vörös and G. Semjén, Int. J. Parasitol. 1995, 25, 753-756; (c)
T. Silverstone, J. Fincham and J. Br. Plumley, J. Clin.
Eur. J. 2014, 20, 17315-17318; (h) M. Maeno, N. Shibata and
D. Cahard, Org. Lett. 2015, 17, 1990−1993; (i) Q. Wang, F. Xie
and X.-W. Li, J. Org. Chem. 2015, 80, 8361-8366; (j) J. Luo, Z.-
C. Zhu and X.-D. Zhao, Org. Lett. 2015, 17, 3620−3623; (k) H.-
Y. Xiong, T. Besset, D. Cahard and X. Pannecoucke, J. Org.
Chem. 2015, 80, 4204−4212; (l) Q. Wang, Z.-S. Qi, F. Xie and
X.-W. Li, Adv. Synth. Catal. 2015, 357, 355-360; (m) W. Wu,
Pharmacol. 1979, 7, 353-356; (d) F.-C. Shioshinden and F.-C.
shizuoka, JP 96/01055, 1996; (e) G. H. Coombs and J. C.
Mottram, Antimicrob. Agents Chemother. 2001, 45, 1743-
1745; (f) G. Zhao, W. Wan and Z.-H. Zhou, Bioorg. Med.
Chem. Lett. 2003, 13, 3897–3900.
X.-X. Zhang, F. Liang and S. Cao, Org. Biomol. Chem. 2015, 13
6992–6999.
,
3
(a) L. M. Yagupol’skii, Aromatic and Heterocyclic Compounds
with Fluorine-containing Substituents, Naukova Dumka, Kiev,
1988 (in Russian); (b) B. E. Smart, J. Fluorine Chem. 2001,
109, 3–11.
11 (a) F. Hu, X.-X. Shao, D.-H. Zhu, L. Lu and Q.-L. Shen, Angew.
Chem. Int. Ed. 2014, 53, 6105–6109; (b) Y. Li, Z.-S. Ye and M.-
J. Dai, Org. Lett. 2015, 17, 2186−2189; (c) X.-X. Shao, C.-F. Xu,
L. Lu and Q.-L. Shen, J. Org. Chem. 2015, 80, 3012−3021; (d)
B.-Q. Ma, X.-X. Shao and Q.-L. Shen, J. Fluorine Chem. 2015,
171, 73-77.
12 (a) Y.-D. Yang, A. Azuma and N. Shibata, J. Am. Chem. Soc.
2013, 135, 8782−8785; (b) X.-X. Shao, X.-Q. Wang, T. Yang, L.
Lu and Q.-L. Shen, Angew. Chem. Int. Ed. 2013, 52, 3457-
3460; (c) Z.-Y. Huang, Y.-D. Yang and N. Shibata, Org. Lett.
2015, 17, 1094−1097.
4
5
C. Hansch, A. Leo and R. W. Taft, Chem. Rev. 1991, 97, 1-
346.
(a) A. Leo, C. Hansch and D. Elkins, Chem. Rev. 1971, 71, 525–
616; (b) R. Filler, Biomedical Aspects of Fluorine Chemistry,
Kodansha, Tokyo, 1982; (c) L. M. Yagupolskii, A. Y. Ilchenko
and N. V. Kondratenko, Russ. Chem. Rev. 1974, 43, 64–94; (d)
C. Hansch, A. Leo and R. W. Taft, Chem. Rev. 1991, 91, 165–
195.
13 (a) S. Andreades, J. F. Jr. Harris and W. A. Sheppard, J. Org.
Chem. 1964, 29, 898-900; (b) A. Haas, M. Lieb and Y. Zhang,
J. Fluorine Chem. 1985, 29, 297-310; (c) A. A. Kolomeitsev, K.
6
(a) V. N. Boiko, Beilstein J. Org. Chem. 2010,
G. Landelle, A. Panossian, S. Pazenok, J.-P. Vors and F. R.
Leroux, Beilstein J. Org. Chem. 2013, , 2476–2536; (c) A. Tlili
6, 880–921; (b)
9
Y. Chabanenko and Y. L. Yagupolskii, Synthesis, 1994, 2, 145-
and T. Billard, Angew. Chem. Int. Ed. 2013, 52, 6818–6819; (d)
F. Toulgoat, S. Alazet and T. Billard, Eur. J. Org. Chem. 2014,
2415–2428; (e) G. Landelle, A. Panossian and F. R. Leroux,
Current Topics in Medicinal Chemistry, 2014, 14, 941-951; (f)
L.-L. Chu and F.-L. Qing, Acc. Chem. Res. 2014, 47, 1513−1522;
(g) X.-X. Shao, C.-F. Xu, L. Lu and Q.-L. Shen, Acc. Chem. Res.
2015, 48, 1227−1236; (h) X.-H. Xu, K. Matsuzaki and N.
Shibata, Chem. Rev. 2015, 115, 731-764; (i) H.-B. Yang, X.
146; (d) A. Kolomeitsev, M. Médebielle and G.-V.
Röschenthaler, J. Chem. Soc., Perkin Trans. 1, 2000, 2183-
2185.
14 (a) T. Umemoto and S. Ishihara, J. Am. Chem. Soc. 1993, 115
,
2156-2164; (b) A. Harsányi, É.Dorkó and J. Rábai, J. Fluorine
Chem. 2011, 132, 1241-1246.
15 (a) Q.-Y. Chen and J.-X. Duan, J. Chem. Soc., Chem. Commun.
1993, 918–919; (b) C. Chen, L.-L. Chu and F.-L. Qing, J. Am.
Chem. Soc. 2012, 134, 12454−12457; (c) C. Chen, Y. Xie, L.-L.
Chu, R.-W. Wang, X.-G. Zhang and F.-L. Qing, Angew. Chem.
Int. Ed. 2012, 51, 2492–2495; (d) Y.-J. Huang, X. He and Z.-Q.
Weng, Org. Lett. 2014, 16, 3284−3287; (e) M.-G. Rong, X.-Y.
Han and Z.-Q. Weng, Eur. J. Org. Chem. 2014, 5010–5016; (f)
L. Zhai, Y. Li, J. Yin, K. Jin, R. Zhang, X. Fu and C. Duan,
Tetrahedron 2013, 69, 10262–10266.
16 D. Inschauspe, J. B. Sortais, T. Billard and B. R. Langlois,
Synlett. 2003, 233-235.
17 W. Zhong and X.-M. Liu, Tetrahedron Lett. 2014, 55, 4909–
4911.
Fan, Y. Wei and M. Shi, Org. Chem. Front. 2015, 2, 1088–
1093.
7
8
W.-Y. Yin, Z.-F. Wang and Y. Huang, Adv. Synth. Catal. 2014,
356, 2998- 3006.
(a) D. J. Adams, A. Goddard and J. H. Clark, Chem. Commun.,
2000, 987–988; (b) X.-L. Zhu, J.-H. Xu, D.-J. Cheng, X.-Y. Liu
and B. Tan, Org. Lett. 2014, 16, 2192−2195; (c) L.-P. Zhu, G.-
Q. Wang, Z.-Q. Xu and R. Wang, Org. Lett. 2014, 16
,
5390−5393; (d) E. Emer, J. Twilton and V. Gouverneur, Org.
Lett. 2014, 16, 6004−6007; (e) C. Bohnen and C. Bolm, Org.
Lett. 2015, 17, 3011−3013; (f) H. Wu, C. Liu and Q.-Y. Chen,
Angew. Chem. Int. Ed. 2015, 54, 4070-4074; (g) K. Zhang, J.-B.
Liu and F.-L. Qing, Chem. Commun. 2014, 50, 14157-14160;
(h) Q. Lefebvre, E. Fava and M. Rueping, Chem. Commun.
2014, 50, 6617-6619; (i) X. Wang, Y.-J. Zhou and J.-B. Wang,
Eur. J. Org. Chem. 2014, 3093–3096; (j) Y.-J. Huang, H.-H. Li
and Z.-Q. Weng, Eur. J. Org. Chem. 2014, 7324–7328; (k) Q.-
18 (a) J. Hess, S. Konatschnig and G. Gasser, Inorg. Chem. 2014,
53, 3662−3667; (b) G. Danoun, B. Bayarmagnai and L. J.
Goossen, Chem. Sci. 2014, 5, 1312-1316; (c) B. Bayarmagnai,
C. Matheis and L. J. Goossena, Adv. Synth. Catal. 2014, 356
2343-2348.
,
19 (a) G. A. R. Brandt, H. J. Emeléus and R. N. Haszeldine, J.
Chem. Soc. 1952, 2198-2200; (b) B. Langlois, D. Montègre
and N. Roidot, J. Fluorine Chem. 1994, 68, 63-66; (c) T. Billard,
N. Roques and B. R. Langlois, J. Org. Chem. 1999, 64, 3813-
3820; (d) T. Billard, N. Roques and B. R. Langlois, Tetrahedron
Lett. 2000, 41, 3069-3072.
F. Lin, L.i Chen and Z.-Q. Weng, Org. Biomol. Chem. 2014, 12
,
5500–5508; (l) F. Yin and X.-S. Wang, Org. Lett. 2014, 16
,
1128−1131; (m) K.-Y. Ye, X. Zhang, S.-L. You, J. Org.
Chem. 2014, 79, 12106–12110; (n) G. Teverovskiy, D. S. Surry
and S. L. Buchwald, Angew. Chem. Int. Ed. 2011, 50, 7312-
7314.
20 (a) L. Z. Gandel’sman and V. N. Boiko, Ukr. Khim. Zh. 1977, 43
1224-1225; (b) V. I. Popov, V. N. Boiko and L. M. Yagupolskii,
J. Fluorine Chem. 1982, 21, 365-369; (c) L. V. Sokolenko, I. I.
Maletina and Y. L. Yagupolskii, Synlett. 2010, 207-2078.
,
9
(a) C.-P. Zhang and D. A. Vicic, J. Am. Chem. Soc. 2012, 134
183−185; (b) C.-P. Zhang, D. A. Vicic, Chem. Asian J. 2012,
1756-1758; (c) G.-Y. Yin, I. Kalvet and F. Schoenebeck, J. Am.
,
,
7
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
Catalysis Science & Technology
Page 5 of 5
View Article Online
DOI: 10.1039/C5CY01561H
Journal Name
COMMUNICATION
21 (a) M. Tordeux, B. R. Langlois and C. Wakselman, J. Org.
Chem. 1989, 54, 2452-2553; (b) Y. Ye, S. A. Künzi and M. S.
Sanford, Org. Lett. 2012, 14, 4979-4981; (c) A. Deb, S. Manna
and D. Maiti, Angew. Chem., Int. Ed. 2013, 52, 9747-9750; (d)
X.-Y. Jiang and F.-L. Qing, Angew. Chem. Int. Ed. 2013, 52
14177-14180.
,
22 M. Tordeux, C. Francese and C. Wakselman, J. Fluorine Chem.
1989, 43, 27-34
23 R. N. Haszeldine, R. B. Rigby and A. E. Tipping, J. Chem. Soc.
Perkin 1, 1972, 2180-2182.
24 T. Umemoto and A. Ando, Bull. Chem. Soc. Jpn. 1986, 59
447-452.
,
25 (a) Z.-J. Hang, Z.-J. Li and Z.-Q. Liu, Org. Lett., 2014, 16, 3648–
3651; (b) X.-J. Shang, Z.-J. Li and Z.-Q. Liu, Tetrahedron Lett.
2015, 56, 233–235.
26 (a) J.-J. Ma, W.-B. Yi and C. Cai, Org. Biomol. Chem. 2015, 13
,
2890-2894; (b) J.-L. Qian, W.-B. Yi and W. Zhang, Org. Lett.
2015, 17, 1090−1093; (c) W-B. Yi, C. Cai and W. Zhang, Green
Chem., 2012, 14, 3185-3189.
27 (a) P. Bingham, T. Kwok and Z. Zachar, 2008,
US 20080262034; (b) L.-X. Xu, Study on the novel technology
of α-lipoic acid, Zhejiang University (China), 2002.
28 (a) A. G. Larsen, A. H. Holm and K. Daasbjerg, J. Am. Chem.
Soc. 2001, 123, 1723-1729; (b) C. Ji, M. Ahmida, M. Chahma
and A. Houmam, J. Am. Chem. Soc. 2006, 128, 15423-15431;
(c) L. Fang, R.-Y. Tang, P. Zhong and J.-H. Li, Synthesis 2009,
24, 4183–4189; (d) F.-H. Xiao, H. Xie, S.-W. Liu and G.-J.
Deng, Adv. Synth. Catal. 2014, 356, 364-368; (e) P. Katrun, C.
Mueangkaew, M. Pohmakotr, V. Reutrakul, T. Jaipetch, D.
Soorukram and C. Kuhakarn, J. Org. Chem. 2014, 79,
1778−1785; (f) Y.-M. Lin, G.-P. Lu and W.-B. Yi, Org. Lett.,
2015, 17, 3310–3313.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins