Trifluoromethylthiolative 1,2-difunctionalization of alkenes with diselenides and AgSCF3

Article abstract of DOI:10.1039/c9cc00815b

An efficient regioselective difunctionalization of alkenes via trifluoromethylthiolation has been accomplished employing diaryl diselenide and AgSCF₃ in the presence of BF₃·OEt₂. Various substituted 1,2-dichalcogenated products having the SCF₃ moiety were synthesized in good to excellent yields under mild conditions. The preliminary mechanistic investigation revealed the possible reaction pathway and unique combination of diselenide and AgSCF₃ for successful transformation.

Full text of DOI:10.1039/c9cc00815b

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DOI: 10.1039/C9CC00815B
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Trifluoromethylthiolative 1,2-Difunctionalization of Alkenes with
Diselenides and AgSCF3
Received 00th January 20xx,
Accepted 00th January 20xx
Perumal Saravanan and Pazhamalai Anbarasan*
DOI: 10.1039/x0xx00000x
www.rsc.org/
An efficient regioselective difunctionalization of alkenes via other functional groups, such as amine, amide, acid, etc.,7 is a
trifluoromethylthiolation have been accomplished employing useful concept to the synthesis of trifluoromethylthiolated
diaryl diselenide and AgSCF3 in the presence of BF3·OEt2. Various molecules, which could provide the excellent opportunity for
substituted 1,2-dichalcogenated products having SCF3 moiety medicinal chemists in the drug evolution. Billard and co-
were synthesized in good to excellent yield under mild conditions. workers reported for the first time trifluoromethylthiolative
The preliminary mechanistic investigation revealed the possible functionalization
of
alkenes
using
electrophilic
reaction pathway and unique combination of diselenide and trifluoromethylthiolating reagents.8 Subsequently, numerous
AgSCF3 for successful transformation.
methods9 were documented employing electrophilic
trifluoromethylthiolating reagents (Scheme 1a). However, use
of nucleophilic trifluoromethylthiolating reagents is rather
limited.10 For instance, the group of Wang10a and Qing10d
utilized AgSCF3 in combination with superstiochiometric
amount of persulfate for the difunctionalization of alkenes.
Wang and co-workers10b utilized the substoichiometric amount
of copper acetate and AgSCF3. On the other hand, the
combination of AgSCF3 and trichloroisocyanuric acid was
exploited by Yang and co-workers10c. However, to the best of
our knowledge, difunctionalization of the alkene with
nucleophilic AgSCF3 in the absence of metal catalyst or oxidant
was not documented in the literature. Thus, we envisioned an
arylselenative trifluoromethylthiolation of alkenes with diaryl
diselenide and nucleophilic AgSCF3 for the synthesis of 1,2-
Fluorinated molecules have found widespread application in
various fields. Notably, significant number of drugs in the
pharmaceuticals and agrochemicals contain at least one
fluorine atom/group in the form of -F, -CF3, -SCF3, and -SOCF3.1
Recently, trifluoromethylthio (-SCF3) containing organic
molecules gained significant attention, due to its unique
properties such as high lipophilicity, bioavailability, and
metabolic stability. The representative examples of -SCF3
containing drug molecules include toltrazuril, cefazaflur,
fipronil, and etc. Thus, the development of an elegant strategy
for the construction of trifluoromethylthiolated molecules has
been continuing interest in organic synthesis and other fields.2
Consequently, enormous efforts have been dedicated to the
development of various strategies for the construction of
trifluoromethylthiolated compounds such as F-exchange,3 and
dichalcogenated
compounds,
where
the
potential
intermediate ArSeSCF3 might afford the expected product in
the presence of Lewis acids (Scheme 1b). We herein disclose
an elegant arylselenative trifluoromethylthiolation of
substituted alkenes.
4
5
direct introduction of -CF3 and -SCF3 groups. Among them,
direct trifluoromethylthiolation, using electrophilic or
nucleophilic ‘SCF3’ reagents, is the most efficient and viable
strategy in the synthesis of trifluoromethyl sulfides via the
direct construction of C-SCF3 bond.
a) Difunctionalization of alkene with 'SCF3' reagent
H+, 'SCF3' reagent
SCF3
On the other hand, difunctionalization of readily accessible
substituted alkenes with electrophiles and nucleophiles is an
efficient multi-component approach for the synthesis of
structurally complex frameworks.6 In this context, the
incorporation of trifluoromethylthio (-SCF3) group along with
R1
Nu
w/wo 'Se-cat.'
R1

Nu
R2
Nu = Cl, CF3COO
RSO3, OH, NR2
R2
AgSCF3, Oxidant
SCF3
b) Present work!
R1
(ArSe)2
SeAr
LA
R1

R2
R2
AgSCF3
· dichalcogenation · operationally simple
a. Department of Chemistry, Indian Institute of Technology Madras, Chennai-
600036, India. Email: anbarasansp@iitm.ac.in. webpage:
https://home.iitm.ac.in/anbarasansp/
Scheme 1. Trifluoromethylthiolative difunctionalization of alkenes.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
Initially, the difunctionalization of styrene 1a with diphenyl
diselenide 2a and AgSCF3 was chosen as a model reaction.
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Initial screening of Lewis acids suggested that BF3·Et2O was the corresponding difunctionalized product 3d, 3e, 3f, and 3g in
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DOI: 10.1039/C9CC00815B
most suitable promoter of the expected difunctionalization excellent yields. The reaction of 2-vinylnaphthalene also
(see Supporting Information). Thus, the reaction of 1 equiv of furnished the similar product 3h in 73% yield. Also, sterically
1a with 1 equiv of both 2a and AgSCF3 in the presence of 1 hindered 2-methylstyrene underwent smooth reaction to give
equiv of BF3·Et2O in acetonitrile at room temperature afforded 3i in 88% yield. However, actively coordinating cyano and
the expected product 3a in 44% yield after 12 h. Having NMe2 group substituted styrenes do not afford
identified the formation of expected product 3a, various difunctionalized products.
conditions were examined to improve the yield of 3a. Thus,
different solvents such as DCM, DCE, CH3CN, etc. were
screened at room temperature to enhance the transformation
(Table 1, entries 1-5). Among them, acetonitrile only showed
better yield.
SCF3
(PhSe)2
AgSCF3, BF3·OEt2
CH3CN, rt, 1 h
SePh

R
2a
R
1
3
SCF3
SCF3
SePh
SCF3
SePh
SePh
Table 1. Difunctionalization of styrene 1a with diphenyldiselenide 2a and AgSCF3:
3c: 75%
3b: 92%
3a: 90%
SCF3
Optimizationa
Me
tBu
SCF3
SCF3
SePh
SePh
SePh
SCF3
Cl
AgSCF3
BF3·OEt2
(PhSe)2
SePh

3d: 82%
MeO
Br
3f: 84%
3e: 76%
Br
2a
OMe
1a
SCF3
CH3
SCF3
SCF3
Solvent, rt, 1 h
3a
SePh
SePh
SePh
Entry
1
2
3
4
5
6
7
8
BF3·OEt2 (equiv)
Solvent
CH3CN
DCE
DCM
THF
Yield (%)b
44
<5%
20
20
<5%
40
3g: 72%
3h: 73%
3i: 88%
1.0
1.0
1.0
1.0
1.0
2.0
0.5
0.2
1.0
1.0
1.0
Scheme 2. Difunctionalization of substituted styrenes
Further to confirm the regioselectivity of difunctionalized
product, oxidative elimination of -SePh was envisioned. Thus,
the isolated difunctionalized compound 3h was treated with
m-CPBA in DCM at room temperature. Interestingly, the
formation of α -(trifluoromethylthio)vinylnaphthalene 4 was
observed in 95% yield (eq 1). Formation of 4 further confirms
that SCF3 and SePh were attached at α-carbon and β-carbon,
respectively.
DMF
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
26
24
48
20
9c
10d
11e
96
a
Reaction conditions: Styrene 1a (0.24 mmol, 1.0 equiv), 2a (0.24 mmol, 1.0
SCF3
SCF3
b
equiv), AgSCF3 (0.24 mmol, 1.0 equiv), BF3·OEt2, Solvent (0.24 M), rt, 1 h.
Isolated yield, c at 50 °C, d 0.5 equiv of styrene, e 2.0 equiv of styrene.
m-CPBA
SePh
(1)
DCM, rt, 30 min
3h
4: 95%
Next, increasing the BF3·OEt2 to 2.0 equivalents doesn't show
much improvement in the yield, but decreasing the
equivalents of BF3·OEt2 shows drastic reduction in the yield
(Table 1, entries 6 and 7). Subsequently, the focus was
directed to study the effect of temperature. Increasing the
reaction temperature to 50 °C with one equivalent of BF3·OEt2
furnished the product 3a in only comparable yield (Table 1,
entry 9). On the other hand, altering the equivalents of styrene
showed a drastic change in the outcome (Table 1, entry 10 and
11). The best yield of 96% for the formation of 3a was
observed with 2.0 equivalents of styrene in the presence of
one equivalent of 2a, AgSCF3 and BF3·OEt2 at room
temperature after 1 h, the same condition was used for the
further studies.
Having achieved the suitable conditions for the tri-component
difunctionalization of 1a for the synthesis of the highly
functionalized molecule, the scope, and generality of the
transformation was investigated. For example, 4-alkyl
(methyl/tert-butyl) substituted styrenes gave the product 3b
and 3c in 92% and 75% yield, respectively (Scheme 2).
Similarly, electron donating group (3,4-dimethoxy) and
halogen (bromo/chloro) substituted styrene was also well
tolerated under the optimized conditions to afford the
After the successful demonstration of the generality of
substituted styrenes, scope and limitations of other
substituted alkenes were examined. Gratifyingly, replacement
of styrene with 1,4-dihydronaphthalene under the optimized
conditions afforded the difunctionalized product 6a in 77%
yield (Scheme 3). Similarly, other cyclic alkenes such as
cyclopentene, cyclohexene, and cycloheptene also underwent
smooth reaction to afford corresponding difunctionalized
product 6b, 6c, and 6d in 65, 75 and 77% yield, respectively.
Also, difunctionalization of simple terminal alkene such as
allylbenzene was achieved in good yield. Consequently, various
substituted homoallylic ethers were subjected under the
optimized conditions to afford difunctionalized product 6f-6i in
good to excellent yield. It is important to note that reactive
functional groups such as formyl, sulfenyl and iodo moieties
were well tolerated under the optimized conditions.
Subsequently, various substituted diaryl diselenides11 were
subjected for the difunctionalization of styrene under the
optimized conditions. Methyl, methoxy, and halogen
substituted diaryl diselenides gave the corresponding
difunctionalized products 3j, 3k, 3l, 3m and 3p in 70, 81, 51, 55
and 79% yields, respectively (Scheme 4).
2 | J. Name., 2012, 00, 1-3
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expected product. A detectable amount of difunctionalized
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SCF3
SePh
19
product 3k was observed in F NMRDuOpI:o1n0.1a0d39d/iCti9oCnC0o0f81a5nB
(PhSe)2
AgSCF3
BF3·OEt2

additive such as silver salt and NaOTs (Scheme 5b).
2a
6
5
CH3CN, rt, 1 h
a)
Se
Se
SCF3
SePh
6d: 77%
SCF3
SePh
SCF3
SePh
SCF3
SePh
AgSCF3
SCF3
2
CH3CN, rt, 30 min
MeO
b)
2k
MeO
7: 84%
6a: 77%
6b: 65%
6c: 75%
SCF3
Se
Additive:
AgSbF6
AgOAc
NaOTs
Additive
SCF3
3k
~10 % yield
Styrene, BF3·OEt2
CH3CN, rt, 30 min
SCF3
SCF3
SePh
MeO
7
O
SePh
SePh
TsO
c)
R = H, 3a
SCF3
6g: 52%
6e: 65%
6f: 79%
R = OMe, 3k
Se
Se
O
Ph
Se
I
SCF3
SCF3
Ag
SCF3
H
Styrene
BF3·OEt2
CH3CN, rt
30 min
SePh
R
7
SePh
O
6i: 60%
MeO
+
O
6h: 64%
R = H, 7a
R = OMe, 7
SCF3
Se
R
Se
2
Scheme 3. Difunctionalization of substituted alkenes
R = H, 2a
R = OMe, 2k
R
Identified by GCMS
Interestingly, sterically hindered o-methoxy substituted diaryl
diselenide furnished the corresponding product 3n in good
yield. Acid-sensitive acetal containing difunctionalized product
3o was synthesized in 73% yield from the corresponding diaryl
diselenide.
Scheme 5. Control experiments
However, the formation of 7, via treatment of diselenide and
AgSCF3 in CH3CN in the presence of BF3·OEt2, followed by the
addition of styrene afforded the expected difunctionalized
product 3k in good yield. These studies suggested that
ArSeSCF3 might not be the intermediate of developed
transformation and the formed ArSeSCF3 might exist in
equilibrium with AgSCF3 and diaryl diselenide. Further to
confirm the reversible formation of ArSeSCF3 from AgSCF3 and
SCF3
(ArSe)2
AgSCF3
BF3·OEt2
SeAr

2
1a
3
CH3CN, rt, 1 h
SCF3
SCF3
SCF3
Se
Se
Se
Ph
Ph
Me
Ph
Ph
diselenides, compound
7
was treated with silver
3j: 70%
OMe
OMe
phenylselenate and styrene in the presence of BF3·OEt2.
Interestingly, a mixture of difunctionalized product 3a and 3k
was observed along with -SCF3 exchanged product 7, 7a and
possible diselenides 2a and 2k in GCMS and 19F NMR analysis
(Scheme 5c). This –SCF3 exchange could be explained via initial
formation of diselenide followed by reaction with AgSCF3. All
the above observations confirm the possible reversible
reaction between diselenide and AgSCF3.
3a: 90%
3k: 81%
SCF3
SCF3
SCF3
Se
Se
Se
Ph
Ph
F
3n: 55%
Cl
3l: 51%
3m: 55%
SCF3
SCF3
Se
Se
OMe
O
O
Ph
Ph
3o: 73%
3p: 79%
Scheme 4. Difunctionalization of styrene with diaryl diselenides 2 and AgSCF3
AgSCF3, CH3CN
SCF3
rt, 1 h then
Styrene
X
After the successful demonstration of BF3·OEt2 induced
difunctionalization of styrenes and alkenes with diaryl
diselenides and AgSCF3, the formation of potential
intermediate and plausible reaction mechanism of the
developed transformation was investigated. 19F NMR analysis
of optimized reactions showed an additional singlet at δ –45.3
along with AgSCF3 and difunctionalized product 3a.
Subsequent, GCMS analysis revealed the formation of possible
(PhX)2
Ph
SCF3
XPh
Ph
BF3·OEt2, 1 h
X = S; Not observed
X = Se; 84% (5 min)
X = Te; 92% (5 min)
X = S; No reaction
X = Se; 96%
X = Te; No reaction
Scheme 6. Reaction of styrene with different dichalcogenides and AgSCF3
Furthermore, the difunctionalization was performed with
other dichalcogenides in place of diselenide. Unfortunately,
both diphenyl disulfide and diphenyl ditelluride did not afford
the expected product (Scheme 6). Further analysis of the
reaction mixture suggested the possible reasons that the
disulfides failed to get activated due to the high bond energy
of S-S bond and no availability of ditelluride due to the rapid,
irreversible formation of PhTeSCF3. Thus, based on the
observed regioselectivity and mechanistic investigation, in the
present strategy diselenide and AgSCF3 acted as electrophilic -
SeAr source and nucleophilic –SCF3 source, respectively.
intermediate
(phenylselanyl)
(trifluoromethyl)sulfane
(PhSeSCF3) from the corresponding diaryl diselenide and
AgSCF3.
Consequently,
((4-methoxyphenyl)selanyl)-
(trifluoromethyl)sulfane
7
was synthesized from bis(4-
methoxyphenyl) diselenide 2k and AgSCF3 in acetonitrile in
84% yield (Scheme 5a).12 After the successful synthesis of 7,
the reactivity of 7 with styrene was investigated under the
optimized conditions. The initial reaction of styrene 1a with 7
in the presence of BF3·OEt2 in CH3CN didn't afford the
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Gruenberg and L. J. Goossen, Chem. Sci., 2014, 5, 1312; f) M.
Based on the mechanistic study, the possible pathway for the
difunctionalization of alkene was proposed as shown in
Scheme 9. Initially, diphenyl diselenide 2a and AgSCF3 will
convert into 7a, which exists in equilibrium with 2a and
AgSCF3. The remaining diselenide on reaction with styrene in
the presence of BF3·OEt2 would afford the episelenonium
intermediate A. Subsequent, regioselective ring opening of
V. Riofski, A. D. Hart and D. A. Colby, Org. LeVtite.w, A2r0tic1le3O, n1lin5e,
DOI: 10.1039/C9CC00815B
208; g) J.-J. Ma, W.-B. Yi, G.-P. Lu and C. Cai, Catal. Sci.
Technol., 2016, 6, 417.
5
a) G. Yin, I. Kalvet, U. Englert and F. Schoenebeck, J. Am.
Chem. Soc., 2015, 137, 4164; b) C. Matheis, V. Wagner and L.
J. Goossen, Chem. –Eur. J., 2015, 22, 79; c) A. B. Durr, G. Yin,
I. Kalvet, F. Napoly and F. Schoenebeck, Chem. Sci., 2016, 7,
1076; d) J.-B. Liu, X.-H. Xu, Z.-H. Chen and F.-L. Qing, Angew.
Chem., Int. Ed., 2014, 54, 897; e) P. Zhu, X. He, X. Chen, Y.
You, Y. Yuan and Z. Weng, Tetrahedron, 2014, 70, 672; f) Y.
Huang, X. He, H. Li and Z. Weng, Eur. J. Org. Chem., 2014,
2014, 7324; g) Y.-D. Yang, A. Azuma, E. Tokunaga, M.
Yamasaki, M. Shiro and N. Shibata, J. Am. Chem. Soc., 2013,
135, 8782; h) A. Ferry, T. Billard, E. Bacque and B. R. Langlois,
J. Fluorine Chem., 2012, 134, 160; i) S. Alazet, L. Zimmer and
T. Billard, Angew. Chem., Int. Ed., 2013, 52, 10814; j) T.
Bootwicha, X. Liu, R. Pluta, I. Atodiresei and M. Rueping,
Angew. Chem., Int. Ed., 2013, 52, 12856; k) X. Wang, T. Yang,
X. Cheng and Q. Shen, Angew. Chem., Int. Ed., 2013, 52,
12860; l) S. Alazet, L. Zimmer and T. Billard, Chem. –Eur. J.,
2014, 20, 8589.
a) R. I. McDonald, G. Liu and S. S. Stahl, Chem. Rev., 2011,
111, 2981; b) M. R. Heinrich, Chem. –Eur. J., 2009, 15, 820; c)
H. Egami and M. Sodeoka, Angew. Chem., Int. Ed., 2014, 53,
8294; d) Y. A. Cheng, W. Z. Yu and Y.-Y. Yeung, Org. Biomol.
Chem., 2014, 12, 2333; e) X.-W. Lan, N.-X. Wang and Y. Xing,
Eur. J. Org. Chem., 2017, 2017, 5821; f) Y. Shimizu and M.
Kanai, Tetrahedron Lett., 2014, 55, 3727; g) K. H. Jensen and
M. S. Sigman, Org. Biomol. Chem., 2008, 6, 4083; h) J.-S.
Zhang, L. Liu, T. Chen and L.-B. Han, Chem. Asian J., 2018, 13,
2277; i) S. R. Chemler, Org. Biomol. Chem., 2009, 7, 3009; j)
T. Besset, T. Poisson and X. Pannecoucke, Chem. –Eur. J.,
2014, 20, 16830; k) E. Merino and C. Nevado, Chem. Soc.
Rev., 2014, 43, 6598.
episelenonium ion
A with AgSCF3 would furnish the
difunctionalized product 3. Even though the concentration of
AgSCF3 is less at equilibrium but the overall reaction yield was
satisfactory, because of the reversible reaction between
AgSCF3 and diphenyl diselenide.
Scheme 9. Plausible mechanism
6
In conclusion, we have developed an efficient regioselective
difunctionalization of alkenes with diaryl diselenide and AgSCF3
in the presence of BF3·OEt2 as an activator. The developed
reaction tolerates various functional groups and allows the
synthesis of diverse 1,2-dichalcogenated products having a
trifluoromethylthio moiety in good to excellent yield. The
preliminary mechanistic investigation revealed the possible
reaction pathway and unique combination of diselenide and
AgSCF3 for successful transformation.
We thank Indian Institute of Technology Madras for financial
support. P.S. thanks CSIR, New Delhi for a fellowship.
7
a) J. Sheng, C. Fan and J. Wu, Chem. Commun., 2014, 50,
5494; b) S. Pan, H. Li, Y. Huang, X.-H. Xu and F.-L. Qing, Org.
Lett., 2017, 19, 3247.
A. Ferry, T. Billard, B. R. Langlois and E. Bacqué, Angew.
Chem., Int. Ed., 2009, 48, 8551.
Conflicts of interest
There are no conflicts to declare.
8
9
a) J. Luo, Z. Zhu, Y. Liu and X. Zhao, Org. Lett., 2015, 17, 3620;
b) Y. Yang, X. Jiang and F.-L. Qing, J. Org. Chem., 2012, 77,
7538; c) C.-C. Xi, Z.-M. Chen, S.-Y. Zhang and Y.-Q. Tu, Org.
Lett., 2018, 20, 4227; d) L. Jiang, T. Ding, W.-b. Yi, X. Zeng
and W. Zhang, Org. Lett., 2018, 20, 2236; e) X. Liu, Y. Liang, J.
Ji, J. Luo and X. Zhao, J. Am. Chem. Soc., 2018, 140, 4782; f) Y.
Jia, H. Qin, N. Wang, Z.-X. Jiang and Z. Yang, J. Org. Chem.,
2018, 83, 2808; g) Z. Zhu, J. Luo and X. Zhao, Org. Lett., 2017,
19, 4940; h) J. Luo, Y. Liu and X. Zhao, Org. Lett., 2017, 19,
3434; i) P. Zhang, M. Li, X.-S. Xue, C. Xu, Q. Zhao, Y. Liu, H.
Wang, Y. Guo, L. Lu and Q. Shen, J. Org. Chem., 2016, 81,
7486; j) C. Xu and Q. Shen, Org. Lett., 2015, 17, 4561; k) J.
Luo, Q. Cao, X. Cao and X. Zhao, Nature Communications,
2018, 9, 527; l) Y. Li, T. Koike and M. Akita, Asian J. Org.
Chem., 2016, 6, 445; m) G. Dagousset, C. Simon, E. Anselmi,
B. Tuccio, T. Billard and E. Magnier, Chem. –Eur. J., 2017, 23,
4282; n) H. Li, C. Shan, C.-H. Tung and Z. Xu, Chem. Sci., 2017,
8, 2610; o) X. Liu, R. An, X. Zhang, J. Luo and X. Zhao, Angew.
Chem., Int. Ed., 2016, 55, 5846.
Notes and references
1
a) J. Wang, M. Sánchez-Roselló, J. L. Aceña, C. del Pozo, A. E.
Sorochinsky, S. Fustero, V. A. Soloshonok and H. Liu, Chem.
Rev., 2014, 114, 2432; b) S. Purser, P. R. Moore, S. Swallow
and V. Gouverneur, Chem. Soc. Rev., 2008, 37, 320.
a) F. Toulgoat, S. b. Alazet and T. Billard, Eur. J. Org. Chem.,
2014, 2014, 2415; b) X.-H. Xu, K. Matsuzaki and N. Shibata,
Chem. Rev., 2015, 115, 731; c) X. Shao, C. Xu, L. Lu and Q.
Shen, Acc. Chem. Res., 2015, 48, 1227; d) H. Zheng, Y. Huang
and Z. Weng, Tetrahedron Lett., 2016, 57, 1397; e) S. Barata-
Vallejo, S. Bonesi and A. Postigo, Org. Biomol. Chem., 2016,
14, 7150.
2
3
4
a) T. Umemoto and S. Ishihara, J. Fluorine Chem., 1998, 92,
181; b) B. Gutmann, D. Obermayer, B. Reichart, B.
Prekodravac, M. Irfan, J. M. Kremsner and C. O. Kappe,
Chem. –Eur. J., 2010, 16, 12182; c) E. A. Nodiff, S. Lipschutz,
P. N. Craig and M. Gordon, J. Org. Chem., 1960, 25, 60; d) B.
R. Langlois, T. Billard, J.-C. Mulatier and C. Yezeguelian, J.
Fluorine Chem., 2007, 128, 851.
a) V. G. Koshechko, L. A. Kiprianova and L. I. Fileleeva,
Tetrahedron Lett., 1992, 33, 6677; b) A. Harsányi, É. Dorkó,
Á. Csapó, T. Bakó, C. Peltz and J. Rábai, J. Fluorine Chem.,
2011, 132, 1241; c) I. Kieltsch, P. Eisenberger and A. Togni,
Angew. Chem., Int. Ed., 2007, 46, 754; d) N. J. W. Straathof,
B. J. P. Tegelbeckers, V. Hessel, X. Wang and T. Noel, Chem.
Sci., 2014, 5, 4768; e) G. Danoun, B. Bayarmagnai, M. F.
10 a) F. Yin and X.-S. Wang, Org. Lett., 2014, 16, 1128; b) L. Zhu,
G. Wang, Q. Guo, Z. Xu, D. Zhang and R. Wang, Org. Lett.,
2014, 16, 5390; c) H. Xiang and C. Yang, Org. Lett., 2014, 16,
5686; d) S. Pan, Y. Huang, X.-H. Xu and F.-L. Qing, Org. Lett.,
2017, 19, 4624.
11 Z. Li, F. Ke, H. Deng, H. Xu, H. Xiang and X. Zhou, Org. Biomol.
Chem., 2013, 11, 2943.
12 M. Jereb and D. Dolenc, RSC Adv., 2015, 5, 58292.
4 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C9CC00815B
Graphical Abstract
Trifluoromethylthiolative 1,2-Difunctionalization of Alkenes with Diselenides and
AgSCF3
Perumal Saravanan and Pazhamalai Anbarasan*
· up to 92% yield
· 26 examples
SCF3
(ArSe)2, AgSCF3
CH3CN, rt, 1 h
SeAr
R
· good FG tolerance
· mild conditions
R