A facile method for hydroxytrifluoromethylation of alkenes with Langlois reagent and DMSO

Article abstract of DOI:10.1039/c9gc00886a

A practical hydroxytrifluoromethylation of alkenes using the Langlois reagent as the trifluoromethyl source and DMSO as the oxidant is described. This reaction is mild and operationally simple, without exclusion of either moisture or oxygen, allowing access to a wide range of β-trifluoromethyl alcohols in useful yields. This transformation is environmentally friendly and can be easily scaled up to gram level.

Full text of DOI:10.1039/c9gc00886a

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DOI: 10.1039/C9GC00886A
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ARTICLE
A facile method for hydroxytrifluoromethylation of alkenes with
Langlois reagent and DMSO
Wei-Guo Shen,‡a Qing-Yan Wu,‡a Xing-Yu Gong, Gui-Zhen Aoa and Feng Liu*a,b
Received 00th January 20xx,
Accepted 00th January 20xx
A practical hydroxytrifluoromethylation of alkenes using Langlois reagent as the trifluoromethyl source and
DMSO as the oxidant is described. This reaction is mild and operationally simple, without exclusion of either
moisture or oxygen, allowing access to a wide range of β-trifluoromethyl alcohols in useful yields. This
transformation is environmentally friendly and can be easily scaled up to gram level.
DOI: 10.1039/x0xx00000x
www.rsc.org/
there are a few examples related to hydroxytrifluoromethylation of
alkenes which provides a strategy for direct access to useful β-
trifluoromethyl alcohols (Scheme 1),16 these methods usually
required transition-metal catalysts, expensive trifluoromethylating
reagents, super-stoichiometric amount of strong oxidants, and/or
environmentally unfriendly reagents. In most cases, the trapping of
the resultant key intermediate β-CF3-substituted carbon-centered
radical by oxygen has been proposed as the key step to form the C–
O bond.16a-d The nucleophilic attack of H2O on the β-CF3-substituted
carbocation could also give the corresponding alcohol product.16e
Introduction
Perfluorinated alkyl groups (especially the CF3 group) can deliver
unique biological, chemical and physical properties on organic
molecules that are often desirable for pharmaceuticals,
agrochemicals and materials.1,2 Consequently, synthetic organic
chemists have a long-standing interest in development of new
methodologies for introducing the CF3 group, which permits the
access to trifluoromethylated compounds with structural
diversity.2,3 Notably, a tremendous amount of progress has been
made in radical trifluoromethylation by the use of CF3 radical
precursors, such as CF3I,4 CF3SO2Cl,5 Togni reagent,6 Umemoto
reagent,7 Langlois/Baran reagents (CF3SO2Na,8 (CF3SO2)2Zn9), and
Ruppert-Prakash reagent10 (TMSCF3). Particularly, sodium triflinate
(CF3SO2Na), developed by Langlois and co-workers in 1991,11
represents one of the cheapest and most convenient reagents for
trifluoromethylation.

[CuCF3] from CF3H, B2Pin2, O2 (ref.16a)
Langlois reagent, NMP, PPh3, O2 (ref.16b)



Langlois reagent, MnCl2 4H2O, O2 (ref.16c)


Langlois reagent, BQ, TBHP, O2 (ref.16d)
Umemoto reagent, photocatalyst, hv, H2O (ref.16e)
R2
CF3
CF3SO2Na
R1
Langlois reagent
In view of that alkenes are a class of easily accessible feedstock,
the vicinal difunctionalization of alkenes could serve as one of the
most versatile approaches to various functionalized alkanes by the
formation of two carbon-carbon and/or carbon-heteroatom
bonds.12 In recent years, the radical addition of a trifluoromethyl
group (CF3) to unfunctionalized olefins has emerged as an
important research area.13-16 Among these reports, the vicinal
oxytrifluoromethylation of alkenes provides a useful strategy to
simultaneously introduce a CF3 group and an oxygen atom,14-16 for
example, for the synthesis of -trifluoromethyl ketones14 and other
diverse molecules containing C–CF3 and C–O bonds.15 Although
S
key intermediate
BF4
CF3
CuCF3
Umemoto reagent
previous reports
R2
R2
OH
CF3
R1
O
R1
CF3SO2Na
S
Langlois reagent Me
Me
this work
S




R2
catalyst- and transtion-metal-free
DMSO as mild oxidant
practical and simple reaction conditions
readily scalabe
O
CF3
R1
alkoxysulfonium ion
Scheme 1 Hydroxytrifluoromethylation of alkenes.
a. Jiangsu Key Laboratory of Neuropsychiatric Diseases and Department of
Medicinal Chemistry, College of Pharmaceutical Sciences, Soochow University,
199 Ren-Ai Road, Suzhou, Jiangsu 215123, People’s Republic of China. E-mail:
fliu2@suda.edu.cn
As a low-toxic and inexpensive solvent, dimethyl sulfoxide (DMSO)
has been widely used in organic reactions, especially as an oxidant
in Swern oxidation,17 Kornblum oxidation,18 and formal C–H
activation.19 In most of these reactions, an alkoxysulfonium
b. Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic
Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032,
People’s Republic of China.
Electronic Supplementary Information (ESI) available: Experimental details,
characterization data, and copies of 1H, 13C and 19F NMR spectra for all compounds. intermediate could be formed by activation of sulfoxide. However,
See DOI: 10.1039/x0xx00000x
the transformation of the alkoxysulfonium ions into alcohols is
‡ These authors contributed equally to this work.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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rarely achieved,19b-c but giving ketones as the over-oxidative
products. In continuation of our research interest in radical
trifluoromethylation,20 we herein report a simple and practical
protocol for the synthesis of β-trifluoromethyl alcohols (Scheme 1).
In this reaction, the inexpensive and shelf-stable langlois reagent
was used as the CF3 radical source, and the solvent DMSO not only
played as an oxidant but also acted as an O-source.
substituents on the phenyl ring (2h−i). In the examples of 2c and 2h,
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the reserved bromine and iodine atoms could provide the options
DOI: 10.1039/C9GC00886A
for further cross-coupling. The mono-substituted ethylene
derivative was also suitable for this protocol (2k) though an
over-oxidative -trifluoromethyl ketone byproduct was found. To
demonstrate the synthetic utility of this protocol, a gram-scale
(1 g of 1b) reaction was conducted, providing the desired
product 2b in 63% yield.
a
Results and discussion
Table 2 Scope of hydroxytrifluoromethylation of unactivated alkenes
R2
OH
CF3SO2Na (2 equiv)
R2
R1
CF3
R1
TFA (2 equiv)
DMSO, 60 °C
7-72 h, under air
a,b
Table
1
Scope of hydroxytrifluoromethylation of styrenes
3
4
R2
OH
R2
CF3SO2Na (2 equiv)
CF3
O
OH
O
O
OH
OH
CF3
CF3
CF3
TFA (1 equiv)
DMSO, 40 °C
10-72 h, under air
O
O
O
R1
R1
F
Cl
2
1
4b, 89%, 48 h
4c, 95%, 18 h
4a, 82%, 48 h
O
O
OH
O
O
Cl
OH
OH
OH
OH
O
O
OH
CF3
CF3
CF3
CF3
CF3
CF3
Cl
Br
F3C
Cl
4d, 80%,48 h
4e
4f, 84%, 18 h
, 93%, 18 h
2b, 69%, 37 h (63%, 40 h)c
2c, 75%, 10 h
2a
, 61%, 72 h
OH
OH
F
OH
O
O
O
OH
O
OH
OH
CF3
CF3
S
CF3
CF3
CF3
CF3
O
O
O
O2N
MeO
4h, 64%, 7 h
4g
, 91%, 7 h
4i
, 84%, 24 h
2e, 75%, 35 h
2f
, 56%, 12 h
OH
2d, 54%, 18 h
O
Cl
OH
OH
OH
OH
OH
BnO
CF3
CF3
O
CF3
N
O
CF3
CF3
Cl
CF3
O
O
OMe
I
4l
, 46%, 43 h
4j
, 65%, 48 h
4k
, 69%, 72 h
2g
, 49%, 11 h
2i
, 49%, 17 h
2h
, 65%, 13 h
O
O
OH
3
OH
CF3
OH
CF3
O
CF3
OH
OH
Cl
N
Cl
CF3
CF3
Ts
O
4o, 55%, 48 h
4m, 38%, 60 h
4n, 47%, 38 h
Ph
O
2k
, 35%, 22 h
2j
O
O
Cl
OH
, 48%, 36 h
OH
CF3
N
O
CF3
3
3
aReaction conditions: 1a (0.8 mmol), CF3SO2Na (1.6 mmol), TFA (0.8 mmol),
DMSO (4 mL), 40 oC, under air, 10- 72 h. bIsolated yield. c1b (1.0 g, 6.6 mmol)
4q, 63%, 72 h
4p, 54%, 48 h
aReaction conditions: 1a (0.2 mmol), CF3SO2Na (0.4 mmol), TFA (0.4 mmol),
DMSO (1 mL), 60oC, under air, 7- 72 h. bIsolated yield.
We speculated that CF3 radical could be generated by oxidation
of the Langlois reagent with DMSO. To verify the hypothesis,
we set out to investigate the reaction using -methylstyrene
1a as the acceptor to capture the CF3 radical. As shown in Table
1, the desired β-trifluoromethyl alcohol 2a was obtained in 61%
yield. Encouraged by this result, a series of styrene derivatives
were tested under air to determine the generality. As shown in
Table 1, -methylstyrenes bearing either electron-donating or
-withdrawing substituents on the aryl ring could be employed
as CF3 radical acceptors to yield the corresponding products 2b-
Next, we examined the scope of the unactivated alkenes. As
revealed in Table 2, a broad range of trifluoromethylated products
with various functional groups were readily furnished in moderate
to excellent yields (4a-q). For this reaction, higher reaction
temperature was required compared to the reaction of the styrene
substrates in Table 1. It is of note that the electron-deficient
alkene 3l and geminally disubstituted alkene 3m were both
employed well in the reaction, affording the desired products
in reasonable yields (4l-m). With respect to mono-substituted
j
in moderate to good yields. A range of functional groups,
such as halogen, methoxy, and nitro substituents were well
tolerated in this reaction. Notably, the efficiency of this
transformation was not impeded by the steric effect of ortho
alkenes, we found that the reaction also proceeded smoothly (4n-q)
2 | J. Name., 2012, 00, 1-3
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though it led to lower chemical yields compared to that of the 1,1-
disubstituted alkenes. However, when extending this protocol to
internal alkene, the reaction gave an inseparable product mixture.
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R2
DOI: 10.1039/C9GC00886A
R2
SET
R1
CF3SO2Na
CF3
CF3
R1
-e, -SO2
Control experiments were performed to gain more mechanistic
insights into the reaction (Scheme 2). With TEMPO ((2,2,6,6-
tetramethylpiperidin-1-yl)oxyl) as radical scavenger, the reaction
led to no desired product 4c formation but gave TEMPO-CF3 as the
product (Scheme 2, eq 1). It was found that the absence of oxygen
(from air) could also provide the desired product 4a in 84% yield (eq
2). In addition, the use of dry DMSO under TFA-free conditions
yielded the desired product 4q as well though much higher reaction
temperature was required for the reaction (eq 3). In order to
confirm the fact that the introduced oxygen atom of the products
was from DMSO, an isotopic labelling experiment using H2O18 was
conducted (eq 4). As might be expected, the result indicated that
the formation of an alkoxysulfonium intermediate could be the
dominated pathway.
A
S
R2
SET
-e
DMSO
R2
O
2 or 4
CF3
CF3
R1
R1
B
C
Scheme 3 Proposed mechanism.
Conclusions
In conclusion, we have developed a mild and practical method for
the hydroxytrifluoromethylation of alkenes using the langlois
reagent as the CF3 radical source and DMSO as the oxidant, oxygen
source, and solvent. This redox reaction demonstrates a broad
substrate scope and good functional group tolerance,
affording various β-trifluoromethyl alcohols. Further studies on
the synthetic applications of this protocol in medicinal and
agrochemical fields are underway in this group.
O
standard conditions
N
O
4c
+
(1)
(2)
O
TEMPO (2 equiv), 25 h
not detected
CF3
Cl
3c
52%
O
OH
O
CF3SO2Na (2 equiv)
CF3
O
O
O
TFA (2 equiv)
DMSO, 60 °C
under argon, 52 h
Conflicts of interest
There are no conflicts to declare.
3a
4a
, 84%
O
CF3SO2Na (2 equiv)
N
CF3
(3)
Acknowledgements
N
OH
, 48%
dry DMSO, 90 °C
under argon, 70 h
O
Financial support from the Natural Science Foundation of the
Jiangsu Higher Education Institutions of China (Grant No.
18KJA350001), the National Natural Science Foundation of
China (Grant No. 21302134), and the Priority Academic
Program Development of the Jiangsu Higher Education
Institutes (PAPD).
O
4q
3q
O
N
CF3
16OH
O
CF3SO2Na (2 equiv)
H2O18 (10 equiv)
O
O
+
(4)
N
dry DMSO, 90 °C
under argon, 70 h
3q
O
N
CF3
18OH
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O
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Green Chemistry
View Article Online
DOI: 10.1039/C9GC00886A
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catalyst- and transtion-metal-free
DMSO as mild oxidant
practical and simple reaction conditions
readily scalabe
CF3SO2Na
R2
R2 OH



CF3
R1
O
S
R1
Me
Me
A simple and mild protocol is developed for the synthesis of β-trifluoromethyl alcohols from
alkenes.