Catalyst-Free Hydroxytrifluoromethylation of Alkenes UsingIodotrifluoromethane

Article abstract of DOI:10.1002/cjoc.201900087

The importance of CF₃-containing molecules in pharmaceuticals, agrochemicals and materials intrigues the intense interest in synthetic methodology of these compounds. With a purpose to enrich trifluoromethylation methodology, we carefully exami

Full text of DOI:10.1002/cjoc.201900087

Accepted Article
Title: Catalyst-free Hydroxytrifluoromethylation of Alkenes Using
Iodotrifluoromethane
Authors: Zhaoben Su, Yong Guo,* Qing-Yun Chen,* Zhi-Gang Zhao,* Bao-Yi Nian
This manuscript has been accepted and appears as an Accepted Article online.
This work may now be cited as: Chin. J. Chem. 2019, 37, 10.1002/cjoc.201900087.
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Catalyst-free Hydroxytrifluoromethylation of Alkenes Using
Iodotrifluoromethane
Zhaoben Sua, Yong Guob,* Qing-Yun Chenb,*, Zhi-Gang Zhaoa,*, Bao-Yi Nianc
aCollege of Chemistry & Environment Protection Engineering, Southwest Minzu University, Chengdu 610041
bKey Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, and University of Chinese Academy
of Sciences, 345 Lingling Road, Shanghai 200032
cSanming Institute of Fluorochemical Industry, Sanming University, Sanming 365004
Email: yguo@sioc.ac.cn.; chenqy@sioc.ac.cn; zzg63129@163.com
Cite this paper: Su, Z., Guo, Y., Chen, Q., Zhao, Z., Nian, B., Chin. J. Chem. 2019, 37, XXX—XXX. DOI: 10.1002/cjoc.201900XXX
The importance of CF3-containing molecules in pharmaceuticals, agrochemicals and materials intrigues the intense interest in synthetic
methodology of these compounds. With a purpose to enrich trifluoromethylation methodology, we carefully examined the substrate
scope of hydroxytrifluoromethylation of alkenes using iodotrifluoromethane, and the reaction provided β-trifluoromethyl alcohols in
good yields under extremely mild conditions without catalysts. We found that our reaction can be applied to not only styrenes but also
to various aliphatic alkenes with excellent selectivity; no ketones were detected in most of our cases. Another feature of our discovery is
“simple”. The reaction was carried out in air, irradiated by visible light, at room temperature and most importantly no catalyst was
needed. A solution of CF3I in DMSO was used as the facile trifluoromethylating reagent, which simplified the utilization of gaseous CF3I.
Based on 19F NMR spectroscopy, we observed a halogen bond between CF3I and tertiary amine in this reaction. The interaction may
promote single electron transfer by the visible light irradiation.
alcohol could be obtained as
a
single product under the
reagent/N-methyl-2-pyrrolidone
conditions of (CF3H)-derived
Background and Originality Content
conditions
(NMP)/O2
of
or
Langlois
the
4a
The
importance
of
CF3-containing
molecules
in
CF3Cu/bis(pinacolato)diboron (B2Pin2)/air4b (Scheme 1c). Both
reactions occurred under air conditions, and oxygen acted as a
green source of oxygen. Very recently, a Ru-catalyzed visible-light
promoted photoredox reaction of a styrene with CF3I provided a
β-trifluoromethyl benzyl alcohol in 51% yield (Scheme 1d).5
Oxytrifluoromethylation of alkenes provided derivatives which
pharmaceuticals, agrochemicals and materials intrigues the
intense interest in synthetic methodology of these compounds.1
β-trifluoromethyl alcohols are one of important CF3-containing
intermediates, and the synthesis of these compounds could be
conveniently realized through hydroxytrifluoromethylation of
alkenes.2-5 Photoredox hydroxytrifluoromethylation of alkenes
was
(S-(trifluoromethyl)dibenzothiophenium) efficiently in 2012
(Scheme It was the first photocatalytic
1a).2
realized
by
Umemoto
reagent
could generate
β-trifluoromethyl alcohols by a two-step
process.6 Therefore, although excellent work was done, the
substrate scope was limited to aromatic alkenes and few
examples used aliphatic alkenes.
hydroxytrifluoromethylation reaction of alkenes, showing the
power of visible light photocatalysis in synthetic chemistry.
However, Umemoto reagent that they used was an expensive
electrophilic trifluoromethylating reagent. Later, the Langlois
reagent (CF3SO2Na) was applied to generate β-trifluoromethyl
3a
alcohols by the catalysis of Mn salt/O2 or by oxidation of
excessive tert-butyl hydroperoxide (TBHP) with one equivalent of
benzoquinone (BQ)3b (Scheme 1b). Langlois reagent (CF3SO2Na)
was also used to produce β-trifluoromethyl alcohols through
paired electrolysis in organic-aqueous media.3c The use of
Langlois reagent (CF3SO2Na) which is cheap and easily available
enriches the method of producing β-trifluoromethyl alcohols. And
no strong oxidative initiator was used in those reactions although
sometimes the selectivity was not very good because the
generation of α-trifluoromethyl ketones were unavoidable.3
When an α-substituted styrene was used and the substituted
group prevented the over-oxidation, a tertiary β-trifluoromethyl
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10.1002/cjoc.201900087
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on on
iti
H
O
C
d
(TMEDA) as base in solvent under visible light irradiation by 24 W
fluorescent lamp in air (Table 1). Among the common solvents
including DMF, DMAc, THF, acetonitrile and DMSO, all of them
promoted the reaction and DMSO was the best solvent giving
product 3a in 90% yield (Table 1, entries 1-5; detected by 19F NMR
spectroscopy). To our delight, employing TMEDA as a base with
white light irradiation provided 3a in 90% yield and other bases
can not provided 3a in a good yield (Table 1, entries 5-7). It is
worth noting that 3a could not be obtained in the dark condition,
in the absence of the base, or under a nitrogen atmosphere
(Table 1, entries 8-10).
a
R
( )
F
C
3
R
memo o rea en ac- r
v s
i ibl li ht H
2O
,
e
t
t
,
I
U
f
[
,
]
g
ppy
g
(
)
3
H
O
O
on on
iti
C
d
b
( )
+
R
F
F
3
C
C
3
R
R
a
F
3SO2
N
B
a
TBHP
O
Q,
,
n
M l 4H
C 2
C
or
,
2
F
N
C
3SO2
O O
,
,
2
2
H
O
R
on on
d
iti
C
c
F
C
( )
3
r
,
A
r
A
R
Table 1. Condition Screening of visible light-promoted catalyst-free
a
NMP PPh
, , ,
3
F
N
F
C
or
3SO2
O
hydroxytrifluoromethylation of aliphatic alkenes
2
OH
u
rom
f
]
n
a r
i
F H B Pi
C C
[
C
,
3
3
2
2
v s
e
g
i ibl li ht
CF3
H
O
CF3I
so ven ase
l
t b
e
M
,
on on
iti
F
3
d
C
C
e
M
d
( )
a
1
a
3
2
a r
i
r. .
t
36 h
,
,
a
b
ase
b
n r
E t
so ven
li ht
g
l
t
e
Yi ld
%
(
y
)
u
v s
e
a r
i
F I R
b
l 6H
3C 2
py
( )
i ibl li ht H
C
O
,
O
,
,
,
g
3
2
2
w
w
e
DMF
TMEDA
s wor
1
2
hit li ht
g
87
84
e
thi
k
( )
c
e
DMA
TMEDA
TMEDA
TMEDA
hit li ht
g
on on
iti
O
H
C
d
R
w
e
THF
F
C
3
4
hit li ht
g
55
78
3
R
w
e
hi
hi
hi
t
t
t
li ht
g
C
H CN
3
v s
e
a r
F I TMEDA i ibl li ht
i
C
,
,
,
g
3
w
w
w
e
e
e
DMSO
DMSO
TMEDA
Et3N
5
6
li ht
g
90
30
no o oca a
h t t l
s
m
nex ens ve eas o o era e
ild i i t t
, , ,
y
p p
t
,
p
y
li ht
g
w
e su s ra e sco e oo se ec v
b t
ti it
y
id
t
d
l
,
p
g
TEEDA
TMEDA
/
7
8
9
hit li ht
g
DMSO
DMSO
DMSO
31
0
Scheme 1. Hydroxytrifluoromethylation of alkenes
a useful and inexpensive starting material for
ar
d
k
CF3I is
w
w
e
e
hi
t
li ht
g
0
trifluoromethylation. CF3I can produce trifluoromethyl radical by
10c
hi
t
li ht
g
0
DMSO
TMEDA
light or heat.7 After continuous exploration, Me3Al8a, Et2Zn8b,
FeSO4/H2O/DMSO8c,
Et3B/O2 ,
Na2S2O4
,
9
10a
aReaction conditions: 1a (0.2 mmol), 2 (0.4 mmol), base (0.8 mmol),
anhydrous solvent (2 mL), irradiated by 24 W fluorescent lamp, room
temperature, under an air atmosphere, 36 h; bYield were determined by
19F NMR spectroscopy using benzotrifluoride as the internal standard; cThe
reaction was carried out under a nitrogen atmosphere.
tetrakis(dimethylamino)ethylene (TDAE) 10b, and Ru10c complex
can all trigger CF3I to give trifluoromethyl radical. Currently, visible
light-promoted photoredox system is extensively applied in the
generation of trifluoromethyl radical from CF3I with the catalysts
of Ir and Ru complexes.5,11 Notably, Ritter et al. discovered a liquid
phase halogen-bonded adduct of CF3I with tetramethylguanidine
(TMG), which reacted with alkenes in photocatalytic conditions.12
Halogen-bond interaction was also applied to the radical addition
reactions of long-chained perfluoroalkyl iodide (e.g. C4F9I) with
versatile alkenes and isonitriles, and specifically these fantastic
reactions were promoted with visible light in the absence of
photocatalysts which were normally expensive and hard to
remove.13,14 Oxygen usually hampers radical reactions. However,
oxygen was found to compatible with photoredox reactions and
acted as a source for hydroxy.5,15 In the end, we applied the
hydroxytrifluoromethylation of alkenes with CF3I in the absence of
photocatalyst under the visible light irradiation and air
atmosphere. The feature of this work is exceptionally wide
substrate scope, not only applied to styrenes, but also to aliphatic
alkenes which are barely realized before.
With the optimal reaction conditions identified (Table 1, entry 5),
the substrate scope of the radical hydroxytrifluoromethylation
reaction was examined. A wide range of unactivated terminal
alkenes were applicable to the reaction and provided the
CF3-substituted alcohols in moderate to good yields. A series of
functional groups, including ester (3b–i, 3l, 3n, 3o, 3q),
heterocyclic (3l–o), halogen (3b, 3g, 3h, 3i), ketone (3p),
phthalimide (3m) moieties, and hydroxy (3r) were well tolerated
under the reaction conditions, and might be attributed to the mild
reaction conditions employed. The natural product eugenol and
its derivatives (3j, 3k) also provide good yields. In addition,
terminal alkenes derived from relatively complex molecules
estrone (3p) were compatible with the reaction conditions and
yielded the desired products in satisfactory yields, which
demonstrates the potential of the hydroxytrifluoromethylation
reaction in late-stage functionalization.
The alkenes with
α-substituted methyl group were compatible in this condition and
the isolated yield of the alcohols were excellent (3n, 96%; 3o,
95%). However, cyclopentene gave a low yield of product 3s.
Table 2. Substrate scope of catalyst-free hydroxytrifluoromethylation of
aliphatic alkenesa,b
Results and Discussion
The protocol was initially evaluated with 4-phenyl-1-butene
(1a) as a model substrate to react with 2 equivalents of CF3I (2)
using 4 equivalents of N,N,N',N'-tetramethylethane-1,2-diamine
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© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2019, 37, XXX－XXX
This article is protected by copyright. All rights reserved.

v s
e
i ibl li ht
g
v s
e
g
R2
R2
i
ibl li ht
OH
TMEDA
H
O
TMEDA
CF3I
F
C
R
CF3
O
3
+
2
DMSO
R
1
2
R
3
R
DM
SO
a r
r
t
i
,
1'
3'
a r r
,
i
t
OH
7
O
OH
OH
R2
R1
CF3
CF3
CF3
R2
O
O
R3
H
O
H
O
R
F
C
3
a
:
=
=
=
=
3
3d R1
e:
H
H
R
R
H
C
F
=
86%
8%
,
,
,
:
=
C
l
=
3b
R
R
98%
2
R4
F
C
3
t
3
R1
9
1
%
c:
u
2
,
3
B
3
9
2
%
:
=
e
M
3f R1
3
3h R1
R
H
O
96%
2
R1
:
g
=
=
=
R1
I
F
R
H
9
7
%
96%
,
2
:
=
H
R
,
2
1
2
O
OH
a
=
=
,
:
3 ' R H R H 72
,
%
%
5
3k' R
l R4
H
=
, ,
r
3
:
=
C
9 %
4
F
F
O
C
3
1
2
CF3
O
:
=
=
3b'
c :
R
F R H 90
,
,
H
=
,
3
:
=
3l' R
B
=
R4
H
=
, ,
93
%
OH
1
2
F
HO
=
=
3 ' R Ph R
8
,
,
%
3
' R
R4
H
83
,
7
8
,
%
3
m
:
e
M
=
,
%
3i
,
5
3
5
8%
,
j
8
%
F
R2 H 4
0
1
:
=
r
3d' R
B
,
%
3
4
n
:
=
=
=
=
=
e
3 ' R H R
M
,
c
B
R2 H 7
0
1
t
e
=
,
:
=
u
O
O
O
N
O
3 ' R
,
%
3
4
4
4
O
o
=
=
r
:
'
:
'
CF3
3
3
R
R
H R
,
H R
,
B
74
e
%
OH
,
R2 H 45
1
:
=
e
M
=
,
R2
H
=
,
=
,
3f' R
O
%
38%
3%
OH
,
3
3
CF3
C
F
O
M
3 %
2
3
O
p
,
1
N
OH
:
=
=
3 ' R
g
3h' R
N
C
e
O2
,
:
=
3 ' R H R
N
O2
54
,
%
q
,
O
N R2 H 7
1
:
,
m
3
3k
,
5
3l 74
9
5
9
%
,
%
,
%
R2
H
=
,
8
2
1
1
:
=
3i' R
M
,
%
OH
OH
OH
O
O
2
S
O
:
=
=
3 ' R H R Ph
5
8
,
,
%
CF3
CF3
j
O
O
H
H
O
O
n
o
,
3
3
96%
9
5
%
,
F
F
C
C
3
3
O
e
M
O
F3C
O
H
OH
s
H
H
3
'
90
,
%
r
3 ' 74
,
%
F3C
O
H
H
O
O
3
5
3
q,
88%
9
%
p,
F
C
S
3
F
C
N
N
F
C
3
3
CF3
c
N
HO
H
O
HO
CF3
OH
N
c
r
3
8
5
%
,
s
3
2
8%
,
v
u
3t' 7
3 ' 71
3 ' 5
8
%
8
,
,
%
,
%
aReaction conditions: 1 (0.2 mmol), 2 (0.4 mmol), TMEDA (0.8 mmol),
aReaction conditions: 1’ (0.2 mmol), 2 (0.4 mmol), TMEDA (0.4 mmol),
anhydrous DMSO (2 mL), 24
W white fluorescent irradiation, room anhydrous DMSO (2 mL), 24 W white fluorescent irradiation, room
c
temperature, under an air atmosphere, 36 h; b Isolated yield. cYield were temperature, under an air atmosphere, 36 h; bIsolated yield. Isolated
determined by 19F NMR spectroscopy using benzotrifluoride as the internal yield of ketone was 5%.
standard.
“Generality” is very important for a reaction. Previous
We also explored the substrate scope of aromatic and
heteroaromatic alkenes (the optimized conditions see the
supporting information). As shown in Table 3, a wide variety of
hydroxytrifluoromethylation focused on styrenes. For examples,
Akita et al. found the reactions of Umemoto reagent with styrenes
could provide β-trifluoromethyl alcohols in good selectivity.2
However, the reaction of 1-octene didn’t occur. To best of our
knowledge, only two examples of aliphatic alkenes were used and
the reactions were not well selective. 1-octene provided 45% yield
of a β-trifluoromethyl alcohol which were mixed with 13% yield of
an α-trifluoromethyl ketone product. When cis-cyclooctene were
used, the yields of the alcohol and the ketone were 35% and 30%,
respectively.3a As we showed in Table 2, we provided nineteen
examples of aliphatic alkenes with various structures. All of them
were in good selectivities, providing β-trifluoromethyl alcohol
products without the detection of any α-trifluoromethyl ketones
by 19F NMR monitoring.
styrenes
bearing
either
electron-withdrawing
or
electron-donating substituents on the aryl ring could be
transformed into the corresponding hydroxytrifluoromethylation
compounds in moderate to good yields. Styrenes bearing different
halogen atoms smoothly produced the corresponding products
(3b’, 3d’, 3k’ and 3l’) in good yields. Styrenes with the
electron-donating substituents (3e’, 3f’, 3i’, 3m’, 3n’, 3p’ and 3s’)
afforded the corresponding products in moderate yields. The
disubstituted alkenes underwent the desired reaction giving
product (3j’) effectively. Remarkably, styrenes with the
electron-withdrawing group efficiently gave product (3g’, 3h’, 3q’)
in good yield. In addition, this reaction could also be applied to
naphthalene and heterocyclic aryl alkenes such as
vinylnaphthalenes (3r’), a thiazole derivative (3t’), 2-vinylpyridine
(3u’), 2-vinylpyrazine (3v’) gain corresponding products in
moderate to good yields.
The selectivity of our reaction were also good for styrene
substrates. As shown in Table 3, most of our examples were the
substrates without α-substituent. The signals assigned to the
ketone products in 19F NMR monitoring were observed only for
three special substrates with electron-donating groups in phenyl
rings
(4-methoxystyrene,
3-methoxystyrene
and
Table 3. Substrate scope of catalyst-free hydroxytrifluoromethylation of
aromatic and heteroaromatic alkenesa,b
4-tert-butylstyrene). For 3f’, the 19F NMR yield of alcohol product
was 83% accompanying with a 14% yield of ketone by-product.
These two products were hard to separate due to the close
polarity. As a result, we only isolated 45% yield of the pure alcohol
Chin. J. Chem. 2019, 37, XXX－XXX
© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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This article is protected by copyright. All rights reserved.

product. 4-tert-Butylstyrene gave a 5% isolated yield of ketone
product 4a (Table 3). The reason for low yield of 3d’ and 3p’ was
unclear. In other cases of Table 3, no ketones were detected.
α-substituent on styrenes could prevent the over-oxidation to
avoid the ketone products as shown in Lei4a and Tsui4b work. In
our experiment, 1,1-diphenylethene gave a 85% yield of the
β-trifluoromethyl alcohol 3j’, which were about two times higher
than the yield reported by Tsui4b.
Iodotrifluoromethane is a readily available trifluoromethylating
reagent and works as a trifluoromethyl radical source.7-12 The
price of iodotrifluoromethane is much lower than electrophilic
trifluoromethylating reagent. However, CF3I are a gas at room
temperature and its operation is not easy. Ritter et al. reported a
CF3I·2DMSO complex.12 Inspired by their work, we found that CF3I
can be well dissolved in DMSO to generate a solution with a
constant concentration for two months (experimental procedure
in supporting information). In Ritter’s and later Jiao’s work,
photocatalyst was needed for trifluoromethylation from CF3I.5,12
But, in our experiments, no photocatalyst was needed and
irradiation by visible light were enough to promote the reactions.
Some mechanistic experiments were carried out (Scheme 2). In
the 19F NMR spectra of pure iodotrifluoromethane and its
mixtures with TMEDA in DMSO solvent, we found that the
fluorine signal of a single CF3I in DMSO was at -12.4 ppm. When
CF3I was combined with TMEDA, the fluorine signal of CF3I was at
-14.3 ppm in DMSO. The Δ|δ (CF3)| was 1.9 ppm. Therefore, we
proposed that there was a halogen bond interaction between the
nitrogen of TMEDA and the iodine atom of CF3I.12,14 On the other
hand, using hydroquinone and 1,4-dinitrobenzene could partially
inhibit the reaction (Scheme 2a). Based on the aforementioned
phenomena, a mechanism is proposed (Scheme 2b). We speculate
that
a halogen bond interaction between the amine and
iodotrifluoromethane produces an electron donor-receptor
complex A. A is then excited by irradiation of visible light and a
single electron transfer occurs. The formed trifluoroiodomethyl
radical is then captured by olefin to produce a free radical
intermediate B. The free radical intermediate B then captures O2
from the air to produce a new peroxide radical C which provides
the final product 3.15
Inhibition
experiments
(a)
2
(1 equiv.)
TMEDA
(1 equiv.)
visible
r.t.
DMSO, air,
light,
1a
3a
Additive
19F NMR
Additive
yield (%)
90
without additive
66
18
HO
OH
(1 equiv.)
NO2
NO2
(1 equiv.)
mechanism
DMSO
Proposed
(b)
I
CF3
N
δF
-12.4
+
ppm
N
I
CF3
δF
-14.3
N
ppm
N
A
1
visible
light
CF3
R
CF3
O O
O2
3
R1
R
R1
B
C
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Chin. J. Chem. 2019, 37, XXX－XXX
This article is protected by copyright. All rights reserved.

Scheme 2. Mechanistic study for the visible light induced
hydroxytrifluoromethylation of alkenes under an air atomosphere
purified with silica gel column chromatography to provide the
desired product.
1.3 General procedures for synthesis of 3’
To a 25 mL Schlenk tube equipped with a rubber septum and
a magnetic stirring bar was charged with DMSO (2 mL). Then
alkene 1 (0.2 mmol), CF3I (0.4 mmol), TMEDA (0.4 mmol) were
added. The mixture was stirred under an air atmosphere by
irradiation of 24 W white fluorescent lamp for 36 h. After the
reaction was complete, the solution was added CH2Cl2 (15 mL)
and washed with saturated brine (25 mL × 3). The organic layer
was dried by anhydrous Na2SO4. After that, the organic layer was
separated and concentrated under vacuum. The residue was
purified with silica gel column chromatography to provide the
desired product.
Conclusions
In summary, we developed a hydroxytrifluoromethylation
reaction of various alkenes which occurred under visible light
irradiation without using
a photocatalyst. The inexpensive
reagent CF3I was used as an effective radical trifluoromethylating
reagent. The substrate scope was wide; both styrenes and
aliphatic alkenes were used. Various olefins can react to give the
corresponding product in yields of up to 98% with a good
selectivity.
1,1,1-trifluoro-5-phenylpentan-3-ol (3a). yellow liquid, yield:
86%. IR (film) vmax: 3410, 3029, 2927, 2861, 1603, 1497, 1386,
1259, 1143, 1073 cm-1. 1H NMR (400 MHz, CDCl3) δ 7.32 (t, J = 7.5
Hz, 2H), 7.22 (m, 3H), 4.09 – 4.00 (m, 1H), 2.88 – 2.67 (m, 2H),
2.39 – 2.22 (m, 2H), 2.01 (br, 1H), 1.90 – 1.81 (m, 2H). 13C NMR
(101 MHz, CDCl3) δ 141.1 (s), 128.5 (s), 128.4 (s), 126.4 (q, J =
275.4 Hz), 126.1 (s), 65.5 (q, J = 2.8 Hz), 41.2 (q, J = 26.4 Hz), 38.6
(s), 31.5 (s). 19F NMR (376 MHz, CDCl3) δ -63.4 (t, J = 11.0 Hz).
HRMS(EI) Calcd for C11H13F3O (M+): 218.0918; found: 218.0916.
5,5,5-trifluoro-3-hydroxypentyl 4-chlorobenzoate (3b). yellow
liquid, yield: 98%. IR (film) vmax: 3467, 2964, 1717, 1596, 1489,
1402, 1277, 1123, 1016 cm-1. 1H NMR (400 MHz, CDCl3) δ 7.92 (d,
J = 8.5 Hz, 2H), 7.39 (d, J = 8.5 Hz, 2H), 4.63 – 4.53 (m, 1H), 4.44 –
4.35 (m, 1H), 4.21 – 4.11 (m, 1H), 2.97 (br, 1H), 2.47 – 2.16 (m,
2H), 2.10 – 1.80 (m, 2H). 13C NMR (101 MHz, CDCl3) δ 166.1 (s),
139.7 (s), 130.9 (s), 128.8 (s), 128.2 (s), 126.1 (q, J = 275.4 Hz),
62.9 (q, J = 3.0 Hz), 61.5 (s), 41.1 (q, J = 26.8 Hz), 36.1 (s). 19F NMR
(376 MHz, CDCl3) δ -63.5 (t, J = 10.8 Hz). HRMS(EI) Calcd for
C12H12ClF3O3 (M+): 296.0427; found: 296.0435.
5,5,5-trifluoro-3-hydroxypentyl 4-(tert-butyl)benzoate (3c).
yellow liquid, yield: 92%. IR (film) vmax: 3466, 2966, 1717, 1610,
1464, 1367, 1281, 1190, 1122, 1018 cm-1. 1H NMR (400 MHz,
CDCl3) δ 7.97 – 7.92 (m, 2H), 7.48 – 7.43 (m, 2H), 4.66 – 4.58 (m,
1H), 4.43 – 4.35 (m, 1H), 4.21 – 4.12 (m, 1H),3.13 – 3.06 (m, 1H),
2.47 – 2.21 (m, 2H), 2.07 – 1.84 (m, 2H), 1.33 (s, 9H). 13C NMR
(101 MHz, CDCl3) δ 167.1 (s), 157.0 (s), 129.5 (s), 126.1 (q, J =
275.4 Hz), 126.9 (s), 125.4 (s), 63.1 – 62.9 (m), 61.0 (s), 41.1 (q, J =
26.8 Hz), 36.3 (s), 35.1 (s), 31.0 (s). 19F NMR (376 MHz, CDCl3) δ
-63.5 (t, J = 10.9 Hz). HRMS(ESI) Calcd for C16H22F3O3 [M + H]+:
319.1516; found: 319.1514.
Experimental
1. General Methods
All reagents were used without further purification. Thin layer
chromatography (TLC) was visualized by staining with potassium
permanganate. Chemical shifts for H NMR spectra are reported
1
in ppm downfield from TMS or residual CHCl3 (δ 7.26 ppm).
Chemical shifts for 19F NMR are reported in ppm downfield from
fluorotrichloromethane (CFCl3). Chemical shifts for 13C NMR
spectra are recorded in ppm relative to residual chloroform (δ
77.0 ppm for CDCl3). 13C NMR was broad-band decoupled from
hydrogen nuclei. Chemical shifts are expressed in parts per million
(ppm) with respect to the residual solvent peak. Coupling
constants are reported as hertz (Hz). Signal shapes and splitting
patterns are indicated as follows: s, singlet; d, doublet; t, triplet; q,
quartet; m, multiplet; br, broad. GC-MS (EI) data were
determined on an Agilent 5975C. HRMS (ESI) data were tested on
a Water Micromass GCT Premier. Unless otherwise noted,
solvents were freshly dried and degassed according to the
purification handbook Purification of Laboratory Chemicals before
using. Flash column chromatography was carried out using 300 -
400 mesh silica gel.
1.1 The preparation of a solution of CF3I in DMSO
To 25 mL of Schlenk tube was added 10 mL of DMSO under air
conditions. Plugged the Schlenk tube with a rubber stopper and
inserted an flat balloon (without filling with gas) to ensure a
stable pressure when filling CF3I gas in. A steady stream of CF3I
gas was passed through the DMSO solution for half an hour to an
hour. After the gas was introduced, 100 μl of the solution sample
was taken out and 0.1 mmol of benzotrifluoride was added into
the sample as an internal standard. By 19F NMR analysis of the
sample, the concentration of CF3I is calculated. The
concentrations were generally at from 3 to 4 mmol/mL. And the
reagent can be stored at a constant concentration for 2 months.
1.2 General procedures for synthesis of 3
7,7,7-trifluoro-5-hydroxyheptyl benzoate (3d). yellow liquid,
yield: 78%. IR (film) vmax: 3462, 2950, 2869, 1717, 1602, 1585,
1453, 1386, 1278, 1147, 1027 cm-1. 1H NMR (400 MHz, CDCl3)δ
8.03 (d, J = 7.3 Hz, 2H), 7.55 (t, J = 7.4 Hz, 1H), 7.43 (t, J = 7.6 Hz,
2H), 4.33 (t, J = 6.5 Hz, 2H), 4.07 – 3.99 (m, 1H), 2.34 – 2.19 (m,
2H), 1.88 – 1.73 (m, 3H), 1.67 – 1.50 (m, 4H). 13C NMR (101 MHz,
CDCl3) δ 166.7 (s), 132.9 (s), 130.3 (s), 129.50 (s), 128.3 (s), 126.4
(q, J = 275.4 Hz), 66.0 – 65.8 (m), 64.7 (s), 41.2 (q, J = 26.4 Hz),
36.6 (s), 28.5 (s), 21.8 (s). 19F NMR (376 MHz, CDCl3) δ -63.5 (t, J =
11.0 Hz). HRMS(EI) Calcd for C14H17F3O3 (M+): 290.1130; found:
290.1135.
To a 25 mL Schlenk tube equipped with a rubber septum and
a magnetic stirring bar was charged with DMSO (2 mL). Then
alkene 1 (0.2 mmol), CF3I (0.4 mmol), TMEDA (0.8 mmol) were
added. The mixture was stirred under an air atmosphere by
irradiation of 24 W white fluorescent lamp for 36 h. After the
reaction was complete, the solution was added CH2Cl2 (15 mL)
and washed with saturated brine (25 mL × 3). The organic layer
was dried by anhydrous Na2SO4. After that, the organic layer was
separated and concentrated under vacuum. The residue was
7,7,7-trifluoro-5-hydroxyheptyl 3-(trifluoromethyl)benzoate
(3e). yellow liquid, yield: 91%. IR (film) vmax: 3446, 2951, 1724,
Chin. J. Chem. 2018, template
© 2018 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
This article is protected by copyright. All rights reserved.

1619, 1386, 1338, 1258, 1132, 1089, 1073 cm-1. 1H NMR (400 MHz,
CDCl3) δ 8.26 (s, 1H), 8.19 (d, J = 7.8 Hz, 1H), 7.78 (d, J = 7.7 Hz,
1H), 7.55 (t, J = 7.8 Hz, 1H), 4.35 (t, J = 6.5 Hz, 2H), 4.06 – 3.96 (m,
1H), 2.46 (br, 1H), 2.34 – 2.18 (m, 2H), 1.89 – 1.74 (m, 2H), 1.68 –
1.47 (m, 4H). 13C NMR (101 MHz, CDCl3) 3C NMR (101 MHz, CDCl3)
δ 165.4 (s), 132.7 (s), 131.1(s), 131.0 (q, J = 32.4 Hz), 129.4 (q, J =
3.6 Hz), 129.0 (s), 126.4 (q, J = 3.8 Hz), 126.4 (q, J = 276.0 Hz),
123.6 (q, J = 270.7 Hz), 65.8 (q, J = 2.6 Hz), 65.3 (s), 41.1 (q, J =
26.4 Hz), 36.6 (s), 28.3 (s), 21.7 (s). 19F NMR (376 MHz, CDCl3) δ
-62.9 (s, 3F), -63.6 (t, J = 11.0 Hz, 3F). HRMS(EI) Calcd for
C15H16F6O3 (M+): 358.1004; found: 358.0994.
7,7,7-trifluoro-5-hydroxyheptyl 4-methoxybenzoate (3f).
yellow liquid, yield: 96%. IR (film) vmax: 3467, 2946, 1710, 1607,
1513, 1386, 1258, 1170, 1147, 1030 cm-1. 1H NMR (400 MHz,
CDCl3) δ 7.96 (d, J = 8.8 Hz, 2H), 6.89 (d, J = 8.8 Hz, 2H), 4.27 (t, J =
6.5 Hz, 2H), 4.05 – 3.96 (m, 1H), 3.82 (s, 3H), 2.54 (br, 1H), 2.34 –
2.16 (m, 2H), 1.83 – 1.70 (m, 2H), 1.65 – 1.44 (m, 4H). 13C NMR
(101 MHz, CDCl3) δ 166.5 (s), 163.3 (s), 131.5 (s), 126.4 (q, J =
275.4 Hz), 122.6 (s), 113.5 (s), 65.8 (q, J = 2.8 Hz), 64.4 (s), 55.3 (s),
41.1 (q, J = 26.4 Hz), 36.6 (s), 28.4 (s), 21.7 (s).19F NMR (376 MHz,
CDCl3) δ -63.5 (t, J = 11.0 Hz). HRMS(EI) Calcd for C15H19F3O4 (M+):
320.1235; found: 320.1234.
2-methoxy-4-(4,4,4-trifluoro-2-hydroxybutyl)phenol
(3j).
yellow liquid, yield: 58%. IR (film) vmax: 3417, 2942, 2849, 1605,
1518, 1432, 1378, 1270, 1143, 1035, 1000 cm-1. 1H NMR (400 MHz,
CDCl3) δ 6.89 – 6.83 (m, 1H), 6.74 – 6.67 (m, 2H), 5.68 (br, 1H),
4.22 – 4.12 (m, 1H), 3.87 (s, 3H), 2.80 (dd, J = 13.6, 4.3 Hz, 1H),
2.69 (dd, J = 13.7, 8.3 Hz, 1H), 2.38 – 2.24 (m, 2H), 2.16 – 2.00 (m,
1H).13C NMR (101 MHz, CDCl3) δ 146.7 (s), 144.6 (s), 128.5 (s),
126.1 (q, J = 275.4 Hz), 122.1 (s), 114.6 (s), 111.8 (s), 67.0 (q, J =
2.7 Hz), 55.9 (s), 43.2 (s), 40.2 (q, J = 27.0 Hz).19F NMR (376 MHz,
CDCl3) δ -63.4 (t, J = 10.9 Hz). HRMS(EI) Calcd for C11H13F3O3 (M+):
250.0817; found: 250.0810.
2-methoxy-4-(4,4,4-trifluoro-2-hydroxybutyl)phenyl acetate
(3k). yellow liquid, yield: 95%. IR (film) vmax: 3475, 2944, 1763,
1606, 1510, 1421, 1374, 1272, 1201, 1151, 1036, 1005 cm-1. H
1
NMR (400 MHz, CDCl3) δ 6.96 (d, J = 8.0 Hz, 1H), 6.80 (s, 1H), 6.76
(d, J = 8.1 Hz, 1H), 4.20 – 4.11 (m, 1H), 3.80 (s, 3H), 2.81 (dd, J =
13.7, 4.4 Hz, 1H), 2.70 (dd, J = 13.7, 8.4 Hz, 1H), 2.37 – 2.23 (m,
6H).13C NMR (101 MHz, CDCl3) δ 169.3 (s), 151.0 (s), 138.6 (s),
136.0 (s), 126.2 (q, J = 275.4 Hz), 122.8 (s), 121.5 (s), 113.6 (s),
66.7 (q, J = 2.8 Hz), 55. 8 (s), 43.4 (s), 40.3 (q, J = 27.0 Hz), 20.6
(s).19F NMR (376 MHz, CDCl3) δ -63.3 (t, J = 10.9 Hz). HRMS(EI)
Calcd for C13H15F3O4 (M+): 292.0922; found: 292.0918.
7,7,7-trifluoro-5-hydroxyheptyl 4-iodobenzoate (3g). white
7,7,7-trifluoro-5-hydroxyheptyl
solid, yield: 97%. m.p.: 56 – 57 ℃. IR (film) vmax: 3486, 2957, 2853, 1-methyl-1H-pyrrole-2-carboxylate (3l). yellow liquid, yield: 74%.
1717, 1702, 1588, 1395, 1181, 1128, 1079, 1008 cm-1. 1H NMR
(400 MHz, CDCl3) δ 7.77 (d, J = 8.2 Hz, 2H), 7.71 (d, J = 8.2 Hz, 2H),
4.30 (t, J = 6.4 Hz, 2H), 4.06 – 3.96 (m, 1H), 2.35 – 2.18 (m, 3H),
IR (film) vmax: 3463, 2949, 1702, 1533, 1483, 1415, 1383, 1323,
1
1250, 1119, 1056, 1018 cm-1. H NMR (400 MHz, CDCl3) δ 6.95 –
6.92 (m, 1H), 6.79 – 6.76 (m, 1H), 6.12 – 6.08 (m, 1H), 4.23 (t, J =
1.84 – 1.72 (m, 2H), 1.66 – 1.45 (m, 4H). 13C NMR (101 MHz, CDCl3) 6.5 Hz, 2H), 4.07 – 3.97 (m, 1H), 3.91 (s, 3H), 2.34 – 2.16 (m, 3H),
δ 166.2 (s), 137.6 (s), 130.9 (s), 129.6 (s), 126.3 (q, J = 275.4 Hz),
100.7 (s), 65.8 (q, J = 3.0 Hz), 64.9 (s), 41.1 (q, J = 26.4 Hz), 36.6 (s), δ 161.4 (s), 129.5 (s), 126.4 (q, J = 275.4 Hz), 122.4 (s), 117.8 (s),
1.81 – 1.69 (m, 2H), 1.67 – 1.53 (m, 4H). 13C NMR (101 MHz, CDCl3)
28.3 (s), 21.7 (s). 19F NMR (376 MHz, CDCl3) δ -63.5 (t, J = 10.9 Hz).
107.8 (s), 65.9 (q, J = 2.8 Hz), 63.4 (s), 41.1 (q, J = 26.4 Hz), 36.7 (s),
63.4 (s), 28.5 (s), 21.7 (s).19F NMR (376 MHz, CDCl3) δ -63.5 (t, J =
11.0 Hz). HRMS(EI) Calcd for C13H18F3NO3 (M+): 293.1239; found:
293.1237.
HRMS(ESI) Calcd for C14H17F3IO3 [M
found: .417.0168.
+
H]+: 417.0169;
7,7,7-trifluoro-5-hydroxyheptyl 4-fluorobenzoate (3h). yellow
liquid, yield: 96%. IR (film) vmax: 3462, 2949, 1698, 1533, 1415,
1384, 1323, 1248, 1116, 1056, 1018 cm-1. 1H NMR (400 MHz,
CDCl3) δ 8.07 – 7.97 (m, 2H), 7.09 (t, J = 8.4 Hz, 2H), 4.31 (t, J = 6.4
Hz, 2H), 4.08 – 3.96 (s, 1H), 2.40 – 2.15 (m, 3H), 1.86 – 1.72 (m,
2H), 1.70 – 1.44 (m, 4H). 13C NMR (101 MHz, CDCl3) δ165.8 (s),
165.7 (d, J = 254.8 Hz), 132.0 (d, J = 9.4 Hz), 126.4 (d, J = 3.0 Hz),
126.3 (q, J = 275.4 Hz), 115.5 (d, J = 22.0 Hz), 65.8 (q, J = 2.8 Hz),
64.8 (s), 41.1 (q, J = 26.4 Hz), 36.6 (s), 28.4 (s), 21.7 (s). 19F NMR
(376 MHz, CDCl3) δ -63.5 (t, J = 10.9 Hz, 3F), -102.8 – -108.6 (m,
1F). HRMS(ESI) Calcd for C14H17F4O3 [M + H]+: 309.1108; found:
309.1107.
2-(6,6,6-trifluoro-4-hydroxyhexyl)isoindoline-1,3-dione (3m).
white solid, yield: 95%. m.p.: 71 - 72 ℃. IR (film) vmax: 3470, 2953,
2928, 1769, 1704, 1440, 1426, 1345, 1269, 1134, 1067, 1054,
1026 cm-1. 1H NMR (400 MHz, CDCl3) δ 7.81 – 7.75 (m, 2H), 7.71 –
7.64 (m, 2H), 4.09 – 3.99 (m, 1H), 3.69 (t, J = 7.0 Hz, 2H), 2.90 (br,
1H), 2.35 – 2.12 (m, 2H), 1.92 – 1.68 (m, 2H), 1.60 – 1.49 (m, 2H).
13C NMR (101 MHz, CDCl3) δ 168.5 (s), 133.9 (s), 131.8 (s), 126.3 (q,
J = 275.4 Hz), 123.1 (s), 65.5 – 65.3 (m), 41.0 (q, J = 26.5 Hz), 37.4
(s), 34.0 (s), 24.4 (s).19F NMR (376 MHz, CDCl3) δ -63.5 (t, J = 10.9
Hz). HRMS(ESI) Calcd for C14H15F3NO3 [M + H]+: 302.0999; found:
302.0997.
7,7,7-trifluoro-5-hydroxyheptyl 3,4,5-trifluorobenzoate (3i).
yellow liquid, yield: 85%. IR (film) vmax: 3447, 2950, 1731, 1625,
1530, 1441, 1356, 1255, 1226, 1148, 1088, 1049 cm-1. 1H NMR
(400 MHz, CDCl3) δ 7.70 – 7.62 (m, 2H), 4.33 (t, J = 6.6 Hz, 2H),
4.08 – 3.99 (m, 1H), 2.35 – 2.19 (m, 2H), 1.88 – 1.71 (m, 3H), 1.68
– 1.45 (m, 4H). 13C NMR (101 MHz, CDCl3)δ 163.9 (s), 151.0 (ddd, J
= 251.8, 10.3, 3.4 Hz), 143.1 (dt, J = 259.2, 15.3 Hz), 126.4 (q, J =
275.4 Hz), 126.2 (td, J = 7.2, 4.3 Hz), 114.1 (dd, J = 16.4, 6.4 Hz),
66.0 – 65.8 (m), 65.6 (s), 41.2 (q, J = 26.1 Hz), 36.6 (s), 28.4 (s),
21.7 (s). 19F NMR (376 MHz, CDCl3) δ -63.6 (t, J = 11.0 Hz, 3F),
-132.7 – -132.9 (m, 2F), -152.7 – -153.0 (m, 1F). HRMS(EI) Calcd
for C14H14F6O3 (M+): 344.0847; found: 344.0857.
5,5,5-trifluoro-3-hydroxy-3-methylpentyl
thiophene-2-carboxylate (3n). yellow liquid, yield: 96%. IR (film)
vmax: 3466, 3105, 2977, 1705, 1526, 1463, 1420, 1362, 1263, 1170,
1101, 1046 cm-1. 1H NMR (400 MHz, CDCl3) δ 7.78 (dd, J = 3.8, 1.2
Hz, 1H), 7.55 (dd, J = 5.0, 1.2 Hz, 1H), 7.09 (dd, J = 5.0, 3.8 Hz, 1H),
4.49 (t, J = 6.6 Hz, 2H), 2.52 – 2.37 (m, 3H), 2.15 – 1.96 (m, 2H),
1.42 (s, 3H).13C NMR (101 MHz, CDCl3) δ 162.1 (s), 133.6 (s), 133.3
(s), 132.6 (s), 127.8 (s), 126.0 (q, J = 275.4 Hz), 69.5 (q, J = 2.0 Hz),
61.1 (s), 44.9 (q, J = 26.1 Hz), 40.2 (s), 27.2 (s).19F NMR (376 MHz,
CDCl3) δ -60.2 (t, J = 11.4 Hz). HRMS(EI) Calcd for C11H13F3O3S (M+):
282.0538; found: 282.0532.
5,5,5-trifluoro-3-hydroxy-3-methylpentyl furan-2-carboxylate
www.cjc.wiley-vch.de
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Chin. J. Chem. 2019, 37, XXX－XXX
This article is protected by copyright. All rights reserved.

(3o). yellow liquid, yield: 95%. IR (film) vmax: 3480, 3144, 2980,
1717, 1582, 1474, 1387, 1304, 1265, 1233, 1182, 1124, 1017 cm-1.
1H NMR (400 MHz, CDCl3) δ 7.56 – 7.55 (m, 1H), 7.17 – 7.14 (m,
1H), 6.50 – 6.48 (m, 1H), 4.49 (t, J = 6.6 Hz, 2H), 2.47 – 2.35 (m,
3H), 2.14 – 1.93 (m, 2H), 1.41 (s, 3H). 13C NMR (101 MHz, CDCl3) δ
158.5 (s), 146.5 (s), 144.4 (s), 125.9 (q, J = 277.8 Hz), 118.2 (s),
111.9 (s), 69.5 (q, J = 2.8 Hz), 61.0 (s), 44.8 (q, J = 26.1 Hz), 40.0 (s),
27.4 – 26.8 (m). 19F NMR (376 MHz, CDCl3) δ -60.3 (t, J = 11.4 Hz).
HRMS(ESI) Calcd for C11H14F3O4 [M + H]+: 267.0839; found:
267.0838.
(8R,9S,13S,14S)-13-methyl-3-((7,7,7-trifluoro-5-hydroxyheptyl
)oxy)-6,7,8,9,11,12,13,14,15,16-decahydro-17H-cyclopenta[a]phe
nanthren-17-one (3p). white solid, yield: 95%. m.p.: 115 – 116 ℃.
IR (film) vmax: 3545, 3420, 2929, 2865, 1725, 1611, 1572, 1499,
1437, 1375, 1339, 1277, 1251, 1145, 1087, 1058, 1028, 1005 cm-1.
1H NMR (400 MHz, CDCl3) δ 7.19 (d, J = 8.3 Hz, 1H), 6.71 (d, J = 8.2
Hz, 1H), 6.64 (s, 1H), 4.08 – 4.00 (m, 1H), 3.98 – 3.89 (m, 2H), 2.97
– 2.78 (m, 2H), 2.58 – 1.93 (m, 10H), 1.87 – 1.73 (m, 2H), 1.71 –
1.39 (m, 9H), 1.33 – 1.19 (m, 1H), 0.90 (s, 3H). 13C NMR (101 MHz,
CDCl3) δ 221.1 (s), 156.9 (s), 137.7 (s), 132.0 (s), 126.4 (q, J = 275.4
Hz), 126.2 (s), 114.5 (s), 112.0 (s), 67.5 (s), 66.0 – 65.8 (m), 50.3 (s),
48.0 (s), 43.9 (s), 41.1 (q, J = 26.4 Hz), 38.3 (s), 36.8 (s), 35.8 (s),
31.5 (s), 29.6 (s), 28.9 (s), 26.5 (s), 25.8 (s), 21.8 (s), 21.5 (s), 13.8
(s).19F NMR (376 MHz, CDCl3) δ -63.5 (t, J = 10.9 Hz). HRMS(EI)
Calcd for C25H33F3O3 (M+): 438.2382; found: 438.2388.
(376 MHz, CDCl3) δ -63.8 (t, J = 10.7 Hz).
3,3,3-trifluoro-1-(4-methoxyphenyl)propan-1-ol
(3f’).3b,3c
1
yellow liquid, yield: 45%. H NMR (400 MHz, CDCl3) δ 7.29 (d, J =
8.7 Hz, 2H), 6.90 (d, J = 8.6 Hz, 2H), 5.02 (dd, J = 8.8, 3.7 Hz, 1H),
3.81 (s, 3H), 2.71 – 2.53 (m, 1H), 2.50 – 2.34 (m, 1H), 2.16 (br, 1H).
19F NMR (376 MHz, CDCl3) δ -63.8 (t, J = 10.6 Hz).
3,3,3-trifluoro-1-(4-nitrophenyl)propan-1-ol (3g’).3 yellow
1
liquid, yield: 38%. H NMR (400 MHz, CDCl3) δ 8.22 (d, J = 8.6 Hz,
2H), 7.57 (d, J = 8.6 Hz, 2H), 5.22 (dd, J = 8.6, 3.1 Hz, 1H) 2.72 –
2.38 (m, 3H). 19F NMR (376 MHz, CDCl3) δ -63.6 (t, J = 10.4 Hz).
4-(3,3,3-trifluoro-1-hydroxypropyl)benzonitrile
(3h’).3b,3c
1
yellow liquid, yield: 73%. H NMR (400 MHz, CDCl3) δ 7.66 (d, J =
8.1 Hz, 2H), 7.51 (d, J = 8.2 Hz, 2H), 5.15 (d, J = 8.7 Hz, 1H), 2.67 –
2.52 (m, 2H), 2.51 – 2.35 (m, 1H). 19F NMR (376 MHz, CDCl3) δ
-63.6 (t, J = 10.4 Hz).
3,3,3-trifluoro-1-(p-tolyl)propan-1-ol (3i’).3b yellow liquid,
1
yield: 82%. H NMR (400 MHz, CDCl3) δ 7.24 (d, J = 8.0 Hz, 2H),
7.18 (d, J = 7.9 Hz, 2H), 5.02 (dd, J = 8.7, 2.2 Hz, 1H), 2.69 – 2.52
(m, 1H), 2.49 – 2.36 (m, 1H), 2.34 (s, 3H), 2.15 (s, 1H). 19F NMR
(376 MHz, CDCl3) δ -63.8 (t, J = 10.7 Hz).
3,3,3-trifluoro-1,1-diphenylpropan-1-ol (3j’).4b yellow liquid,
1
yield: 85%. H NMR (400 MHz, CDCl3) δ 7.44 (d, J = 7.8 Hz, 4H),
7.35 (t, J = 7.7 Hz, 4H), 7.28 (t, J = 7.3 Hz, 2H), 3.22 (q, J = 10.3 Hz,
2H), 2.68 (s, 1H).19F NMR (376 MHz, CDCl3) δ -58.2 (t, J = 10.3 Hz).
1-(2-chlorophenyl)-3,3,3-trifluoropropan-1-ol (3k’).3a,3c yellow
liquid, yield: 94%. 1H NMR (400 MHz, CDCl3) δ 7.60 (dd, J = 7.7, 1.4
Hz, 1H), 7.37 – 7.28 (m, 2H), 7.24 (td, J = 7.6, 1.6 Hz, 1H), 5.51 –
5.44(m, 1H), 2.66 – 2.34 (m, 3H). 19F NMR (376 MHz, CDCl3) δ
-63.9 (t, J = 10.5 Hz).
methyl
12,12,12-trifluoro-10-hydroxydodecanoate
(3q).
yellow liquid, yield: 88%. IR (film) vmax: 3424, 2927, 2851, 1728,
1467, 1439, 1385, 1282, 1153, 1097, 1047, 1026 cm-1. 1H NMR
(400 MHz, CDCl3) δ 4.00 – 3.92 (m, 1H), 3.63 (s, 3H), 2.31 – 2.15
(m, 5H), 1.63 –1.17 (m, 14H). 13C NMR (101 MHz, CDCl3) δ 174.4
(s), 126.5 (q, J = 277.1 Hz), 66.2– 66.0 (m), 51.4 (s), 41.1 (q, J =
26.3 Hz), 37.1 (s), 34.0 (s), 29.2 (s), 29.1 (s), 29.0 (s), 25.1 (s), 24.8
(s).19F NMR (376 MHz, CDCl3) δ -63.6 (t, J = 11.0 Hz). HRMS(EI)
Calcd for C13H23F3O3 (M+): 284.1599; found: 284.1592.
1-(2-bromophenyl)-3,3,3-trifluoropropan-1-ol (3l’). yellow
liquid, yield: 93%. IR (film) vmax: 3421, 3068, 2926, 1710, 1570,
1469, 1378, 1250, 1200, 1141, 1107, 1029 cm-1. 1H NMR (400 MHz,
CDCl3) δ 7.60 (d, J = 7.7 Hz, 1H), 7.54 (d, J = 8.0 Hz, 1H), 7.37 (t, J =
7.6 Hz, 1H), 7.22 – 7.15 (m, 1H), 5.48 – 5.40 (m, 1H), 2.62 – 2.51
(m, 2H), 2.50 – 2.36 (m, 1H). 13C NMR (101 MHz, CDCl3) δ 141.1 (s),
132.9 (s), 129.6 (s), 128.0 (s), 127.2 (s), 125.9(q, J = 276.2 Hz),
121.2 (s), 67.6 (q, J = 3.3 Hz), 41.2 (q, J = 27.3 Hz). 19F NMR (376
MHz, CDCl3) δ -63.8 (t, J = 10.5 Hz). HRMS(EI) Calcd for C9H8BrF3O
(M+): 267.9711; found: 267.9708
3,3,3-trifluoro-1-phenylpropan-1-ol (3a’).3 yellow liquid, yield:
72%. 1H NMR (400 MHz, CDCl3) δ 7.43 – 7.29 (m, 5H), 5.07 (dd, J =
9.0, 3.5 Hz, 1H), 2.71 – 2.55 (m, 1H), 2.52 – 2.37 (m, 1H), 2.23 (br,
1H). 19F NMR (376 MHz, CDCl3) δ -63.9 (t, J = 10.6 Hz).
3,3,3-trifluoro-1-(4-fluorophenyl)propan-1-ol (3b’).3 yellow
liquid, yield: 90%. 1H NMR (400 MHz, CDCl3) δ (dd, J = 8.4, 5.5 Hz,
2H), 7.06 (t, J = 8.6 Hz, 2H), 5.05 (d, J = 8.4 Hz, 1H), 2.69 – 2.51 (m,
1H), 2.49 – 2.34 (m, 2H). 19F NMR (376 MHz, CDCl3) δ -63.8 (t, J =
10.6 Hz, 3F), -113.6 – -113.8 (m, 1F).
3,3,3-trifluoro-1-(o-tolyl)propan-1-ol (3m’).3a yellow liquid,
yield: 83%. 1H NMR (400 MHz, CDCl3) δ 7.50 – 7.45 (m, 1H), 7.28 –
7.13 (m, 3H), 5.34 – 5.22 (m, 1H), 2.62 – 2.47 (m, 1H), 2.43 – 2.31
(m, 5H). 19F NMR (376 MHz, CDCl3) δ -64.2 (t, J = 10.7 Hz).
3,3,3-trifluoro-1-(m-tolyl)propan-1-ol (3n’).3a yellow liquid,
1-([1,1'-biphenyl]-4-yl)-3,3,3-trifluoropropan-1-ol
(3c’).3c
1
1
yellow liquid, yield: 85%. H NMR (400 MHz, CDCl3) δ 7.65 – 7.55
(m, 4H), 7.50 – 7.42 (m, 4H), 7.41 – 7.33 (m, 1H), 5.18 – 5.09 (m,
1H), 2.75 – 2.40 (m, 2H), 2.27 – 2.11 (m, 1H). 19F NMR (376 MHz,
CDCl3) δ -63.7 (t, J = 10.6 Hz).
yield: 78%. H NMR (400 MHz, CDCl3) δ 7.23 (t, J = 3.7 Hz, 1H),
7.13 (dd, J = 17.1, 7.6 Hz, 3H), 5.02 (dd, J = 8.8, 2.3 Hz, 1H), 2.67 –
2.53 (m, 1H), 2.52 – 2.38 (m, 2H), 2.35 (s, 3H). 19F NMR (376 MHz,
CDCl3) δ -63.8 (t, J = 10.7 Hz).
1-(4-bromophenyl)-3,3,3-trifluoropropan-1-ol (3d’).3a,3b yellow
1-(3-bromophenyl)-3,3,3-trifluoropropan-1-ol (3o’). yellow
liquid, yield: 74%. IR (film) vmax: 3399, 3066, 2918, 1573, 1475,
1431, 1378, 1258, 1199, 1138, 1071 cm-1. 1H NMR (400 MHz,
CDCl3) δ 7.56 (m, 1H), 7.49 (dt, J = 7.3, 1.7 Hz, 1H), 7.34 – 7.27 (m,
2H), 5.09 – 5.01 (m, 1H), 2.72 (d, J = 2.2 Hz, 1H), 2.67 – 2.36 (m,
2H). 13C NMR (101 MHz, CDCl3) δ 144.5 (s), 131.4 (s), 130.4 (s),
128.8 (s), 125.7 (q, J = 275.8 Hz), 124.3 (s), 122.8 (s), 68.1 (q, J =
3.2 Hz), 42.7 (q, J = 27.1 Hz). 19F NMR (376 MHz, CDCl3) δ -63.7 (t, J
= 10.5 Hz). HRMS(EI) Calcd for C9H8BrF3O (M+): 267.9711; found:
1
liquid, yield: 40%. H NMR (400 MHz, CDCl3) δ 7.49 (d, J = 7.9 Hz,
2H), 7.23 (d, J = 8.1 Hz, 2H), 5.02 (d, J = 8.2 Hz, 1H), 2.66 – 2.50 (m,
1H), 2.47 – 2.25 (m, 2H). 19F NMR (376 MHz, CDCl3) δ -63.7 (t, J =
10.5 Hz).
1-(4-(tert-butyl)phenyl)-3,3,3-trifluoropropan-1-ol
(3e’).3c
1
yellow liquid, yield: 70%. H NMR (400 MHz, CDCl3) δ 7.41 (d, J =
8.2 Hz, 2H), 7.29 (d, J = 8.2 Hz, 2H), 5.02 (dd, J = 9.1, 3.3 Hz, 1H),
2.67 – 2.52 (m, 1H), 2.50 – 2.32 (m, 2H), 1.34 (s, 9H). 19F NMR
Chin. J. Chem. 2019, 37, XXX－XXX
© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
This article is protected by copyright. All rights reserved.

267.9704.
3,3,3-trifluoro-1-(3-methoxyphenyl)propan-1-ol (3p’). yellow
1-(4-(tert-butyl)phenyl)-2-hydroxyethan-1-one(4a’).16 yellow
liquid, yield: 5%. H NMR (400 MHz, CDCl3) δ 7.88 (d, J = 8.4 Hz,
1
liquid, yield: 32%. IR (film) vmax: 3431, 2947, 2841, 1603, 1490,
1436, 1377, 1320, 1262, 1127, 1047 cm-1. 1H NMR (400 MHz,
CDCl3)δ 7.29 (t, J = 7.9 Hz, 1H), 6.96 – 6.91 (m, 2H), 6.88 – 6.83 (m,
1H), 5.04 (dd, J = 9.0, 3.0 Hz, 1H), 3.82 (s, 3H), 2.69 – 2.52 (m, 1H),
2.51 – 2.37 (m, 1H), 2.28 (br, 1H). 13C NMR (101 MHz, CDCl3) δ
159.9 (s), 144.0 (s), 129.9 (s), 125.9 (q, J = 275.7 Hz), 117.8 (s),
113.8(s), 111.2(s), 68.7 (q, J = 3.2 Hz), 55.3(s), 42.8 (q, J = 27.0 Hz).
19F NMR (376 MHz, CDCl3) δ -63.8 (t, J = 10.7 Hz). HRMS(EI) Calcd
for C10H11F3O2 (M+): 220.0711; found: 220.0706.
2H), 7.52 (d, J = 8.4 Hz, 2H), 3.77 (q, J = 10.1 Hz, 2H), 1.35 (s, 9H).
19F NMR (376 MHz, CDCl3) δ -62.0 (t, J = 10.1 Hz).
Supporting Information
The supporting information for this article is available on the
WWW under https://doi.org/10.1002/cjoc.2018xxxxx.
Acknowledgement
3,3,3-trifluoro-1-(3-nitrophenyl)propan-1-ol (3q’).3a yellow
liquid, yield: 52%. 1H NMR (400 MHz, CDCl3) δ 8.24 (s, 1H), 8.14 (d,
J = 8.2 Hz, 1H), 7.72 (d, J = 7.7 Hz, 1H), 7.55 (t, J = 7.9 Hz, 1H), 5.20
(dd, J = 8.6, 3.2 Hz, 1H), 3.01 (s, 1H), 2.71 – 2.39 (m, 2H). 19F NMR
(376 MHz, CDCl3) δ -63.6 (t, J = 10.5 Hz).
The support of our work by the National Natural Science
Foundation of China (No. 21672239, 21737004 and 21421002),
Key Laboratory of Photochemical Conversion and Optoelectronic
Materials, TIPC, CAS, the Sanming Institute of Fluorochemical
Industry (Nos. FCIT201704GR, FCIT201705GR, FCIT201701BR),
and STS program of Chinese Academy of Science
(KF-STS-QYZX-068) is gratefully acknowledged.
3,3,3-trifluoro-1-(naphthalen-2-yl)propan-1-ol (3r’).3a,3b yellow
liquid, yield: 74%. 1H NMR (400 MHz, CDCl3) δ 7.89 – 7.76 (m, 4H),
7.57 – 7.43 (m, 3H), 5.23 (dd, J = 8.7, 2.7 Hz, 1H), 2.79 – 2.63 (m,
1H), 2.60 – 2.39 (m, 2H). 19F NMR (376 MHz, CDCl3) δ -63.7 (td, J =
10.6, 2.2 Hz).
References
1-(2,5-dimethylphenyl)-3,3,3-trifluoropropan-1-ol (3s’). yellow
liquid, yield: 90%. IR (film) vmax: 3236, 2924, 2872, 1618, 1506,
1456, 1376, 1310, 1271, 1245, 1138, 1093 cm-1. 1H NMR (400 MHz,
CDCl3) δ 7.32 (br, 1H), 7.08 – 7.02 (m, 2H), 5.30 – 5.28 (m, 1H),
2.65 – 2.42 (m, 2H), 2.34 (s, 3H), 2.31 (s, 3H), 2.15 (br, 1H). 13C
NMR (101 MHz, CDCl3) δ 140.2 (s), 136.2 (s), 130.8 (s), 130.6 (s),
128.7 (s), 126.1 (q, J = 275.9 Hz), 125.6 (s), 65.1 (q, J = 3.2 Hz),
41.9 (q, J = 26.8 Hz), 21.0 (s), 18.2 (s). 19F NMR (376 MHz, CDCl3) δ
-64.2 (t, J = 10.7 Hz). HRMS(EI) Calcd for C11H13F3O (M+): 218.0918;
found: 218.0914.
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1417, 1380, 1258, 1178, 1142, 1104, 1022 cm-1. 1H NMR (400 MHz,
CDCl3) δ 8.62 (s, 1H), 5.39 (dd, J = 7.7, 4.2 Hz, 1H), 3.62 (s, 1H),
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1
1252, 1135, 1066, 1005 cm-1. H NMR (400 MHz, CDCl3) δ 8.53 –
8.46 (m, 2H), 7.32 (d, J = 5.3 Hz, 2H), 5.08 (dd, J = 8.8, 2.8 Hz, 1H),
3.37 – 2.33 (m, 3H). 13C NMR (101 MHz, CDCl3) δ 155.5 (s), 144.2
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41.4 (q, J = 27.3 Hz). HRMS(EI) Calcd for C8H8F3NO (M+): 191.0558;
found: 191.0553.
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www.cjc.wiley-vch.de
© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2019, 37, XXX－XXX
This article is protected by copyright. All rights reserved.

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Manuscript received: XXXX, 2019
Manuscript revised: XXXX, 2019
Manuscript accepted: XXXX, 2019
Accepted manuscript online: XXXX, 2019
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Entry for the Table of Contents
XXX
Catalyst-free Hydroxytrifluoromethylation of
Alkenes Using Iodotrifluoromethane
The reaction can be applied to not only styrenes but also to various aliphatic
alkenes with excellent selectivity. We propose a halogen bond interation promotes a
single electron transfer under the visble light irradiation. No catalyst was needed. A
solution of CF3I in DMSO was used as the facile trifluoromethylating reagent.
Zhaoben Sua, Yong Guob,* Qing-Yun Chenb,*,
Zhi-Gang Zhaoa,*, Bao-Yi Nianc
Chin. J. Chem. 2018, template
© 2018 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
This article is protected by copyright. All rights reserved.