Synthesis of trifluoromethylated compounds from alcohols via alkoxydiphenylphosphines

Article abstract of DOI:10.1016/j.jfluchem.2015.08.011

The transformation of hydroxyl group in benzyl or allyl alcohols to trifluoromethyl was achieved via the reaction of the corresponding alkyloxydiphenylphosphine and CuCF₃, generated in situ from methyl fluorosulfonyldifluoroacetate and CuI, under mild conditions. A plausible mechanism was proposed on the basis of experimental results.

Full text of DOI:10.1016/j.jfluchem.2015.08.011

Journal of Fluorine Chemistry 178 (2015) 254–259
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Synthesis of trifluoromethylated compounds from alcohols via
alkoxydiphenylphosphines
Jun-Li Li a, Xian-Jin Yang a,b, Yanan Wang a, Jin-Tao Liu a,
*
a Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032,
China
b Laboratory of Advanced Materials and Institute of Fine Chemicals, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237,
China
A R T I C L E I N F O
A B S T R A C T
Article history:
The transformation of hydroxyl group in benzyl or allyl alcohols to trifluoromethyl was achieved via the
reaction of the corresponding alkyloxydiphenylphosphine and CuCF3, generated in situ from methyl
fluorosulfonyldifluoroacetate and CuI, under mild conditions. A plausible mechanism was proposed on
the basis of experimental results.
Received 17 May 2015
Received in revised form 3 August 2015
Accepted 12 August 2015
Available online 15 August 2015
ß 2015 Elsevier B.V. All rights reserved.
Keywords:
Trifluoromethylation
Alcohol
Alkyloxydiphenylphosphine
Methyl fluorosulfonyldifluoroacetate
Hydroxyl group
1. Introduction
of benzyl halides [7] via the Cu-CF3 species generated from different
precursors are convenient ones. Copper-mediated trifluoromethy-
Recently, organofluorine chemistry has been developed greatly
and played a significant role in a wide range of applications [1].
Among various fluorine-containing compounds, trifluoromethy-
lated compounds received more and more attention due to their
unique physical, physiological, and pharmacokinetic properties.
Accordingly, considerable efforts have been made to introduce
trifluoromethyl group selectively and directly [2]. So far many
effective methods have been developed, for example, the
transformation of methyl group to trifluoromethyl group by
chlorination and the following fluorination with hydrogen fluoride
or metal fluoride [3]. In late 1980s, an efficient trifluoromethyla-
tion strategy involving trifluoromethyl copper (CuCF3) intermedi-
ate formed in situ from methyl fluorosulfonyldifluoroacetate and
copper iodide (CuI) was developed by Chen and coworkers, and has
been extensively applied in academic and industrial fields [4].
More recently, trifluoromethyl copper as a trifluoromethylation
reagent was extensively investigated due to its high efficiency [5].
Similarly, many methods have been developed for the synthesis
of (trifluoroethyl)arenes. The direct transition metal-mediated
trifluoroethylation of arylboronic acids [6] and trifluoromethylation
lation of allylic chlorides and trifluoroacetates was also achieved by
using a Cu-CF3 reagent. These reactions are suitable for selective
synthesis of allyl trifluoromethyl species. Although these methods
are proven efficient, it is still highly desirable to develop new
protocols for their synthesis.
The hydroxyl group is one of the most common functional
groups in organic molecules. If it can be transformed to
trifluoromethyl group, various trifluoromethylated compounds
´
would be conveniently obtained [8]. In 2013, Szabo and coworkers
reported the trifluoromethylation of allylic chlorides and trifluor-
oacetates using a convenient Cu-CF3 reagent [9a]. Qing et al. also
reported the Cu-mediated trifluoromethylation of benzyl metha-
nesulfonates [9b]. On the other hand, Mukaiyama and coworkers
developed an oxidation–reduction condensation reaction which is
known as one of the most useful synthetic methods in organic
synthesis [10]. Various esters, ethers, nitriles and sulfides can be
prepared from alcohols in excellent yields under mild conditions
by the combined use of alkoxydiphenylphosphines and quinones
[11]. In 2003, the one-pot cross-coupling reaction of alkoxy-
methyldiphenylphosphonium iodides and Grignard reagents in the
presence of iodomethane was reported (Scheme 1) [12]. In the
reaction, an ionic intermediate (A) was firstly formed and reacted
with Grignard reagents to give the corresponding cross-coupling
product along with Ph2MeP55O and MgXI.
*
Corresponding author.
E-mail address: jtliu@sioc.ac.cn (J.-T. Liu).
http://dx.doi.org/10.1016/j.jfluchem.2015.08.011
0022-1139/ß 2015 Elsevier B.V. All rights reserved.

J.-L. Li et al. / Journal of Fluorine Chemistry 178 (2015) 254–259
255
Scheme 1. The cross-coupling reaction of alkoxymethyldiphenylphosphonium iodides and Grignard reagents.
Table 1
Optimization of reaction conditions.
Scheme 2. The trifluoromethylation reaction of 4-trifluormethylbenzyl alcohol.
Inspired by above-mentioned reactions, we envisioned that
intermediate A might react with the CuCF3 species formed in situ
from methyl fluorosulfonyldifluoroacetate and CuI in a similar way
to afford trifluoromethyl compounds and phosphine oxide. Herein,
we report the realization of a mild method to transform the
hydroxyl group in benzyl or allyl alcohols to trifluoromethyl via
alkyloxydiphenylphosphines.
Entrya CH3I (equiv) FO2SCF2CO2CH3 (equiv) CuI (equiv) DMF (mL) Yieldb (%)
1
2
3
4
5
6
7
8
1
2
3
3
3
3
3
3
2
2
2
2
2
2
3
4
0.2
0.2
0.2
0.1
0.3
0.2
0.2
0.2
3
3
3
3
3
6
6
6
32
38
42
35
40
65
70
72
a
Reaction conditions: (1) 2a (1.5 mmol), CH3I, DMF, rt, 1 h; (2) FO2SCF2CO2CH3,
2. Results and discussion
CuI, 80 8C, 15 h.
b
Isolated yields.
According to literatures [10,11], 4-trifluoromethylbenzyloxy-
diphenylphosphine (2a) was easily prepared by the reaction of 4-
trifluoromethylbenzyl alcohol (1a) with n-BuLi and the subsequent
reaction with Ph2PCl in tetrahydrofuran (THF). Initially, phosphi-
nite 2a was treated with 1.0 equiv of methyl iodide in dimethyl-
formide (DMF) at room temperature. After 1 h, 2.0 equiv of methyl
fluorosulfonyldifluoroacetate and 20 mol% of copper iodide were
added and the mixture was stirred at 80 8C. Full conversion of 2a
was achieved in 15 h, and gratifyingly the desired product 1-(2,2,2-
trifluoroethyl)-4-(trifluoromethyl)benzene (3a) was obtained in
32% yield (Scheme 2).
Optimization of the reaction conditions was then carried out
and the results were shown in Table 1. Increasing the amount of
methyl iodide to 3.0 equiv, the yield of 3a was improved to 42%
(Table 1, entries 1–3). Changing catalyst loading had little influence
on the reaction (entries 4–5). Considering the low solubility of CuI
in DMF, more DMF was tried and it was found that when the
amount of DMF was increased from 3.0 to 6.0 mL, the yield of 3a
Table 2
The reaction of substituted benzyl alcohols and allyl alochols with trifluoromethylating reagent.
.
Entrya
1
1 (R, n)
Product 3
Yield (%)b
70
1a (p-CF3, 0)
2
1b (H, 0)
70

256
J.-L. Li et al. / Journal of Fluorine Chemistry 178 (2015) 254–259
Table 2 (Continued )
Entrya
1 (R, n)
Product 3
Yield (%)b
26
3
1c (p-OMe, 0)
1d (p-Me, 0)
1e (p-Br, 0)
1f (p-Cl, 0)
4
5
6
57
57
60
7
1g (o-Cl, 0)
51
8
9
1h (H, 1)
51
55
54
1i (p-Cl, 1)
1j (o-Cl, 1)
10
11
12
1k (p-Me, 1)
45
10c
13
0
14
0
a
Reaction conditions: (a) 1 (1.5 mmol), n-BuLi (1.5 mmol), Ph2PCl (1.5 mmol), THF, 0 8C, 1 h; (b) MeI (4.5 mmol), DMF, rt, 1 h; (c) FO2SCF2CO2CH3 (4.5 mmol), CuI (0.3 mmol),
80 8C, 15 h.
b
Isolated yields.
Determined by 19F NMR.
c

J.-L. Li et al. / Journal of Fluorine Chemistry 178 (2015) 254–259
257
synthesized from the corresponding alcohols under mild
conditions.
4. Experimental
4.1. General
Infrared spectra were recorded on Shimadzu IR-440 spectrom-
eter. High-resolution mass spectra (HRMS) were determined on a
Finnigan MAT 8430 spectrometer. Low-resolution mass spectra
were obtained on a HP-5989A spectrometer. 1H, 13C and 19F NMR
spectra were recorded on Bruker AM-300 (300 MHz) and Varian
VXR (300 MHz) spectrometers in CDCl3 at ambient temperature
using tetramethylsilane (1H NMR) or residual CHCl3 (1H and 13C
NMR) as the internal standard, or CFCl3 (19F NMR) as the external
standard, J values are reported in Hz. Flash column chromatogra-
phy was performed using silica gel (300–400 mesh). Unless
otherwise noted, all commercially available compounds (1a–1h,
CuI, FO2SCF2CO2CH3, CH3I, Ph2PCl, DIBAL-H, triethylphosphonoa-
cetate and p-chlorobenzaldehyde) were used as received without
further purification. Solvents were purified according to literature
[15].
Scheme 3. The plausible reaction mechanism.
was improved to 65% (entry 6). Using 3.0 equiv of FO2SCF2CO2CH3,
3a was obtained in 70% yield (entry 7). Continuing to increase the
amount of FO2SCF2CO2CH3 improved the yield of 3a slightly
(4.0 equiv, 72%, entry 8). Therefore, the optimal conditions were
set to 20 mol% of CuI, 3.0 equiv of FO2SCF2CO2CH3 and 3.0 equiv of
MeI in DMF (6 mL) at 80 8C.
4.2. General procedure for the preparation of compounds 1i–1k
Under the optimized conditions, the scope of alcohols was
examined and a variety of trifluoromethylated compounds were
synthesized. As shown in Table 2, the reaction tolerated a broad
range of functional groups. The electronic nature of alcohols had
obvious influence on the reaction. Good yield was obtained with
benzyl alcohol (1b) (Table 2, entry 2). Benzyl alcohols bearing
electron-donating substituents such as methoxy and methyl group
gavelower yields(entries 3 and4). The reaction of halide substituted
benzyl alcohols 1e–1g proceeded well to give the corresponding
products3e–3ginmoderateyields (entries 5–7). Underthe standard
conditions, the reaction of allyl alcohols occurred smoothly to give
the desired trifluoromethylated products 3h–3k in moderate yields
(entries 8–11). Secondary alcohol 1l showed low activity and only
10% yield was achieved because of the steric hindrance (entry 12).
The reactions ofalcohols 1mand 1nwereunsuccessful, partially due
to their low reactivity (entries 13–14).
To a solution of (E)-ethyl-3-phenylacrylate (12 mmol) in
toluene (20 mL), DIBAL-H (29 mL, 1.0 M) was added at À78 8C.
The mixture was allowed to rise to room temperature and
quenched with 2 N HCl (50 mL). The resulting mixture was
extracted with CH2Cl2 and the combined organic solution was
dried over sodium sulfate. After the removal of solvent, the residue
was purified by column chromatography on silica gel to give 1
(eluent: ethyl acetate/n-hexane = 1:20).
4.2.1. (E)-3-(4-Chlorophenyl)prop-2-en-1-ol (1i)
Colorless oil (1.5 g, yield: 57%). 1H NMR (300 MHz, CDCl3):
d
7.30–7.26 (m, 4H), 6.58 (d, J = 15.9 Hz, 1H), 6.35 (dt, J = 15.7, 4.5 Hz,
1H), 4.33 (m, 2H).
4.2.2. (E)-3-(2-Chlorophenyl)prop-2-en-1-ol (1j)
Colorless oil (2.08 g, yield: 79%). 1H NMR (300 MHz, CDCl3):
d
On the basis of the above experimental results and related
literatures [5,12,13], a plausible reaction mechanism was proposed
for the formation of 3 as shown in Scheme 3. Initially, the
salification of 2 with methyl iodide gave intermediate alkox-
ymethyldiphenylphosphonium iodide A, which reacted with
CuCF3 generated in situ to give product 3 and regenerate CuI via
intermediate B. From this hypothesis, it is reasonable that the
transformation of alcohols with electron-donating substituent on
the phenyl ring was difficult to occur because the substituent made
the alkoxymethyldiphenylphosphonium species less reactive to
trifluoromethyl anion. There is another possibility. It was reported
that intermediate A could decompose to RI in the presence of
copper salt [14]. We also observed the formation of RI in the
reaction of intermediate A and catalytic amount of copper iodide at
80 8C. Therefore, the trifluoromethylation of RI may also occur to
afford product 3.
7.51 (d, J = 7.5 Hz, 1H), 7.33 (d, J = 7.5 Hz, 1H), 7.23–7.16 (m, 2H),
6.99 (d, J = 16.2 Hz, 1H), 6.39–6.29 (dt, J = 16.2, 5.7 Hz, 1H), 4.32 (d,
J = 5.7 Hz, 2H), 2.07 (s, 1H).
4.2.3. (E)-3-(p-Tolyl)prop-2-en-1-ol (1k)
Colorless oil (1.58 g, yield: 66%). 1H NMR (300 MHz, CDCl3):
d
7.32–7.27 (m, 2H), 7.21–7.14 (m, 2H), 6.60 (d, J = 15.6 Hz, 1H),
6.39–6.31 (dt, J = 15.6, 6.0 Hz, 1H), 4.67 (s, 1H), 4.32 (d, J = 6.0 Hz,
2H), 2.37 (s, 3H).
4.3. General procedure for the preparation of compound 3
To a stirred solution of benzyl or allyl alcohol (1, 1.5 mmol) in
THF (10 mL) was added n-BuLi (1.6 M in hexane, 0.95 mL) at 0 8C.
The mixture was warmed to room temperature. After stirring for
1 h, a solution of Ph2PCl (1.5 mmol) in THF (5 mL) was added at
0 8C, and the resulted mixture was continuously stirred at room
temperature for 1 h and quenched with water after completion of
the reaction (detected by TLC). The aqueous layer was extracted
with dichloromethane. The combined organic layer was dried over
anhydrous sodium sulfate. Compound 2 was obtained after
filtration and evaporation.
3. Conclusion
In summary, a mild method for the preparation of trifluor-
omethylated compounds from benzyl or allyl alcohols has been
developed. Alkyloxydiphenylphosphine was prepared and used
as key intermediate to react with methyl iodide and methyl
fluorosulfonyldifluoroacetate in the presence of CuI. A series
of trifluoromethyl-containing aromatics and alkenes were
To a solution of 2 in DMF (10 mL) was added CH3I (4.5 mmol) at
room temperature. After stirring for 1 h, methyl fluorosulfonyldi-
fluoroacetate (4.5 mmol) and CuI (0.30 mmol) were added. The

258
J.-L. Li et al. / Journal of Fluorine Chemistry 178 (2015) 254–259
mixture was heated and stirred at 80 8C for 15 h. Then the reaction
was quenched with water and the resulting mixture was extracted
with diethyl ether. The extract was dried over sodium sulfate. After
removal of solvent, the crude product was purified by chromatog-
raphy on silica gel to give 3 (eluent: n-hexane).
4.3.11. (E)-1-Methyl-4-(4,4,4-trifluorobut-1-en-1-yl)benzene (3k)
[8i]
Colorless oil (135 mg, 45%); 1H NMR (300 MHz, CDCl3):
d 7.31
(d, J = 8.0 Hz, 2H), 7.40 (d, J = 8.0 Hz, 2H), 6.60 (d, J = 16.0 Hz, 1H),
6.08 (dt, J = 16.0, 7.0 Hz, 1H), 3.07 (dq, J = 11.0, 7.0 Hz, 2H), 2.38 (s,
3H). 19F NMR (282 MHz, CDCl3):
d
À66.3 (t, J = 11.0 Hz, 3F).
4.3.1. 1-(2,2,2-Trifluoroethyl)-4-(trifluoromethyl)benzene (3a) [8g]
Colorless oil (239 mg, 70%); 1H NMR (300 MHz, CDCl3):
d
7.64–
Acknowledgement
7.61 (m, 2H), 7.42 (d, J = 8.4 Hz, 2H), 3.43 (q, J = 10.5 Hz, 2H); 19F
NMR (282 MHz, CDCl3):
J = 10.5 Hz, 3F).
d
À62.73 (d, J = 17.8 Hz, 3F), À65.69 (t,
The authors thank the National Natural Science Foundation of
China for financial support (Nos. 21172243 and 21421002).
4.3.2. (2,2,2-Trifluoroethyl)benzene (3b) [16]
Colorless oil (168 mg, 70%); 1H NMR (300 MHz, CDCl3):
d 7.35–
Appendix A. Supplementary data
7.28 (m, 5H), 3.35 (q, J = 10.8 Hz, 2H). 19F NMR (282 MHz, CDCl3):
À66.38 (t, J = 10.8 Hz, 3F).
d
Supplementary material related to this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.jfluchem.2015.08.011.
4.3.3. 1-(2,2,2-Trifluoroethyl)-4-(trifluoromethyl)benzene (3c) [6]
Colorless oil (74 mg, 26%); 1H NMR (300 MHz, CDCl3):
d 7.21 (d,
References
J = 8.8 Hz, 2H), 6.88 (d, J = 8.8 Hz, 2H), 3.80 (s, 3H), 3.24 (q,
J = 11.2 Hz, 2H). 19F NMR (282 MHz, CDCl3):
J = 11.2 Hz, 3F).
d
À66.39 (t,
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4.3.4. 1-Methyl-4-(2,2,2-trifluoroethyl)benzene (3d) [8g]
Colorless oil (149 mg, 57%); 1H NMR (300 MHz, CDCl3):
7.20 (m, 4H), 3.35 (q, J = 10.8 Hz, 2H), 2.38 (s, 3H). 19F NMR
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À66.10 (t, J = 10.8 Hz, 3F).
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7.50 (m, 2H), 7.20 (d, J = 8.4 Hz, 2H), 3.35 (q, J = 10.8 Hz, 2H). 19F
NMR (282 MHz, CDCl3):
d
À65.99 (t, J = 10.8 Hz, 3F).
4.3.6. 1-Chloro-4-(2,2,2-trifluoroethyl)benzene (3f) [8g]
Colorless oil (174 mg, 60%); 1H NMR (300 MHz, CDCl3):
d 7.36
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(d, J = 8.4 Hz, 2H), 7.25 (d, J = 8.4 Hz, 2H), 3.36 (q, J = 10.8 Hz, 2H).
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À66.04 (t, J = 10.8 Hz, 3F).
d
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d 7.44–
7.19 (m, 4H), 3.61 (q, J = 10.5 Hz, 2H). 19F NMR (282 MHz, CDCl3):
À65.21 (t, J = 10.5 Hz, 3F).
d
4.3.8. (E)-(4,4,4-Trifluorobut-1-en-1-yl)benzene (3h) [8i]
Colorless oil (142 mg, 51%); 1H NMR (300 MHz, CDCl3):
d 7.40–
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3.36 (dq, J = 10.9, 7.5 Hz, 2H). 19F NMR (282 MHz, CDCl3):
(t, J = 10.9 Hz, 3F).
d
À66.04
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4.3.9. (E)-1-Chloro-4-(4,4,4-trifluorobut-1-en-1-yl)benzene (3i) [8i]
Colorless oil (181 mg, 55%); 1H NMR (300 MHz, CDCl3):
7.33–
d
7.29 (m, 4H), 6.58 (d, J = 15.6 Hz, 1H), 6.11 (dt, J = 15.6, 7.2 Hz, 1H),
3.01 (dq, J = 10.8, 7.2 Hz, 2H). 19F NMR (282 MHz, CDCl3):
(t, J = 10.8 Hz, 3F).
d
À66.14
4.3.10. (E)-1-Chloro-2-(4,4,4-trifluorobut-1-en-1-yl)benzene (3j)
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Colorless oil (178 mg, 54%); IR (film): 3060, 1593, 1367, 1258,
1142, 968, 751 cmÀ1. 1H NMR (300 MHz, CDCl3):
d 7.57–7.54 (m,
1H), 7.41–7.37 (m, 1H), 7.29–7.21 (m, 2H), 7.04 (d, J = 16.2 Hz, 1H),
6.13 (dt, J = 16.2, 7.2 Hz, 1H), 3.07 (dq, J = 11.0, 7.2 Hz, 2H). 19F
NMR (282 MHz, CDCl3):
(75 MHz, CDCl3):
d
À66.08 (t, J = 11.0 Hz, 3F). 13C NMR
d
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(3.30), 69 (9.65). HRMS (EI): Calcd. for C10H8ClF3 (M+): 220.0267;
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