Metal-free catalyzed regioselective allylic trifluoromethanesulfonylation of aromatic allylic alcohols with sodium trifluoromethanesulfinate

Article abstract of DOI:10.1021/acs.joc.5b02674

An efficient procedure for the preparation of allylic trifluoromethanesulfones with high regioselectivity from aromatic allylic alcohols/esters and NaSO₂CF₃ under transition-metal-free conditions is described. A wide range of functional groups were tolerated. This is the first example to realize different types of allylic alcohols, including primary, secondary, and tertiary allylic alcohols, all of which transferred to the corresponding products efficiently in good to excellent yields with readily available and inexpensive NaSO₂CF₃. The synthetic utility of the method was demonstrated by performing the reaction at gram scale.

Full text of DOI:10.1021/acs.joc.5b02674

Note
pubs.acs.org/joc
Metal-Free Catalyzed Regioselective Allylic
Trifluoromethanesulfonylation of Aromatic Allylic Alcohols with
Sodium Trifluoromethanesulfinate
Jianhua Liao,†,‡ Wei Guo,† Zhenming Zhang,† Xiaodong Tang,† Wanqing Wu,*,† and Huanfeng Jiang*,†
†School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, China
‡School of Pharmaceutical Sciences, Gannan Medical University, Ganzhou, Jiangxi 341000, China
S
* Supporting Information
ABSTRACT: An efficient procedure for the preparation of
allylic trifluoromethanesulfones with high regioselectivity from
aromatic allylic alcohols/esters and NaSO2CF3 under transition-
metal-free conditions is described. A wide range of functional
groups were tolerated. This is the first example to realize
different types of allylic alcohols, including primary, secondary,
and tertiary allylic alcohols, all of which transferred to the
corresponding products efficiently in good to excellent yields
with readily available and inexpensive NaSO2CF3. The synthetic
utility of the method was demonstrated by performing the
reaction at gram scale.
Scheme 1. Reported Methods for the Synthesis of Allylic
he incorporation of fluorine-containing groups into
Triflones
T
organic molecules has received increasing attention in
the pharmaceutical and agrochemical industries, since fluorine-
containing organic molecules exhibit unique chemical, physical,
and biological properties.1 To date, the trifluoromethane-
sulfonyl (triflyl) group is an intensely studied fluorine-
containing group for its strong electron-withdrawing power
and high lipophilicity.2 Consequently, due to their potential
applications in chemistry, pharmacy, and biology, allylic
trifluoromethanesulfonylated compounds have become a
vibrant research area in synthetic organic chemistry.3 However,
few successful approaches have been developed over the past
decades,4−7 such as the reactions of isoprenoid perfluoroalkyl
sulfones and alkyllidenemalonates,4 radical-mediated atom-
transfer addition from iodomethyl trifluoromethanesulfone
(triflone) and alkynes,5 rearrangement of cinnamyl triflinate
synthesized from allylic alcohol with trifluoromethane sulfonyl
chloride,6 and substitution of a diaryl-type tertiary allylic
alcohol with trifluoromethyl sulfinic acid7 (Scheme 1). Despite
these important advances, the traditional approaches to allylic
triflones are limited in scope due to the limited availability of
triflone reagents, prefunctionalization, harsh reaction con-
ditions, formation of the isomeric products, low yields, and
narrow substrate scope. Therefore, many attempts can still be
anticipated by the creation of a new and efficient strategy
capable of overcoming these limitations in current processes.
Allylic functionalization has long been intensely studied for
its diversity of bond-forming types and extensive applications in
chemical synthesis.8 For most of the earlier history of allylic
functionalization reactions, activated precursors of π-allyl
fragments, such as allylic esters and carbonates derived from
allylic alcohols and acetic acid, have predominantly been
employed to accept the nucleophilic attack of nucleophiles.9 In
this respect, stoichiometric amounts of alcohols and organic
waste inevitably are produced. Recently, transition-metal-
Received: November 22, 2015
© XXXX American Chemical Society
A
DOI: 10.1021/acs.joc.5b02674
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
a
catalyzed allylic functionalization has become an attractive
synthetic method via the formation of cationic η3-allyl
intermediates.10−14 The direct use of allylic alcohols as
allylating reagents would be highly active for their synthetic
reliability and step economy. While significant progress in the
catalysis of allylic sulfonylation with sodium arenesulfinates has
been made in recent years,15 the use of allylic alcohols as
allylating reagents for the synthetic incorporation of the
trifluoromethanesulfonyl moiety is still an imposing challenge
for chemists.
Table 1. Optimization of the Reaction Conditions
b
entry
additive
TfOH
solvent
T (°C) time (h) yield (%)
1
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
DMSO
DMF
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
110
80
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
12
6
n.d.
88
72
2
TsOH
3
HBF4
4
HOAc
68
It was noteworthy that NaSO2CF3 was developed by
Langlois as a trifluoromethylating reagent at the beginning.16
Notably, various examples of the use of NaSO2CF3 as a triflyl
source have also been reported.17 Given the increasing
prevalence of triflones in medicinally relevant compounds,18
the significant challenges in introducing the triflyl group by
using the readily available and inexpensive NaSO2CF3 as a
nucleophile will be of synthetic value. However, the coupling
partners with NaSO2CF3 usually occur with strongly electron-
withdrawing electrophilic reagents, such as diaryliodonium
salts17a and arenediazonium tetrafluoroborates,17b owing to the
poor nucleophilicity of NaSO2CF3. Thus, we envisioned that
the allylic triflones could be prepared from the coupling
reactions between allylic alcohols and NaSO2CF3, proceeding
via cationic π-allyl intermediates generated by Lewis or
Brønsted acid catalysis.10d,19 As we have continuing interest
in sodium sulfinates and based on our previous work with allylic
alcohols,20 we herein report a concise and efficient metal-free
catalyzed method for coupling of allylic alcohols/esters using
NaSO2CF3 as a trifluoromethanesulfonylation (triflylation)
source to generate allylic triflones with high regioselectivity
via nucleophilic substitution. To the best of our knowledge, it is
the first example to realize different types of allylic alcohols,
including primary, secondary, and tertiary allylic alcohols, all of
which were transferred to the corresponding products
efficiently in good to excellent yields.
5
TFA
75
6
HCl
65
7
H2SO4
67
8
PdCl2
15
9
CuCl2
65
10
11
12
13
14
ZnCl2
25
FeCl3
51
TsOH
trace
trace
46
TsOH
TsOH
toluene
CH3CN
THF
c
15
TsOH
n.d.
n.d.
21
c
16
c
TsOH
17
TsOH
DCE
18
19
20
21
22
23
24
25
26
27
TsOH
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
86
TsOH
75
TsOH
50
<5
n.d.
55
TsOH
rt
TsOH
100
100
100
100
100
100
TsOH
30
TsOH (1.5 equiv)
TsOH (1.0 equiv)
TsOH (0.5 equiv)
TsOH (0.2 equiv)
20
20
20
20
83
80
68
30
a
Reaction conditions: unless otherwise noted, all reactions were
performed with 1aa (0.25 mmol), 2 (0.75 mmol), additive (0.5
mmol), solvent (3 mL), 100 °C, 20 h. Isolated yields based on 1aa.
b
c
We initiated our investigations using vinylbenzyl alcohol
(1aa) with NaSO2CF3 (2) as the substrates. Performing the
reaction using 2 equiv of trifluoromethanesulfonic acid (TfOH)
in dioxane was expected to generate (E)-(3-((trifluoromethyl)
sulfonyl)prop-1-en-1-yl)benzene (3a) in good yield (Table 1,
entry 1). Disappointingly, the desired product 3a was not
obtained with recovery of starting material. To improve the
yield of 3a, various Brønsted acids were screened. To our
delight, the use of the p-toluenesulfonic acid (TsOH) gave an
excellent yield of 3a (88%) (Table 1, entry 2). Other Brønsted
acids were studied and found to be inferior in terms of product
yields (Table 1, entries 3−7). Lewis acidic catalysts previously
reported to activate the hydroxyl group of alcohols in
nucleophilic substitution reaction were also evaluated,16 and
the results were unsatisfactory (Table 1, entries 8−11). Solvent
studies revealed that the use of dioxane as solvent provided the
best result (Table 1, entries 12−17). Additionally, the reaction
temperatures, reactions time, and the amount of additive were
also screened (Table 1, entries 18−27). At lower temperatures
and with a shorter reaction time, significantly lower yields were
observed, while decreasing the amount of TsOH resulted in the
yields decreasing accordingly. We also investigated the effect of
concentration on the reaction. A higher concentration is not
beneficial to the solubility of the materials, although no further
decrease in yields was observed below 0.08 M.
At 65 °C.
(Table 2). A series of para-substituted phenyl rings with
electron-donating (1aa−1ac) and electron-withdrawing (1ad−
1af) groups generated products 3a−3f in good to excellent
yields. The presence of both a strongly electron-donating
methoxy group and an electron-withdrawing trifluoromethyl
group were also tolerated in moderate yields (Table 2, 3g, h).
Meanwhile, the substrates with a substituted phenyl ring were
converted to the desired products in good yields (Table 2, 3i−
k). Notably, the heteroaryl substituents, such as furan and
thiophene, were also compatible with the transformation, and
the corresponding products could be afforded in moderate
yields (Table 2, 3l, m). 1-(Naphthalen-2-yl)prop-2-en-1-ol
(1an) proceeded smoothly to give the desired product 3n in an
excellent yield of 92%. To our delight, the steric effect of
substituents seemed to have no influence on the reaction, and
the corresponding allylic triflones were generated in good yields
(Table 2, 3o, p).
To expand the substrate scope of the transformation,
nonterminal allylic alcohols were screened (Table 3). In
general, the phenyl substituted cinnamyl alcohols with both
electron-donating and -withdrawing groups in the para- and
meta-positions reacted efficiently to afford the corresponding
allylic triflones in good to excellent yields (Table 3, entries 1−
5). Heteroaryl substrates were also compatible under the
Having established the optimal reaction conditions (Table 1,
entry 2), the scope of various allylic alcohols was investigated
B
DOI: 10.1021/acs.joc.5b02674
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The Journal of Organic Chemistry
Note
a b
,
a b
,
Table 2. Scope of Allyl Alcohols
Table 3. Scope of Cinnamyl Alcohols
a
Reaction conditions: 1b (0.25 mmol), 2 (0.75 mmol), TsOH (0.5
b
mmol), dioxane (3 mL), 100 °C, 20 h. Isolated yields based on 1b.
a b
,
Table 4. Scope of Cinnamyl Esters
a
Reaction conditions: 1a (0.25 mmol), 2 (0.75 mmol), TsOH (0.5
b
mmol), dioxane (3 mL), 100 °C, 20 h. Isolated yields based on 1a.
standard reaction conditions (Table 3, entry 6). Additionally,
the R2, and R3 substituted cinnamyl alcohols also worked well
to finish the C−S bond transformation (Table 3, entries 7, 8).
To further demonstrate the generality of this protocol, we
explored the scope of allylic esters for allylic triflone synthesis
(Table 4). Delightfully, a wide range of cinnamyl esters could
be converted into the corresponding product 3a in moderate to
good yields, such as cinnamyl alkyl esters, cinnamyl-2-
aminobenzoate, and cinnamyl cinnamate compounds (Table
4, entries 1−7). On the basis of the our results and previous
reports,12,16 we propose that the current reaction proceeds
through an SN1-type pathway by the formation of cationic π-
allyl intermediates with strongly electrophilic properties. The
direct substitution of the hydroxyl group of alcohols would be
activated by p-toluenesulfonic acid. Thus, the reaction of allylic
alcohols/esters coupled with NaSO2CF3 could be realized
smoothly.
a
Reaction conditions: 1c (0.25 mmol), 2 (0.75 mmol), TsOH (0.5
b
mmol), dioxane (3 mL), 100 °C, 20 h. Isolated yields based on 1c.
As a demonstration of the scalability of this transformation,
the allylic triflylation of cinnamyl alcohol (1ba) with
NaSO2CF3 was performed at the gram scale (Scheme 2).
Analytically pure 3a was isolated in 81% yield (1.620 g)
through a pad of silica gel.
In summary, a convenient and highly efficient method for
direct allylic triflylation with excellent regioselectivity from the
reaction of allylic alcohols/esters with NaSO2CF3 has been
developed. Both electron-rich and -poor substituted allylic
alcohols provided the coupled products in good yields. The
synthetic utility of the method was demonstrated by perform-
ing the reaction on a gram scale. Such a new and
C
DOI: 10.1021/acs.joc.5b02674
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
3478, 3415, 1434, 1366, 618; HRMS (ESI) m/z: calcd for
C11H11F3NaO2S [M + Na]+, 287.0324; found, 287.0321.
Scheme 2. Gram-Scale Allylic Triflylation of Cinnamyl
Alcohol
(E)-1-(tert-Butyl)-4-(3-((trifluoromethyl)sulfonyl)prop-1-en-1-yl)-
1
benzene (3c). Yield: 85% (65.0 mg); colorless oil; H NMR (400
MHz, CDCl3) δ 7.37 (q, J = 8.5 Hz, 4H), 6.78 (d, J = 15.8 Hz, 1H),
6.09 (td, J = 7.6 Hz, J = 15.5 Hz, 1H), 4.12 (d, J = 7.6 Hz, 2H), 1.32 (s,
9H); 13C NMR (100 MHz, CDCl3) δ 152.6, 141.5, 132.3, 126.8,
125.8, 119.7 (q, J = 328.3 Hz), 109.3, 54.6, 34.8, 31.2; 19F NMR (376
MHz, CDCl3) δ −76.19 ppm; νmax (KBr)/cm−1 3201, 2964, 1402,
1368, 1209, 1195, 620; HRMS (ESI) m/z: calcd for C14H17F3NaO2S
[M + Na]+, 329.0794; found, 329.0794.
(E)-1-Fluoro-4-(3-((trifluoromethyl)sulfonyl)prop-1-en-1-yl)-
benzene (3d). Yield: 80% (53.6 mg); colorless solid, mp = 48−49 °C;
1H NMR (400 MHz, CDCl3) δ 7.41−7.38 (m, 2H), 7.04 (t, J = 7.9
Hz, 2H), 6.78 (d, J = 15.8 Hz, 1H), 6.09−6.02 (m, 1H), 4.13 (d, J =
7.5 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 163.3 (d, J = 249.5 Hz),
140.5, 131.3 (d, J = 3.4 Hz), 128.7, 128.6, 119.7 (q, J = 328.6 Hz),
116.0, 115.8, 109.9 (d, J = 2.0 Hz), 54.3; 19F NMR (376 MHz, CDCl3)
δ −76.33, −111.59 ppm; νmax (KBr)/cm−1 3169, 1401, 1120, 622;
HRMS (ESI) m/z: calcd for C10H8F4NaO2S [M + Na]+, 291.0073;
found, 291.0070.
straightforward protocol, which utilizes the commercially ready
and inexpensive NaSO2CF3 reagent as a triflyl source, would
extend the potential application of allylic triflones in
pharmaceutical and synthetic chemistry.
EXPERIMENTAL SECTION
■
General Information. Melting points were measured with a
melting point instrument and were uncorrected. H and 13C NMR
1
spectra were recorded using a 400 MHz NMR spectrometer. The
chemical shifts are referenced to signals at 7.26 and 77.0 ppm,
respectively, with CDCl3 as the solvent and TMS as the internal
standard. IR spectra were obtained either as potassium bromide pellets
or as liquid films between two potassium bromide pellets with a
spectrometer. GC-MS was obtained using electron ionization. HRMS
was obtained with an LCMS-IT-TOF mass spectrometer or recorded
on an EI-ion trap High Resolution mass spectrometer. TLC was
performed by using commercially prepared 100−400 mesh silica gel
plates, and visualization was effected at 254 nm. Starting materials of
terminal allylic alcohols were prepared according to previously
reported methods.1 Nonterminal allylic alcohols were synthesized
from reduction of commercial available cinnamyl aldehydes by NaBH4.
NaSO2CF3, cinnamyl esters, vinylbenzyl alcohol, 1-phenylprop-2-en-1-
ol, 2-methyl-1-phenylprop-2-en-1-ol, (E)-3-phenylprop-2-en-1-ol, and
(E)-2-methyl-3-phenylprop-2-en-1-ol were commercially available.
General Procedure for Synthesis of Cinnamyl Trifluoro-
methanesulfone. In a sealed test tube, a mixture of allylic alcohol (or
allylic esters), 1 (0.25 mmol), NaSO2CF3 2 (117 mg, 0.75 mmol),
TsOH (86 mg, 0.5 mmol), and 3 mL of dioxane was vigorously stirred
at 100 °C for 20 h. After completion of the reaction, the mixture was
quenched by saturated brines and extracted with ethyl acetate (3 × 10
mL). The combined ethyl acetate layer was then dried over sodium
sulfate and concentrated in vacuum. And the resulting crude product
was purified by silica gel chromatography using a mixture of EtOAc−n-
hexane (1:50) as eluent to afford the desired product.
(E)-1-Chloro-4-(3-((trifluoromethyl)sulfonyl)prop-1-en-1-yl)-
benzene (3e). Yield: 84% (59.6 mg); colorless solid, mp = 56−57 °C;
1H NMR (400 MHz, CDCl3) δ 7.39−7.30 (m, 4H), 6.77 (d, J = 15.8
Hz, 1H), 6.15−6.08 (m, 1H), 4.13 (d, J = 7.3 Hz, 2H); 13C NMR (100
MHz, CDCl3) δ 140.4, 135.1, 133.4, 129.1, 128.2, 119.6 (q, J = 328.3
Hz), 110.9, 54.3; 19F NMR (376 MHz, CDCl3) δ −76.26 ppm; νmax
(KBr)/cm−1 3148, 1401, 1122; HRMS (EI) m/z: calcd for
C10H8ClF3O2S [M]+, 283.9886; found, 283.9881.
(E)-1-Bromo-4-(3-((trifluoromethyl)sulfonyl)prop-1-en-1-yl)-
benzene (3f). Yield: 88% (72.2 mg); colorless solid, mp = 75−76 °C;
1H NMR (400 MHz, CDCl3) δ 7.51 (d, J = 8.3 Hz, 2H), 7.30 (d, J =
8.4 Hz, 2H), 6.78 (d, J = 15.8 Hz, 1H), 6.16 (td, J = 7.6 Hz, J = 15.5
Hz, 1H), 4.16 (d, J = 7.6 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ
140.5, 133.9, 132.0, 128.4, 123.3, 119.7 (q, J = 328.6 Hz), 111.1, 54.3;
19F NMR (376 MHz, CDCl3) δ −76.29 ppm; νmax (KBr)/cm−1 3160,
1402, 1120, 621; HRMS (ESI) m/z: calcd for C10H8BrF3NaO2S [M +
Na]+, 350.9273; found, 350.9276.
(E)-1-Methoxy-4-(3-((trifluoromethyl)sulfonyl)prop-1-en-1-yl)-
benzene (3g). Yield: 58% (40.6 mg); colorless solid, mp = 55−56 °C;
1H NMR (400 MHz, CDCl3) δ 7.36 (d, J = 8.6 Hz, 2H), 6.88 (d, J =
8.6 Hz, 2H), 6.75 (d, J = 15.7 Hz, 1H), 5.98 (td, J = 7.6 Hz, J = 15.5
Hz, 1H), 4.11 (d, J = 7.6 Hz, 2H), 3.82 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 160.5, 141.3, 128.4, 127.8, 119.7 (q, J = 328.5 Hz), 114.2,
107.4, 55.4, 54.6; 19F NMR (376 MHz, CDCl3) δ −76.23 ppm; νmax
(KBr)/cm−1 3134, 1604, 1119, 622; HRMS (ESI) m/z: calcd for
C11H11F3NaO3S [M + Na]+, 303.0273; found, 303.0273.
(E)-1-(Trifluoromethyl)-4-(3-((trifluoromethyl)sulfonyl)prop-1-en-
1-yl)benzene (3h). Yield: 43% (34.2 mg); colorless solid, mp = 84−85
°C; 1H NMR (400 MHz, CDCl3) δ 7.54 (d, J = 8.2 Hz, 2H), 7.44 (d, J
= 8.1 Hz, 2H), 6.78 (d, J = 15.9 Hz, 1H), 6.17 (td, J = 7.6 Hz, J = 15.5
Hz, 1H), 4.09 (d, J = 7.6 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ
140.1, 138.3, 130.9 (q, J = 31.8 Hz), 127.2, 125.8, 125.8, 121.8 (q, J =
328.3 Hz), 113.2, 54.2; 19F NMR (376 MHz, CDCl3) δ −62.83,
−76.30 ppm; νmax (KBr)/cm−1 3136, 1605, 1401, 1119, 621; HRMS
(EI) m/z: calcd for C11H8F6O2S [M]+, 318.0149; found, 318.0145.
(E)-1-Methyl-2-(3-((trifluoromethyl)sulfonyl)prop-1-en-1-yl)-
benzene (3i). Yield: 82% (54.1 mg); colorless solid, mp = 73−74 °C;
1H NMR (400 MHz, CDCl3) δ 7.43 (d, J = 7.2 Hz, 1H), 7.25−7.16
(m, 3H), 7.04 (d, J = 15.6 Hz, 1H), 6.00 (td, J = 7.5 Hz, J = 15.3 Hz,
1H), 4.15 (d, J = 7.4 Hz, 2H), 2.35 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 139.9, 136.0, 134.3, 130.6, 129.1, 126.4, 126.2, 119.8 (q, J =
328.5 Hz), 111.7, 54.6, 19.6; 19F NMR (376 MHz, CDCl3) δ −76.05
ppm; νmax (KBr)/cm−1 3175, 3012, 1602, 1401, 1122; HRMS (ESI)
m/z: calcd for C11H11F3NaO2S [M + Na]+, 287.0324; found,
287.0324.
Procedure for Gram-Scale Allylic Trifluoromethane-
sulfonylation of Cinnamyl Alcohol. A mixture of cinnamyl alcohol
1ba (8 mmol), NaSO2CF3 2 (3.744 g, 24 mmol), TsOH (2.752 g, 16
mmol), and 60 mL of dioxane were added to a 150 mL round-
bottomed flask, which was connected to a condenser and sealed with a
balloon, and then vigorously stirred at 100 °C for 72 h. After
completion of the reaction, the mixture was extracted with ethyl
acetate (3 × 50 mL). The combined ethyl acetate layer was then dried
over sodium sulfate and concentrated in vacuum. After evaporation of
the solvent, the crude mixture was purified by silica gel column
chromatography, to afford 3a (1.620 g, >98% purity, 81% yield).
(E)-(3-(Ttrifluoromethyl)sulfonyl)prop-1-en-1-yl)benzene (3a).
1
Yield: 88% (55.0 mg); colorless oil; H NMR (400 MHz, CDCl3) δ
7.41−7.33 (m, 5H), 6.80 (d, J = 15.8 Hz, 1H), 6.15−6.08 (m, 1H),
4.12 (d, J = 7.3 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 141.7, 135.0,
129.3, 128.9, 127.0, 119.7 (q, J = 328.5 Hz), 110.2, 54.5; 19F NMR
(376 MHz, CDCl3) δ −76.22 ppm; νmax (KBr)/cm−1 3169, 3135,
3012, 1401, 1119; HRMS (ESI) m/z: calcd for C10H9F3NaO2S [M +
Na]+, 273.0168; found, 273.0169.
(E)-1-Methyl-4-(3-((trifluoromethyl)sulfonyl)prop-1-en-1-yl)-
1
benzene (3b). Yield: 85% (56.1 mg); colorless oil; H NMR (400
MHz, CDCl3) δ 7.30 (d, J = 7.3 Hz, 2H), 7.16 (d, J = 7.5 Hz, 2H),
6.77 (d, J = 15.8 Hz, 1H), 6.07 (td, J = 7.5 Hz, J = 15.4 Hz, 1H), 4.11
(d, J = 7.4 Hz, 2H), 2.35 (s, 3H); 13C NMR (100 MHz, CDCl3) δ
141.6, 139.4, 132.3, 129.5, 126.9, 123.2 (q, J = 328.3 Hz), 108.9, 54.6,
21.3; 19F NMR (376 MHz, CDCl3) δ −76.22 ppm; νmax (KBr)/cm−1
(E)-2,4-Dimethyl-1-(3-((trifluoromethyl)sulfonyl)prop-1-en-1-yl)-
benzene (3j). Yield: 81% (56.3 mg); colorless solid, mp = 70−71 °C;
1H NMR (400 MHz, CDCl3) δ 7.33 (d, J = 7.7 Hz, 1H), 7.02−6.99
(m, 3H), 5.96 (td, J = 7.6 Hz, J = 15.4 Hz, 1H), 4.13 (d, J = 7.5 Hz,
D
DOI: 10.1021/acs.joc.5b02674
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The Journal of Organic Chemistry
Note
2H), 2.31 (d, J = 3.1 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ 139.8,
139.1, 135.9, 131.5, 131.3, 127.1, 126.1, 119.8 (q, J = 328.6 Hz), 110.5,
54.8, 21.1, 19.6; 19F NMR (376 MHz, CDCl3) δ −76.06 ppm; νmax
(KBr)/cm−1 3133, 1617, 1401, 1203, 1120; HRMS (ESI) m/z: calcd
for C12H13F3NaO2S [M + Na]+, 301.0481; found, 301.0484.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.joc.5b02674.
■
S
1H and 13C NMR spectra for all compounds prepared
(PDF)
(E)-1,3,5-Trimethyl-2-(3-((trifluoromethyl)sulfonyl)prop-1-en-1-
1
yl)benzene (3k). Yield: 86% (62.8 mg); colorless oil; H NMR (400
MHz, CDCl3) δ 6.88 (s, 2H), 6.84 (d, J = 8.2 Hz, 1H), 5.72−5.64 (m,
1H), 4.15 (d, J = 7.4 Hz, 2H), 2.27 (s, 9H); 13C NMR (100 MHz,
CDCl3) δ 140.5, 137.6, 136.0, 131.8, 128.9, 119.8 (q, J = 328.4 Hz),
115.4, 54.7, 21.0, 20.7; 19F NMR (376 MHz, CDCl3) δ −76.37 ppm;
νmax (KBr)/cm−1 3134, 1618, 1401, 1206, 1121, 625; HRMS (ESI) m/
z: calcd for C13H15F3NaO2S [M + Na]+, 315.0637; found, 315.0639.
(E)-2-(3-((Trifluoromethyl)sulfonyl)prop-1-en-1-yl)furan (3l).
AUTHOR INFORMATION
Corresponding Authors
*E-mail: cewuwq@scut.edu.cn.
*E-mail: jianghf@scut.edu.cn.
Notes
■
1
Yield: 51% (30.6 mg); colorless solid, mp = 55−56 °C; H NMR
The authors declare no competing financial interest.
(400 MHz, CDCl3) δ 7.40 (s, 1H), 6.60 (d, 1H, J = 15.6 Hz), 6.40 (s,
2H), 6.04 (td, 1H, J = 7.8 Hz, J = 15.6 Hz), 4.09 (d, 2H, J = 7.8 Hz);
13C NMR (100 MHz, CDCl3) δ 150.7, 143.5, 129.0, 119.7 (q, J =
328.5 Hz), 112.3, 111.7, 111.2, 108.1, 54.3; 19F NMR (376 MHz,
CDCl3) δ −76.35 ppm; νmax (KBr)/cm−1 3140, 1627, 1401, 1126;
HRMS (EI) m/z: calcd for C8H7F3O3S [M]+, 240.0069, found,
240.0064.
ACKNOWLEDGMENTS
■
The authors thank the National Natural Science Foundation of
China (21420102003) and the Fundamental Research Funds
for the Central Universities (2015ZY001) for financial support.
(E)-2-(3-((Trifluoromethyl)sulfonyl)prop-1-en-1-yl)thiophene
(3m). Yield: 68% (43.5 mg); colorless solid, mp = 89−90 °C; H
REFERENCES
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(E)-1-(3-((Trifluoromethyl)sulfonyl)prop-1-en-1-yl)naphthalene
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(400 MHz, CDCl3) δ 8.01 (d, J = 8.1 Hz, 1H), 7.84 (dd, J = 7.8 Hz, J
= 8.8 Hz, 2H), 7.58−7.49 (m, 4H), 7.44 (t, J = 8.0 Hz, 1H), 6.14 (td, J
= 7.6 Hz, J = 15.3 Hz, 1H), 4.21 (d, J = 7.6 Hz, 2H); 13C NMR (100
MHz, CDCl3) δ 139.4, 133.6, 132.8, 130.9, 129.5, 128.7, 126.7, 126.2,
125.6, 124.7, 123.3, 119.8 (q, J = 328.7 Hz), 113.5, 54.6; 19F NMR
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(3-((Trifluoromethyl)sulfonyl)prop-1-ene-1,1-diyl)dibenzene (3o).
1
Yield: 72% (58.7 mg); colorless oil; H NMR (400 MHz, CDCl3) δ
7.45−7.39 (m, 3H), 7.33−7.29 (m, 3H), 7.27−7.25 (m, 2H), 7.23−
7.19 (m, 2H), 6.12 (t, J = 7.7 Hz, 1H), 4.09 (d, J = 7.7 Hz, 2H); 13C
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(E)-(2-Methyl-3-((trifluoromethyl)sulfonyl)prop-1-en-1-yl)-
benzene (3p). Yield: 83% (54.8 mg); colorless solid, mp = 86−87 °C;
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Hz), 60.8, 18.7; 19F NMR (376 MHz, CDCl3) δ −76.57 ppm; νmax
(KBr)/cm−1 3465, 3171, 3126, 1401, 1349, 1195, 1122, 620; HRMS
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287.0325.
(E)-1-Chloro-3-(3-((trifluoromethyl)sulfonyl)prop-1-en-1-yl)-
1
benzene (3q). Yield: 70% (49.7 mg); colorless oil; H NMR (400
MHz, CDCl3) δ 7.40 (s, 1H), 7.31−7.27 (m, 3H), 6.76 (d, J = 15.8
Hz, 1H), 6.19−6.11 (m, 1H), 4.14 (d, J = 7.5 Hz, 2H); 13C NMR (100
MHz, CDCl3) δ 140.2, 136.8, 134.9, 130.1, 129.2, 126.9, 125.1, 119.7
(q, J = 328.1 Hz), 112.0, 54.2; 19F NMR (376 MHz, CDCl3) δ −76.26
ppm; νmax (KBr)/cm−1 3127, 1603, 1402, 1128, 625; HRMS (ESI) m/
z: calcd for C10H8ClF3NaO2S [M + Na]+, 306.9778; found, 306.9775.
E
DOI: 10.1021/acs.joc.5b02674
J. Org. Chem. XXXX, XXX, XXX−XXX

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DOI: 10.1021/acs.joc.5b02674
J. Org. Chem. XXXX, XXX, XXX−XXX