Perfluoroalkanesulfonylation of Alkynyl(phenyl)iodonium Tosylates by the Weakly Nucleophilic Sodium Perfluoroalkanesulfinates

Article abstract of DOI:10.1002/adsc.201600717

An additive- and transition metal-free perfluoroalkanesulfonylation of alkynyl(phenyl)iodonium tosylates with sodium perfluoroalkanesulfinates (R_fnSO₂Na) is described. The poorly nucleophilic R_fnSO₂Na reacted with alkynyl(phenyl)iodonium salts in dichloromethane at room temperature under a nitrogen atmosphere for 5–60 minutes to afford a variety of acetylenic triflones and alkynyl perfluoroalkyl sulfones in good to quantitative yields. The position of substituents on the phenyl rings of the arylethynyl moiety in the iodonium salts had a big influence on the reaction. The formation of five-membered cyclic vinyl sulfones suggested that the reaction proceeds via an alkylidene carbene intermediate. Furthermore, successful scaling-up of the reaction demonstrates the practicality of the new method. Advantages of the method include short reaction times, mild conditions, and the easy access to perfluoroalkanesulfonylation reagents (R_fnSO₂Na). (Figure presented.).

Full text of DOI:10.1002/adsc.201600717

UPDATES
DOI: 10.1002/adsc.201600717
Perfluoroalkanesulfonylation of Alkynyl(phenyl)iodonium
Tosylates by the Weakly Nucleophilic Sodium Perfluoroalkane-
A
Jia-Bin Han,a Lian Yang,a Xing Chen,a Gao-Feng Zha,a and Cheng-Pan Zhanga,*
a
School of Chemistry, Chemical Engineering and Life Science, Wuhan University of Technology, 205 Luoshi Road, Wuhan
430070, Peopleꢀs Republic of China
E-mail: cpzhang@whut.edu.cn or zhangchengpan1982@hotmail.com
Received: July 7, 2016; Revised: September 18, 2016; Published online: && &&, 0000
Supporting information for this article can be found under: http://dx.doi.org/10.1002/adsc.201600717.
Abstract: An additive- and transition metal-free
perfluoroalkanesulfonylation of alkynyl(phenyl)io-
donium tosylates with sodium perfluoroalkanesulfi-
nates (RfnSO2Na) is described. The poorly nucleo-
philic RfnSO2Na reacted with alkynyl(phenyl)iodo-
nium salts in dichloromethane at room temperature
under a nitrogen atmosphere for 5–60 minutes to
afford a variety of acetylenic triflones and alkynyl
perfluoroalkyl sulfones in good to quantitative
yields. The position of substituents on the phenyl
rings of the arylethynyl moiety in the iodonium
salts had a big influence on the reaction. The for-
mation of five-membered cyclic vinyl sulfones sug-
gested that the reaction proceeds via an alkylidene
carbene intermediate. Furthermore, successful scal-
ing-up of the reaction demonstrates the practicality
of the new method. Advantages of the method in-
clude short reaction times, mild conditions, and the
easy access to perfluoroalkanesulfonylation re-
agents (RfnSO2Na).
tant functionalities in the construction of new organic
scaffolds due to its strong electron-withdrawing ability
and high lipophilicity.[1,4] The combination of RfnSO2
segments with alkynes has resulted in alkynyl per-
fluoroalkyl sulfones which have been confirmed as
highly reactive building blocks.[4] Acetylenic triflones
are useful building blocks for the preparation of vinyl
triflones,[5] and they are reliable reagents for the radi-
cal alkynylation of Csp3–H bonds.[6] They can also un-
dergo [4+2] or [3+2] cycloaddition with dienes or 1,3-
dipoles to furnish a variety of CF3SO2-substituted het-
erocycles.[7] In view of their wide applications, the de-
velopment of an effective method to prepare alkynyl
perfluoroalkyl sulfones is of broad interest.
To the best of our knowledge, the known synthetic
methods to prepare acetylenic triflones require n-
BuLi or Na as the base and Tf2O as the trifluometh-
AHCTUNGTREGaNNUN nesulfonylation reagent. Such methods suffer from
disadvantages such as a narrow range of substrates,
harsh reaction conditions, and the use of toxic and ex-
pensive agents.[5–8] Because of the lack of variety of
perfluoroalkanesulfonylation reagents [RfnSO2X (X=
F, Cl) or (RfnSO2)2O], the production of diversified al-
kynyl perfluoroalkyl sulfones from terminal alkynes is
severely limited.
Keywords: alkynes; fluorine; iodonium salts; per-
fluoroalkanesulfonylation; substituent effects; tran-
sition metal-free conditions
Perfluoroalkanesulfinates (RfnSO2M) including
Langoisꢀ reagent (CF3SO2Na), derived from RfnX
(X=I, Br) by a sulfinatodehalogenation reaction and
Fluorine has a small atomic size and the highest elec- others,[3j] have been exploited as versatile perfluoroal-
tronegativity among all elements (Pauling scale), and kylation and perfluoroalkylthiolation reagents in the
it forms the strongest C–X single bonds with carbon last several years (especially CF3SO2Na as trifluoro-
atoms.[1] The introduction of fluorine and fluorine- methylation and trifluoromethylthiolation reagents).[9]
containing groups into organic molecules can desira- They can also be used as perfluoroalkanesulfonylation
bly modulate their physical, chemical, and biological reagents.[10,11] Trifluoromethanesulfonylation of sp3
properties.[2] Fluorination has been widely used in the carbon electrophiles by CF3SO2Na provided the cor-
synthesis of potent pharmaceuticals, agrochemicals, responding triflated products, the utility of which was
and functional materials.[2,3] Among the prevalent flu- fully demonstrated in organic synthesis.[10a–c] Owing
orine-containing moieties, the perfluoroalkanesulfonyl to the strong electronegativity of the CF3 group,[3j]
(RfnSO2) group has become one of the most impor- CF3SO2Na reacts slowly with electrophiles, leading to
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Table 1. Trifluoromethanesulfonylation
of
1a
by
a limited substrate scope in reactions involving nucle-
ophilic CF3SO2Na components.[10] Transition metal-
catalyzed trifluoromethanesulfonylation of sp2 carbon
electrophiles by CF3SO2Na could be accomplished to
build C(sp2)–SO2CF3 bonds.[11] However, in these re-
actions only diaryliodonium salts, arenediazonium tet-
rafluoroborates, and aryl triflates have been investi-
gated.[11] Compared to perfluoroalkylation and per-
fluoroalkylthiolation, the perfluoroalkanesulfonyla-
tion with RfnSO2Na is much less studied, and the con-
struction of C(sp)–SO2Rfn bonds by RfnSO2Na is
rarely reported.[12] Given the great interest in alkynyl
perfluoroalkyl sulfones, we were motivated to develop
a convenient synthetic method to these compounds
with the easily accessed and bench-stable RfnSO2Na
salts.
CF3SO2Na.[a]
Entry
1a:2a[b]
Conditions
Yield (3a [%])[c]
1
2
3
4
1:1
1:1.5
1:2
1:3
1:4
1:2
1:2
1:2
1:2
1:2
1:2
1:2
1:2
1:2
CH2Cl2, 2 h
CH2Cl2, 6 h
CH2Cl2, 6 h
CH2Cl2, 6 h
CH2Cl2, 6 h
CH2Cl2, 0.5 h
CH2Cl2, 2 h
CHCl3, 0.5 h
toluene, 0.5 h
CH3CN, 0.5 h
THF, 0.5 h
70
87
91
86
67
91
57
45
35
0
5
6
7[d]
8
9
10
11
On the other hand, hypervalent alkynyl(aryl)iodo-
nium salts are very versatile reagents capable of react-
0
0
0
0
ing with a variety of nucleophiles.[13,14] Reactions be- 12
DMF, 0.5 h
acetone, 0.5 h
CH2Cl2, 4 h
13
tween alkynyl(aryl)iodonium salts and the non-fluori-
nated alkyl or aryl sulfinates have supplied a large
number of alkynyl sulfones and/or cyclic vinyl sul-
fones.[15] Although 1-alkynyl-l3-bromanes can undergo
a tandem reaction with trifluoromethanesulfinate,[12a]
the interaction between alkynyl(phenyl)iodonium
salts and CF3SO2Na was unknown. Alkynyl(phen-
14[e]
[a]
Reaction conditions: 1a (0.1 mmol), CF3SO2Na (0.1, 0.15,
0.2, 0.3, or 0.4 mmol), solvent (1 mL), room temperature,
N2.
Molar ratio.
[b]
[c]
Yields were determined by HPLC using [(trifluorometh-
AHCTUNGTREGaNNNU nesulfonyl)ethynyl]benzene (3a) as the external stan-
dard [tR =6.922 min, lmax =260.6 nm, CH3CN/H2O=
ACHTUNGTRENNUNGyl)iodonium salts are less electrophilic than 1-alkynyl-
l3-bromanes,[12] and sodium perfluoroalkanesulfinates
bearing long-chain perfluoroalkyl groups have much
poorer nucleophilicity than the non-fluorinated ana-
logues (even poorer than CF3SO2Na).[3j,10] Neverthe-
less, it is notable that all these reagents can be con-
veniently synthesized.[3j,12,13] Hence, we wondered
whether the reaction of RfnSO2Na with alkynyl(phe-
65:35 (v/v)].
[d]
[e]
Phenyl(phenylethynyl)iodonium trifluoroacetate was
used instead of 1a.
1-Phenylethynyl-1,2-benziodoxol-3(1H)-one (EBX) was
used instead of 1a.
nyl)iodonium salts could expediently form the useful and toluene for 0.5 h afforded 3a in 45% and 35%
alkynyl triflones. yield, respectively (entries 8 and 9, Table 1). Nonethe-
To our delight, the reaction of phenylethynyl(phe- less, when using CH3CN, THF, DMF, and acetone as
nyl)iodonium tosylate (1a) with an equal equivalent solvents, there was no 3a obtained (entries 10–13,
of CF3SO2Na in CH2Cl2 at room temperature under Table 1). These results implied that CH2Cl2 is a suita-
a nitrogen atmosphere for 2 h provided 3a in 70% ble solvent for the reaction. In addition, the reaction
yield (entry 1, Table 1). By varying the molar ratio of of CF3SO2Na with 1-phenylethynyl-1,2-benziodoxol-
CF3SO2Na from 1.0 to 1.5 or 2.0 equivalents and a re- 3(1H)-one (EBX, the commonly used alkynylation re-
action time of 6 h, 3a was obtained in 87% or 91% agent) instead of 1a failed to afford 3a (entry 14,
yield, respectively (entries 2 and 3, Table 1). Further Table 1). EBX had successfully been used for the al-
increments of CF3SO2Na to 3.0 or 4.0 equivalents did kynylation of the non-fluorinated sulfinates.[13,15] This
not improve the trifluoromethanesulfonylation (en- lack of reactivity is believed to stem from the poor
tries 4 and 5, Table 1). Furthermore, reaction of 1a nucleophilicity of sodium trifluoromethanesulfinate.
with CF3SO2Na (2 equiv.) in CH2Cl2 at room tempera-
ture for 0.5 h also afforded 3a in 91% yield, suggest- scope of the reaction was investigated. Arylethynyl-
ing that the trifluoromethanesulfonylation is complet- (phenyl)iodonium tosylates like 1b–l reacted smoothly
ed in 30 min (entry 6, Table 1). Taking phenylethyn- with CF3SO2Na in CH2Cl2 at room temperature under
yl(phenyl)iodonium trifluoroacetate instead of 1a in N2 to give the corresponding acetylenic triflones (3b–
With the optimized reaction conditions in hand, the
AHCTUNGTRENNUNG
ACHTUNGTRENNUNG
the same reaction for 2 h provided 3a only in 57% l) in moderate to quantitative yields (Table 2). Treat-
yield (entry 7, Table 1), despite the former being ment of (3,3-dimethylbutynyl)(phenyl)iodonium tosy-
more stable than the latter (1a).[15c] Moreover, the late (1m) with CF3SO2Na afforded 3,3-dimethyl-1-(tri-
choice of solvent had a big influence on the reaction. fluoromethanesulfonyl)butyne (3m) in 85% yield (de-
Reactions of 1a with CF3SO2Na (2 equiv.) in CHCl3 termined by 19F NMR). TLC technique was employed
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Table 2. Transition metal- and additive-free trifluorometh-
ACHTUNGTRENNUNGanesulfonylation of 1b–p by CF3SO2Na.
3g vs. 3h). [(4-Methoxyphenyl)ethynyl](phenyl)iodo-
nium tosylate (1e) reacted with CF3SO2Na under the
standard conditions for 15 min to provide 1-methoxy-
4-[(trifluoromethanesulfonyl)ethynyl]benzene (3e) in
63% yield, whereas the reaction of [(2-methoxyphe-
nyl)ethynyl](phenyl)iodonium tosylate (1n) with
CF3SO2Na afforded 3-(trifluoromethanesulfonyl)ben-
zofuran (3n) in 67% yield. Additionally, treatment of
[(2-ethylphenyl)ethynyl](phenyl)iodonium
tosylate
(1o) with CF3SO2Na under the standard reaction con-
ditions gave a mixture of 1-methyl-3-(trifluorometh-
AHCTUNGTRENNUNG
19% yield). These findings indicated that an alkyli-
dene carbene intermediates might be formed in the
reaction, which underwent 1,2-rearrangement to yield
acetylenic triflones (e.g., 3a–m and 3o) or was insert-
ed into an appropriate C–H bond to form five-mem-
bered cyclic vinyl sulfones (e.g. 3o’).[12,14–16] Also, alky-
nyl(phenyl)iodoniums bearing stronger para-electron-
withdrawing groups such as CO2Me and COCH3 on
the arylethynyl moieties could also give the desired
trifluoromethanesulfonylation products, which were
unstable and rapidly decomposed during the work-up.
Although the insertion of an alkylidene carbene
into the C–H bond of an adjacent alkyl group to form
five-membered rings is well documented,[12,14–16] the
reaction between an alkylidene carbene and the
ortho-OCH3 group on the phenyl ring has never been
reported. Here we report a new method to access 3-
trifluoromethanesulfonylbenzofuran. A proposed re-
action mechanism is suggested (Scheme 1), which in-
volves the formation of alkylidene carbene (II), the
bonding of II with an oxygen atom of an ortho-OCH3
group, the demethylation of III by nucleophilic attack
of tosylate anion, and the protonation by residual
moisture in CH2Cl2.[16,17] These assumptions are sup-
ported in part by the isolation of methyl 4-methylben-
zenesulfonate from the reaction mixture and by the
formation of 2-deuterated-3-(trifluoromethanesulfo-
nyl)benzofuran (3n-D) when 4 equiv. of D2O were
used at the beginning of the reaction (see the Sup-
porting Information). Nevertheless, the exact details
of the mechanism are still unclear.
[a]
[b]
Reaction
conditions:
1
(0.2 mmol),
CF3SO2Na
(0.4 mmol), CH2Cl2 (2 mL), room temperature, N2. Iso-
lated yield.
Reaction
conditions:
1
(0.3 mmol),
CF3SO2Na
(0.2 mmol), CH2Cl2 (2 mL), room temperature, N2. Iso-
lated yield.
[c]
[d]
Yield was determined by 19F NMR using C6H5CF3 as an
internal standard.
Reaction conditions: 1-octyne (6.0 mmol), Koserꢀs re-
agent (2.0 mmol), CH2Cl2 (10 mL), reflux, 4 h, then
CF3SO2Na (4.0 mmol), room temperature, 30 min. Isolat-
ed yield.
Sodium perfluoroalkanesulfinates with long-chain
perfluoroalkyl groups that have stronger electronega-
tivity than CF3 group[3j] were also suitable reagents in
the reaction. Sulfinates like C2F5SO2Na (2b),
to monitor the progress of the reaction. Once the io- C4F9SO2Na (2c), C6F13SO2Na (2d), and C8F17SO2Na
donium salt was completely consumed, the product (2e) reacted with alkynyl(phenyl)iodonium salts in
was isolated from the reaction mixture by flash CH2Cl2 at room temperature under a nitrogen atmos-
column chromatography. The position of the substitu- phere to afford 3ab–ae, 3db, 3ec, 3gd, and 3be in 44–
ents on the phenyl rings of arylethynyl iodonium salts 72% yields (Table 3). Notably, if disodium 2,2’-
had a significant impact on the reaction. It was found oxybis(1,1,2,2-tetrafluoroethanesulfinate) (2f) was
that iodoniums bearing meta-substitution on the aryl- treated with 1a and 1d under the standard reaction
ACHTUNGTRENNUNG
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tioned again that alkynyl perfluoroalkyl sulfones (e.g.,
3af and 3df) are difficult to synthesize by the known
means due to the lack of appropriate electrophilic
RfnSO2X or (RfnSO2)2O reagents.[8] This transition
metal-free reaction does not require RfnSO2X or
(RfnSO2)2O and proceeds very rapidly, thus allowing
for a simple, efficient, and reliable access to these
compounds.
Furthermore, a 10 mmol scale reaction of 1a with
CF3SO2Na was performed to test the practicality of
the method. The reaction at room temperature under
standard conditions for 30 min provided 3a in 97%
yield (2.28 g), indicating that alkynyl perfluoroalkyl
sulfones could be prepared in a large scale by our
method (Scheme 2). In addition, the one-pot reaction
Scheme 1. A proposed reaction mechanism for the forma-
tion of 3n.
Scheme 2. Scaled-up synthesis of 3a from 1a and 2a.
Table 3. Transition metal- and additive-free perfluoroalkane-
sulfonylation of alkynyl(phenyl)iodonium tosylates by
RfnSO2Na.[a]
was explored. Treatment of ethynylbenzene with
Koserꢀs reagent in CH2Cl2 at room temperature for
16 h without purification followed by addition of 2a
provided 3a in 33% isolated yield (Scheme 3). A simi-
lar one-pot reaction was also performed for 1-octyne,
which gave 3p in 21% yield (Table 2). These results
demonstrate the feasibility of a one-pot synthesis of
acetylenic triflones from the corresponding arylacety-
lenes, albeit at the cost of lower product yields being
obtained.
Scheme 3. One-pot synthesis of 3a from ethynylbenzene and
2a.
In conclusion, we have developed a fast, conven-
ient, and transition metal-free method for the prepa-
ration of acetylenic triflones that are valuable build-
ing blocks in organic sythesis. Alkynyl perfluoroalkyl
sulfones bearing long perfluoroalkyl chains that are
difficult to synthesize by the known approaches are
also favorably prepared under our reaction condi-
tions. Since sodium perfluoroalkanesulfinates can be
[a]
Reaction conditions: 1 (0.2 mmol), RfnSO2Na (0.4 mmol),
CH2Cl2 (2 mL), room temperature, N2. Isolated yield.
[b]
Reaction conditions:
1 (0.3 mmol), NaO2SRfnSO2Na
(0.1 mmol), CH2Cl2 (2 mL), room temperature, N2.
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60 min), mild reaction conditions, the easy prepara-
tion of perfluoroalkanesulfinates, and provides an ef-
ficient way to numerous alkynyl perfluoroalkyl sul-
fones without the use of additives.
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Typical Procedure for the Synthesis of 3b
In a nitrogen-filled glovebox, a reaction tube was charged
with phenyl(p-tolylethynyl)iodonium tosylate (1b, 98.1 mg,
0.2 mmol), CF3SO2Na (62.4 mg, 0.4 mmol), and CH2Cl2
(2 mL) with vigorous stirring. The mixture was reacted at
room temperature for 30 minutes, concentrated to dryness,
and purified by flash column chromatography on silica gel
using petroleum ether/ethyl acetate=20:1 (v/v) as eluents to
give 3b as a yellow solid; yield: 42.5 mg (0.17 mmol, 86%).
1H NMR (500 MHz, CDCl3): d=7.58 (d, J=8.2 Hz, 2H),
7.29 (d, J=8.1 Hz, 2H), 2.44 (s, 3H); 19F NMR (471 MHz,
CDCl3): d=À79.7 (s, 3F); 13C NMR (126 MHz, CDCl3): d=
144.8, 133.8, 129.9, 119.0 (q, J=323.9 Hz), 112.6, 101.8, 77.2,
22.0.
Acknowledgements
We thank Wuhan University of Technology, the Natural Sci-
ence Foundation of Hubei Province (China) (2015CFB176),
the “Chutian Scholar” Program from Department of Educa-
tion of Hubei Province (China), and the “Hundred Talent”
Program of Hubei Province for financial support. We thank
Professor David A. Vicic at Leigh University for proofread-
ing this manuscript.
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UPDATES
Perfluoroalkanesulfonylation of Alkynyl(phenyl)iodonium
Tosylates by the Weakly Nucleophilic Sodium
7
PerfluoroalkaneACHTUNGTRENNUNGsulfinates
Adv. Synth. Catal. 2016, 358, 1 – 7
Jia-Bin Han, Lian Yang, Xing Chen, Gao-Feng Zha,
Cheng-Pan Zhang*
Adv. Synth. Catal. 0000, 000, 0 – 0
7
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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These are not the final page numbers!