Mild synthesis of triarylsulfonium salts with arynes

Article abstract of DOI:10.1039/c7ob01596h

Reactions between arynes and alkyl sulfides have been extensively studied over the past few decades. These reactions commonly end with a dealkylation process and thus deliver thioethers as final products. In contrast, the transformation described furnishes valuable triarylsulfonium salts, in lieu of thioethers, from arynes and diarylsulfides. The reaction features mild conditions and a broad substrate scope. A suite of functional groups such as ketones, esters, nitriles, aryl ethers and aryl halides is tolerated, which can be issues faced by traditional synthetic methods. The practicality of the reaction and its extension to the synthesis of triphenyl selenonium salt are also exhibited herein.

Full text of DOI:10.1039/c7ob01596h

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Takeharu Haino et al.
Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
benzene
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Mild Synthesis of Triarylsulfonium Salts with Arynes
Lei Zhang,a Xiaojin Li,‡a Yan Sun,‡a Weizhao Zhao,a Fan Luo,a Xin Huang,a Lihui Lin,a Ying Yang,a and
Bo Peng*a,b
Received 00th January 20xx,
Accepted 00th January 20xx
Reactions between arynes and alkyl sulfides have been extensively studied over the past few decades. These reactions
commonly end with a dealkylation process and thus deliver thioethers as final products. In contrast, the transformation
described furnishes valuable triarylsulfonium salts, in lieu of thioethers, from arynes and diarylsulfides. The reaction
features mild conditions and a broad substrate scope. A suite of functional groups such as ketones, esters, nitriles, aryl
ethers and aryl halides are tolerated, which can be issues faced by traditional synthetic methods. The practicality of the
reaction and its extension to the synthesis of triphenyl selenonium salt are also exhibited herein.
DOI: 10.1039/x0xx00000x
www.rsc.org/
we envisioned that a simple treatment of benzyne with
Introduction
diarylsulfides might directly produce a betaine intermediate
(Scheme 1, eq 3). Subsequent protonation of phenyl anion of
intermediate would accomplish the desired triarylsulfonium
salt.15 Since the stability of triarylsulfoniums under similar
conditions has been well established,14a it can be expected
that dearylation of triarylsulfoniums would not occur even
though its analogy, the dealkylation of alkyl sulfoniums has
been encountered rather frequently in this area (Scheme 1, eq
1 and 2).6
I
Arynes are widely used as highly electrophilic aryl synthons in
the synthesis of natural products and bioactive compounds.1,2
Owing to the bent triple bond, distorted aromatic ring and
low-lying LUMO,3 arynes can directly arylate amines,4
phosphines,5 sulfides,6 carbonyls7 and various O-nucleophiles8.
Among them, sulfur compounds recognized as soft nucleophile
properly cooperate with the soft nature of arynes.9 As a result,
significant efforts from synthetic community have been made
on incorporation of thioethers into aryne chemistry.6a-i The
reported reactions essentially consist of two common steps
including the formation of arylsulfonium salts and subsequent
dealkylation process (Scheme 1, eq 1 and 2). The sulfonium
intermediates can be formed by either nucleophilic addition of
alkyl sulfides to benzyne6a-g or [3+2] cycloaddtion of vinyl
sulfides to benzyne6i. Eventually these transformations were
terminated by S-dealkylation of sulfoniums to deliver
thioethers as final products.
I
1962-2017: Mertz, Nakayama, Xu and Shen, Hoye, Biju
R1
S
R1
S
R3
S
R2
R2
(1)
transformations depend on
substrates
2016: Studer
R1
S
R2
R1
S
R1
Triarylsulfonium salts are well known for their capability of
releasing proton under UV conditions and thus they have been
widely used as superior photo initiators in polymerization
reactions10 and lithographic process11. They also serve as
useful aryl sources in various organic transformations.12
Therefore, efficient and practical methods to access these
compounds are highly desired.13 Inspired by the reported
nucleophilicity6 of sulfides toward arynes, alongside our
continuing interests in the synthesis of triarylsulfonium salts,14
S
EWG
R2
(2)
R2
EWG
EWG
This work
Ar1
S
Ar1
S
S
Ar1
Ar2
H+
Ar2
Ar2
(3)
OTf
I
Scheme 1 Reactions of benzyne with thioethers
Results and discussion
To test the hypothesis, we selected Kobayashi aryne precursor
1a16 and diphenyl sulfide 2a as model substrates to optimize
reaction conditions (Table 1). Pleasingly, the desired
triphenylsulfonium salt 3aa was obtained in the first trial albeit
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with a relatively low yield (entry 1). “F-” sources (KF and TBAT) and 2l
) exhibited much better reactivity than the bi-
other than CsF proved to be ineffective for the reaction halogenated sulfide 2f
.
(entries 2 and 3). In view of the weak nucleophility of diphenyl
Table 2 Scope of diaryl sulfidea
sulfide, we raised the reaction temperature to 50
℃, but no
improvement was observed (entry 4). Further attempts by
lowering the reaction temperature (entry 5) or switching to
other solvents (entry 6, for solvent screen, see supporting
information) did not enhance the selectivity of the reaction.
Notably the deterioration of benzyne precursor was observed
during the optimization study (entries 1-6). To compensate for
its consumption, excess of 1a was used in further
optimizations. Indeed, the chemical yield of 3aa was
significantly improved when 2.0 or 3.0 equiv of 1a was
R2
1a
S
S
CsF, MeCN
OTf
R1
R2
R1
25 °C, 36 h
2
3
R
R = H, 3aa: 90%
R = Me, 3ab: 98%
R = OMe, 3ac: 98%
R = OBn, 3ad: 87%
R = Ph, 3ae: 41%
R = Cl, 3af: 27%b
S
R
OTf
employed (entries
7 and 8). Eventually we found that
delivering CsF to the reaction mixture in three portions over
time afforded 3aa in the best yield (entry 9)
.
Table 1 Optimization of reaction conditionsa
X-ray of 3aa
X-ray of 3ac
Me
OTf
S
S
S
Me
Me
entry
“F-” source /solvent
CsF/MeCN
x/y
yield (%)b
33c
tracec
tracec
21c
temp (℃)
Me
MeO
OTf
OTf
1
2
3
4
5
6
7
8
9
25
25
25
50
0
1.0/2.0
1.0/2.0
1.0/2.0
1.0/2.0
1.0/2.0
1.0/2.0
2.0/2.0
3.0/3.0
3.0/3.0
Me
KF/18-crown-6/THF
TBAT/THF
3ag, 55%
3ah, 63%
3ai, 72%
Me
Me
Cl
F
CsF/MeCN
S
CsF/MeCN
CsF/MeCN/toluenee
34c,d
28c
S
S
Me
Me
Me
OTf
OTf
25
25
25
25
OTf
CsF/MeCN
54
Me
Me
H
CsF/MeCN
67
92(90)d,f,g
3aj, tracec
3ak, 83%
3al, 75%
CsF/MeCN
O
OR
OTf
S
aUnless otherwise noted, reactions were performed with 1a (x equiv), diphenyl
R =
3an, 38%
Me
O
sulfide 2a (0.2 mmol), and “F” source (y equiv) for 22 h. bNMR yield (mesitylene
S
d
as the internal standard); c1a decomposed after reaction; Reaction time is 36 h.
eMeCN/toluene=3/1. fIsolated yield in parenthesis. gCsF was added in three
portions. For details, see supporting information.
OTf
R =
R =
3ao, 44%
3ap, 39%
OMe
MeO
OR
3am, 67%
N
With suitable reaction conditions in hand, we first
evaluated the scope of diarylsulfides as shown in Table 2. A
wide range of diarylsulfides were successfully phenylated by
aAll the reactions were performed in 0.3 mmol scale under optimum conditions.
b70% of sulfide 2f was recovered. c85% of sulfide 2j was recovered.
benzyne to produce the desired triarylsulfonium salts
3 in
Notably, an array of functional groups including a ketone (2n),
an ester (2o), a nitrile (2p), aryl ethers (2c, 2d, 2h and 2m) and
typically good to excellent yield. Electron-donating para-
substituents (-Me, -OMe, -OBn) are beneficial for the reaction
aryl halides (2k and 2l) are tolerated in the reaction. In view of
limitations of conventional methods13 to prepare
triarylsulfonium salts, the reaction proceeding with such
functional group compatibility is particularly noteworthy.
Interestingly, a cyclic ketone sulfide 2q dually capatured
one benzene with its nucleophilic “S” atom and electronphilic
carbonyl group.17 As a consequence, a novel axial symmetry
triarylsulfonium 3aq was achieved in good yield (78%).
According to our hypothesis (eq 3, Scheme 1), the formation of
3aq may involve S-phenylation of diarylsulfide 2q, subsequent
yielding 3ab, 3ac, 3ad in excellent yields. In contrast, electron
withdrawing groups (-Ph, -Cl) have detrimental influence
resulting in relative low yields of triarylsulfoniums (3ea and
3ef). The dramatically decreased reactivity might be ascribed
to the weaker nucleophilicity of electron poor diarylsulfides
toward benzyne. Sterically hindered substrates with ortho-
substituents (2g-2i) also proved to be suitable to the reaction
and produced synthetic useful yields. However more hindered
substrate, the fully ortho-substituted diarylsulfide 2j is inert to
the reaction conditions. Mono-halogenated diarylsulfides (2k
2 | J. Name., 2012, 00, 1-3
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moieties were all anchored on 2r to assemble a phenyloxy
sulfonium salt 3ar (eq 5).4c,8a Although the chemical yield was
relative low (35%) from the optimum conditions, it could be
significantly enhanced to 77% by increasing the use of aryne
precusor 1a
.
Next we evaluated the reaction using various aryne
precursors and diarylsulfides (Table 3). To our delight,
regardless of the substituents, aryne precursors 1b
-1e
afforded triarylsulfonium salts 3 in synthetic useful yields
although slightly lower than the prototype 1a. In contrast,
difluorinated benzyne from 1f exhibited less reactivity with
sulfide 2a in which no desired 3fa was attained. However,
electron rich sulfide 2b could still capture the electron poor
benzyne to furnish 3fb in a respectable yield (43%).
Table 3 Reactions of diarylsulfides with benzynesa
R3
R2
Scheme 2 Deuterium-labeling experiments
1
S
S
CsF, MeCN
OTf
R1
R2
R1
25 °C, 36 h
2
3
aryne precursor 1
product 3
Me
R
R = H, 3ba: 63%
Me
OTf
Me
S
R = Me, 3bb: 71%
R = OMe, 3bc: 81%
OTf
Me
TMS
1b
R
S
R
O
O
R = H, 3ca: 61%
R = Me, 3cb: 74%
R = OMe, 3cc: 78%
OTf
O
O
OTf
TMS
1c
R
OMe
To gain insight into the reaction process, labeling
experiments were conducted as shown in Scheme 2. The
R
OMe
R = H, 3da: 59%
R = Me, 3db: 96%
R = OMe, 3dc: 94%
TMS
reaction using CD3CN as solvent afforded a mixture of 3ac/d-
S
3ac in a ratio of 40/60 (eq 6). The formation of ortho-
deuterated sulfonium salt d-3ac is consistent with our original
hypothesis (Scheme 1, eq 3).
Meanwhile we found the formation of d-3ac can be
dramatically inhibited by introducing other proton sources like
MeCN and H2O (eq 7 and 8). This result indicates that the
unlabeled-3ac shown in eq 5 might be attributed to the
protonation by small amount of MeCN (CD3CN, Isotopic
Enrichment, 99.8%) or trace amount of water.
OTf
OTf
1d
R
Br
R
Br
R = H, 3ea: 67%
R = Me, 3eb: 86%
R = OMe, 3ec: 94%
OTf
S
OTf
TMS
1e
R
S
F
F
R
R = H, 3fa: traceb
R = Me, 3fb: 43%
F
F
OTf
OTf
TMS
1f
R
aAll the reactions were performed in 0.3 mmol scale under optimum conditions.
b84% of sulfide 2a was recovered.
nucleophilic addition of phenyl anion to carbonyl of ketone
and O-phenylation of tertiary alcohol (eq 4). While sulfide 2r
bearing two phenol groups was submitted to the reaction, the
S- and O-arylation of 2r occurred in one batch. Three aryl
The practicability of the reaction was then examined by a
gram-scale reaction as shown in eq 9. Under optimum
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1
conditions, 4.5 mmol of diphenylsulfide 2a was efficiently DCM/MeOH = 15/1). H NMR (600 MHz, CDCl3: δ 7.70 – 7.66
converted to triphenylsulfonium salt 3aa in a good yield (71%). (m, 3H), 7.65 – 7.55 (m, 12H). 13C NMR (151 MHz, CDCl3): δ
Triggered by the obtained results, we became curious whether 134.4, 131.3, 130.7, 123.8, 120.5 (q, J = 323.1 Hz, TfO-). 19F
the reaction could be extended to the synthesis of NMR (565 MHz, CDCl3): δ -78.0. IR (neat): 3089, 3062, 1474,
triarylselenonium salts (eq 10). Delightfully, diphenylselane
4
1447, 1258, 1223, 1148, 1066, 1030, 996, 840, 752, 681, 636.
indeed incorporated with benzyne to furnish the expected HRMS: calculated for C18H15S+([M-TfO-]+): 263.0895; found:
triphenylselenonium
5, albeit in a relative low yield (31%).
263.0883. The 3aa is a known compound13e,18,19
.
phenyldi-p-tolylsulfonium
trifluoromethanesulfonate
(3ab). Yellow solid, mp: 98-100
℃, 129.5 mg, 98% yield. (Rf =
0.28, eluent: DCM/MeOH = 15/1). 1H NMR (600 MHz, CDCl3): δ
7.73 – 7.68 (m, 1H), 7.67 – 7.59 (m, 4H), 7.55-7.52 (m, 4H),
7.46-7.44 (m, 4H), 2.41 (s, 6H). 13C NMR (151 MHz, CDCl3): δ
146.1, 134.3, 132.2, 131.4, 130. 8, 130.5, 124.8, 120.8 (q, J =
323.1 Hz, TfO-), 120.6, 21.5. 19F NMR (565 MHz, CDCl3): δ -78.1.
IR (neat): 3060, 2925, 1591, 1448, 1259, 1145, 1072, 1029,
807, 748, 684, 634. HRMS: calculated for C20H19S+([M-TfO-]+):
291.1208; found: 291.1200.
Conclusions
In summary, we have developed an efficient and practical
synthesis of triarylsulfonium salts using diarylsulfides and
arynes. The reaction proceeds under mild conditions providing
a
wide range of triarylsulfonium salts in good yields.
Remarkably, an array of functional groups including ketones,
esters, nitriles, aryl ethers and aryl halides were tolerated in
the reaction which can be challenges faced by conventional
approaches. In addition, the reaction proceeding in a gram-
scale with high efficiency demonstrated its practicality.
However, excess amount of aryne precursors is required to
maintain the chemical yield in a satisfactory level. Further
studies aiming to reduce the use of aryne precursors and
application of the method to prepare new photo initiators are
currently under way.
bis(4-methoxyphenyl)(phenyl)sulfonium trifluoromethane
sulfonate (3ac). Yellow solid, mp: 114-116
℃, 138.9 mg, 98%
yield. (Rf = 0.30, eluent: DCM/MeOH = 15/1). 1H NMR (600
MHz, CDCl3): δ 7.71 –7.66 (m, 1H), 7.65 –7.62 (m, 6H), 7.58 –
7.55 (m, 2H), 7.17-7.14 (m, 4H), 3.86 (s, 6H). 13C NMR (151
MHz, CDCl3): δ 164.5, 133.9, 133.1, 131.3, 129.9, 126.2, 120.9
(q, J = 324.7 Hz, TfO-), 117.2, 113.9, 56.1. 19F NMR (565 MHz,
CDCl3): δ -78.1. IR (neat): 3056, 2976, 2941, 1588, 1574, 1493,
1259, 1223, 1176, 1147, 1073, 1029, 827, 761, 688, 635.
HRMS: calculated for C20H19O2S+([M-TfO-]+): 323.1106; found:
323.1103. The 3ac is a known compound20.
Experimental section
General Information
bis(4-(benzyloxy)phenyl)(phenyl)sulfonium
trifluoro
methanesulfonate (3ad). Yellow oil, 163.0 mg, 87% yield. (Rf =
0.28, eluent: DCM/MeOH = 15/1). 1H NMR (400 MHz, CDCl3): δ
7.70 – 7.57 (m, 9H), 7.42 – 7.37 (m, 8H), 7.36 – 7.33 (m, 2H),
7.25-7.22 (m, 4H), 5.13 (s, 4H). 13C NMR (151 MHz, CDCl3): δ
163.6, 135.2, 134.0, 133.2, 131.4, 130.1, 128.7, 128.5, 127.7,
126.3, 120.9 (q, J = 314.8 Hz, TfO-), 118.0, 114.3, 70.8. 19F NMR
(565 MHz, CDCl3): δ -78.1. IR (neat): 3098, 3064, 1587, 1492,
1252, 1175, 1149, 1028, 830, 743, 698, 635. HRMS: calculated
for C32H27O2S+([M-TfO-]+):475.1732; found: 475.1726.
Unless otherwise indicated, all glassware was oven dried by a
heat gun before use and all reactions were performed under
an atmosphere of Nitrogen. All solvents were distilled from
appropriate drying agents prior to use. All reagents were used
as received from commercial suppliers. Melting points
reported here were measured using
a melting point
instrument and are uncorrected. Neat infrared spectra were
recorded using a NEXUS670 FT-IR spectrometer. 1H, 13C, and
19F NMR spectra were measured on a 400 or 600 MHz NMR.
High-resolution mass spectroscopy (HRMS) analysis was
performed by a TOF MS instrument using an ESI source. The
products were purified by column chromatography using silica
gel (160-200 mesh).
di([1,1'-biphenyl]-4-yl)(phenyl)sulfonium trifluoromethane
sulfonate (3ae). Yellow solid, mp: 117-118
℃, 76.8 mg, 41%
yield. (Rf = 0.30, eluent: DCM/MeOH = 15/1). 1H NMR (600
MHz, CDCl3): δ 7.90 – 7.88 (m, 4H), 7.86 – 7.84 (m, 4H), 7.81 –
7.74 (m, 3H), 7.73– 7.70 (m, 2H), 7.59 (d, J = 8.2 Hz, 4H), 7.50 –
7.42 (m, 6H). 13C NMR (151 MHz, CDCl3): δ 147.7, 138.0, 134.5,
131.7, 131.6, 131.0, 130.0, 129.3, 127.4, 124.8, 122.5. Carbon
of triflate anion cannot be found. 19F NMR (565 MHz, CDCl3): δ
-78.1. IR (neat): 3065, 2952, 2916, 1593, 1478, 1446, 1253,
1150, 1028, 750, 682, 636. HRMS: calculated for C30H23S+([M-
TfO-]+):415.1521; found: 415.1511.
General procedure for the reaction between aryne precursor
1 and diarylsulfide 2.
To a flame-dried reaction tube (25 mL) was added CsF (45.5
mg, 0.3 mmol, 1.0 equiv) under nitrogen atmosphere. Then
MeCN (3 mL), diarylsulfide
(0.9 mmol) were sequentially added to the reaction tube. After
stirring under 25 for the first 12 h, another portion of CsF
2 (0.3 mmol,) and aryne precursor 1
℃
bis(4-chlorophenyl)(phenyl)sulfonium
trifluoromethane
(1.0 equiv) was added to the mixture. It was then stirred for
the second 12 h and the last portion of CsF (1.0 equiv) was
added to the mixture. After stirring for the last 12 h, the
mixture was filtrated through a short plug of silica gel,
concentrated and purified by flash column chromatography on
silica gel to afford the desired product.
sulfonate (3af). Yellow oil, 39.0 mg, 27% yield. (Rf = 0.28,
1
eluent: DCM/MeOH = 15/1). H NMR (400 MHz, CDCl3): δ 7.79
– 7.77 (m, 7H), 7.72 – 7.68 (m, 2H), 7.67 – 7.63 (m, 4H). 13C
NMR (151 MHz, CDCl3): δ 142.0, 134.9, 132.6, 131.9 131.8,
131.0, 123.8, 122.4, 120.7 (q, J = 320.1 Hz, TfO-). 19F NMR (565
MHz, CDCl3): δ -78.2. IR (neat): 3088, 3009, 1568, 1475, 1397,
triphenylsulfonium trifluoromethanesulfonate (3aa). White
solid, mp: 135-136
℃, 111.2 mg, 90% yield. (Rf = 0.28, eluent:
4 | J. Name., 2012, 00, 1-3
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1254, 1153, 1091, 1029, 824, 743, 683, 637. HRMS: calculated
for C18H13Cl2S+([M-TfO-]+): 331.0115; found: 331.0105.
(3-methoxyphenyl)diphenylsulfonium
trifluoromethane
sulfonate (3am). Yellow oil, 88.9 mg, 67% yield. (Rf = 0.28,
1
diphenyl(o-tolyl)sulfonium
trifluoromethanesulfonate eluent: DCM/MeOH = 15/1). H NMR (600 MHz, CDCl3): δ 7.76
℃, 70.4 mg, 55% yield. (Rf = – 7.71 (m, 2H), 7.70 – 7.65 (m, 8H), 7.59 – 7.54 (m, 1H), 7.26 –
(3ag). Yellow solid, mp: 122-123
0.30, eluent: DCM/MeOH = 15/1). 1H NMR (600 MHz, CDCl3): δ 7.25 (m, 1H), 7.23 (dd, J = 8.4, 2.3 Hz, 1H), 7.11 (dd, J = 8.0, 1.9
7.79 – 7.74 (m, 2H), 7.72 – 7.67 (m, 4H), 7.67 – 7.63 (m, 4H), Hz, 1H), 3.81 (s, 3H). 13C NMR (151 MHz, CDCl3): δ 161.4, 134.7,
7.62 (d, J = 8.6 Hz, 1H), 7.51 – 7.43 (m, 2H), 7.05 (d, J = 9.0 Hz, 132.4, 131.6, 131.0, 125.0, 124.1, 122.4, 120.8, 120.8 (q, J =
1H), 2.53 (s, 3H). 13C NMR (151 MHz, CDCl3): δ 140.6, 134.7, 321.6 Hz, TfO-), 116.0, 56.1. 19F NMR (565 MHz, CDCl3): δ -78.1.
134.5, 133.1, 131.7, 131.2, 129.8, 129.1, 123.1, 122.6, 120.7 (q, IR (neat): 3070, 2941, 2834, 1597, 1488, 1446, 1328, 1251,
J = 322.4 Hz, TfO-), 19.7. 19F NMR (565 MHz, CDCl3): δ -78.1. IR 1160, 1137, 1026, 795, 750, 690, 635. HRMS: calculated for
(neat): 3067, 2916, 1474, 1446, 1258, 1149, 1029, 754, 683, C19H17OS+([M-TfO-]+): 293.1000; found: 293.0989.
635. HRMS: calculated for C19H17S+([M-TfO-]+): 277.1051;
found: 277.1043.
bis(4-(2-oxopropoxy)phenyl)(phenyl)sulfonium
trifluoro
methanesulfonate (3an). Yellow oil, 63.5 mg, 38% yield. (Rf =
(2-methoxyphenyl)diphenylsulfonium
trifluoromethane 0.30, eluent: DCM/MeOH = 15/1). 1H NMR (600 MHz, CDCl3): δ
℃, 83.6 mg, 63% 7.71– 7.69 (m, 1H), 7.66 – 7.62 (m, 2H), 7.60 – 7.57(m, 4H),
sulfonate (3ah). Yellow solid, mp: 120-122
yield. (Rf = 0.30, eluent: DCM/MeOH = 15/1). 1H NMR (600 7.53 (d, J = 7.7 Hz, 2H), 7.20 – 7.15 (m, 4H), 4.80 (s, 4H), 2.24
MHz, CDCl3): δ 7.77 – 7.72 (m, 3H), 7.70 – 7.67 (m, 4H), 7.60 – (s, 6H). 13C NMR (151 MHz, CDCl3): δ 202.6, 162.8, 134.2,
7.56 (m, 4H), 7.24 (dd, J = 8.5, 0.9 Hz, 1H), 7.18 – 7.15 (m, 1H), 133.1, 131.5, 130.0, 125.8, 120.8 (q, J = 320.6 Hz, TfO-), 117.9,
6.94 (dd, J = 8.1, 1.5 Hz, 1H), 3.87 (s, 3H). 13C NMR (151 MHz, 114.6, 72.8, 26.3. 19F NMR (565 MHz, CDCl3): δ -78.1. IR (neat):
CDCl3): δ 157.9, 137.0, 134.6, 131.6, 130.7, 130.5, 123.1, 122.8, 3096, 3017, 2918, 1731, 1587, 1493, 1446, 1257, 1171, 1073,
113.5, 110.7, 57.1. Carbon of triflate anion cannot be found. 1029, 832, 749, 684, 637. HRMS: calculated for C24H23O4S+([M-
19F NMR (565 MHz, CDCl3): δ -78.1. IR (neat): 3063, 2950, 2854, TfO-]+): 407.1317; found: 407.1310.
1587, 1477, 1447, 1254, 1221, 1148, 1072, 1029, 753, 685,
bis(4-(2-methoxy-2-oxoethoxy)phenyl)(phenyl)sulfonium
635. HRMS: calculated for C19H17OS+([M-TfO-]+): 293.1000; tri-fluoromethanesulfonate (3ao). Yellow oil, 77.7 mg, 44%
found: 293.0999.
yield. (Rf = 0.30, eluent: DCM/MeOH = 15/1). 1H NMR (600
bis(2,4-dimethylphenyl)(phenyl)sulfonium
methanesulfonate (3ai). Yellow solid, mp: 103-105
trifluoro MHz, CDCl3) δ: 7.72 – 7.61 (m, 7H), 7.62 – 7.56 (m, 2H), 7.20 –
℃
, 101.2 7.14 (m, 4H), 4.73 (s, 4H), 3.78 (s, 6H). 13C NMR (151 MHz,
mg, 72% yield. (Rf = 0.28, eluent: DCM/MeOH = 15/1). 1H NMR CDCl3) δ: 168.1, 162.6, 134.2, 133.2, 131.4, 130.1, 125.7, 120.8
(400 MHz, CDCl3): δ 7.80 – 7.70 (m, 3H), 7.62 – 7.60 (m, 2H), (q, J = 321.6 Hz, TfO-), 117.8, 115.2, 65.1, 52.5. 19F NMR (565
7.32 (s, 2H), 7.27 – 7.25 (m, 2H), 6.87 (d, J = 8.3 Hz, 2H), 2.48 MHz, CDCl3): δ -78.1. IR (neat): 3096, 3017, 2956, 1749, 1587,
(s, 6H), 2.41 (s, 6H). 13C NMR (151 MHz, CDCl3): δ 146.1, 140.4, 1492, 1445, 1256, 1212, 1171, 1073, 1029, 832, 751, 699, 636.
134.7, 133.9, 131.8, 131.2, 130.1, 129.9, 121.9, 120.8 (q, J = HRMS: calculated for C24H23O6S+([M-TfO-]+): 439.1215; found:
322.4 Hz, TfO-), 118.5, 21.4, 19.5. 19F NMR (565 MHz, CDCl3): δ 439.1199.
-78.1. IR (neat): 3065, 2922, 1600, 1476, 1446, 1256, 1142,
bis(4-(cyanomethoxy)phenyl)(phenyl)sulfonium trifluoro
1028, 809, 757, 688, 634. HRMS: calculated for C22H23S+([M- methanesulfonate (3ap). Yellow oil, 61.1 mg, 39% yield. (Rf =
TfO-]+): 319.1521; found: 319.1519.
0.30, eluent: DCM/MeOH = 15/1). 1H NMR (600 MHz, CDCl3) δ:
(4-chlorophenyl)(phenyl)(p-tolyl)sulfonium
trifluoro 7.79 – 7.75 (m, 1H), 7.72 – 7.68 (m, 6H), 7.64 – 7.61 (m, 2H),
methanesulfonate (3ak). Yellow oil, 114.8 mg, 83% yield. (Rf = 7.35-7.31 (m, 4H), 4.96 (s, 4H). 13C NMR (151 MHz, CDCl3) δ:
0.28, eluent: DCM/MeOH = 15/1). 1H NMR (600 MHz, CDCl3): δ 161.3, 134.6, 133.4, 131.7, 130.4, 125.1, 118.2, 116.4, 114.2,
7.76 – 7.66 (m, 7H), 7.65 – 7.60 (m, 4H), 7.49 (d, J = 8.1 Hz, 2H), 53.77. Carbon of triflate anion cannot be found. 19F NMR (565
2.45 (s, 3H). 13C NMR (151 MHz, CDCl3): δ 146.6, 141.6, 134.6, MHz, CDCl3): δ -78.2. IR (neat): 3026, 2919, 2849, 2232, 1602,
132.5, 132.4, 131.8, 131.7, 131.1, 130.9, 124.4, 123.1, 120.8 (q, 1493, 1452, 1261, 1156, 1029, 966, 911, 759, 699, 636. HRMS:
J = 320.9 Hz, TfO-), 120.2, 21.6. 19F NMR (565 MHz, CDCl3): δ - calculated for C22H17N2O2S+([M-TfO-]+): 373.1011; found:
78.1. IR (neat): 3088, 3067, 2926, 1590, 1477, 1447, 1258, 373.1010.
1155, 1029, 745, 638. HRMS: calculated for C19H16ClS+([M-TfO-
]+): 311.0661; found: 311.0660.
9-phenoxy-9H-9,10-[1,2]benzenothioxanthen-10-ium
trifluoromethanesulfonate (3aq). Yellow solid, mp: 235-236
(4-fluorophenyl)diphenylsulfonium
trifluoromethane
℃, 121.0 mg, 78% yield. (Rf = 0.30, eluent: DCM/MeOH =
sulfonate (3al). Yellow solid, mp: 111-113
℃
, mg, 75% yield. 15/1). 1H NMR (600 MHz, CDCl3): δ 8.50 (dd, J = 7.7, 0.6 Hz, 3H),
(Rf = 0.28, eluent: DCM/MeOH = 15/1). 1H NMR (600 MHz, 7.82 (dd, J = 7.7, 0.9 Hz, 3H), 7.49 – 7.45 (m, 3H), 7.43 – 7.40
CDCl3): δ 7.87 – 7.82 (m, 2H), 7.77 – 7.73 (m, 2H), 7.72 – 7.67 (m, 3H), 7.35 – 7.30 (m, 2H), 7.16 – 7.13 (m, 1H), 6.99– 6.96 (m,
(m, 8H), 7.41 – 7.35 (m, 2H). 13C NMR (151 MHz, CDCl3): δ 2H). 13C NMR (151 MHz, CDCl3): δ 153.5, 142.2, 132.2, 130.4,
166.2 (d, J= 259.7 Hz), 134.7, 134.3, 134.2, 131.7, 130.9, 124.3, 129.3, 129.2, 128.2, 126.8, 122.8, 120.7 (q, J = 320.9 Hz, TfO-),
120.8 (q, J= 320.9 Hz, TfO-), 119.3 (d, J= 24.2 Hz). 19F NMR (565 117.9, 84.5. 19F NMR (565 MHz, CDCl3): δ -78.0. IR (neat): 3072,
MHz, CDCl3): δ -78.1, -100.3. IR (neat): 3097, 3066, 1588, 1492, 2966, 2358, 1598, 1488, 1447, 1250, 1222, 1160, 1140, 1026,
1473, 1261, 1223, 1147, 1030, 746, 680, 636. HRMS: calculated 750, 635. HRMS: calculated for C25H17OS+([M-TfO-]+): 365.1000;
for C18H14FS+([M-TfO-]+): 281.0800; found: 281.0790. The 3al is found: 365.0983.
a known compound20.
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bis(4-phenoxyphenyl)(phenyl)sulfonium trifluoromethane 0.28, eluent: DCM/MeOH = 15/1). 1H NMR (600 MHz, CDCl3): δ
sulfonate (3ar). Yellow oil, 62.6 mg, 35% yield. (Rf = 0.30, 7.54 – 7.52 (m, 4H), 7.48 – 7.46 (m, 4H), 7.33 (dd, J = 8.3, 2.0
1
eluent: DCM/MeOH = 15/1). H NMR (600 MHz, CDCl3): δ 7.73 Hz, 1H), 7.03 (d, J = 8.3 Hz, 1H), 6.96 (d, J = 2.0 Hz, 1H), 6.13 (s,
– 7.66 (m, 9H), 7.43 – 7.38 (m, 4H), 7.25 – 7.22 (m, 2H), 7.18 – 2H), 2.45 (s, 6H). 13C NMR (151 MHz, CDCl3): δ 153.4, 150.3,
7.14 (m, 4H), 7.08 – 7.04 (m, 4H). 13C NMR (151 MHz, CDCl3): δ 146.0, 132.2, 130.5, 128.0, 121.6, 120.8 (q, J = 321.6 Hz, - TfO-),
163.4, 154.0, 134.2, 133.3, 131.5, 130.4, 125.8, 125.7, 120.8 (q, 115.5, 110.6, 109.6, 103.3, 21.6. 19F NMR (565 MHz, CDCl3): δ -
J = 320.1 Hz, TfO-), 120.7, 119.6, 116.0. 19F NMR (565 MHz, 78.1. IR (neat): 3084, 3048, 2920, 1591, 1479, 1245, 1151,
CDCl3): δ -78.1. IR (neat): 3093, 3063, 1575, 1483, 1245, 1167, 1027, 926, 807, 636. HRMS: calculated for C21H19O2S+([M-TfO -
1071, 1029, 869, 755, 694, 637. HRMS: calculated for ]+): 335.1106; found: 335.1089.
C30H23O2S+([M-TfO-]+): 447.1418; found: 4447.1405.
benzo[d][1,3]dioxol-5-ylbis(4-methoxyphenyl)sulfonium
(3,4-dimethylphenyl)diphenylsulfonium trifluoromethane trifluoromethanesulfonate (3cc). Yellow oil, 120.9 mg, 78%
sulfonate (3ba). Yellow oil, 83.3 mg, 63% yield. (Rf = 0.30, yield. (Rf = 0.30, eluent: DCM/MeOH = 15/1). 1H NMR (600
1
eluent: DCM/MeOH = 15/1). H NMR (600 MHz, CDCl3): δ 7.75 MHz, CDCl3): δ 7.62 – 7.58 (m, 4H), 7.20 (dd, J = 8.3, 2.1 Hz,
– 7.71 (m, 2H), 7.70 – 7.64 (m, 8H), 7.46 (d, J = 2.0 Hz, 1H), 7.42 1H), 7.16 – 7.13 (m, 4H), 6.99 (d, J = 8.3 Hz, 1H), 6.92 (d, J = 2.1
(d, J = 8.2 Hz, 1H), 7.35 (dd, J = 8.2, 2.2 Hz, 1H), 2.33 (s, 3H), Hz, 1H), 6.11 (s, 2H), 3.86 (s, 6H). 13C NMR (151 MHz, CDCl3):δ
2.30 (s, 3H). 13C NMR (151 MHz, CDCl3): δ 145.2, 141.1, 134.4, 164.3, 153.0, 150.2, 132.6, 126.9, 120.8 (q, J = 321.6 Hz, TfO-),
132.6, 131.6, 131.5, 130.8, 128.4, 124.6, 120.8 (q, J = 320.1 Hz, 117.1, 116.9, 114.7, 110.4, 109.1, 103.3, 56.0. 19F NMR (565
TfO-), 120.2, 20.0, 19.8. 19F NMR (565 MHz, CDCl3): δ -78.1. IR MHz, CDCl3): δ -78.1. IR (neat): 3093, 3012, 2916, 1587, 1479,
(neat): 3064, 2924, 1605, 1447, 1255, 1153, 1029, 750, 684, 1246, 1153, 1027, 927, 833, 755, 637. HRMS: calculated for
636. HRMS: calculated for C20H19S+([M-TfO-]+): 291.1207; C21H19O4S+([M-TfO-]+): 367.1004; found: 367.1001.
found: 291.1204.
(3,4-dimethylphenyl)di-p-tolylsulfonium trifluoromethane sulfonate (3da). Yellow oil, 78.3 mg, 59% yield. (Rf = 0.30,
sulfonate (3bb). Yellow solid, mp: 100-102
, 99.8 mg, 71% eluent: DCM/MeOH = 15/1).1H NMR (600 MHz, CDCl3): δ 7.78
(3-methoxyphenyl)diphenylsulfonium
trifluoromethane
℃
yield. (Rf = 0.30, eluent: DCM/MeOH = 15/1). 1H NMR (600 – 7.72 (m, 2H), 7.71 – 7.67 (m, 8H), 7.58 – 7.56 (m, 1H), 7.28 –
MHz, CDCl3): δ 7.53 – 7.50 (m, 4H), 7.46 – 7.44 (m, 4H), 7.39 (d, 7.27 (m, 1H), 7.24 (dd, J = 8.3, 2.2 Hz, 1H), 7.12 (dd, J = 7.9, 1.3
J = 8.3 Hz, 2H), 7.29 (dd, J = 8.1, 2.2 Hz, 1H), 2.42 (s, 6H), 2.32 Hz, 1H), 3.82 (s, 3H). 13C NMR (151 MHz, CDCl3): δ 161.4, 134.7,
(s, 3H), 2.29 (s, 3H). 13C NMR (151 MHz, CDCl3): δ 145.9, 144.8, 132.4, 131.6, 131.0, 125.0, 124.1, 122.5, 120.8, 120.8 (q, J =
141.0, 132.5, 132.1, 131.1, 130.6, 128.0, 121.1, 120.9, 120.8 (q, 320.1 Hz, TfO-), 116.1, 56.1. 19F NMR (565 MHz, CDCl3): δ -78.1.
J = 321.6 Hz, TfO-), 21.5, 19.9, 19.8. 19F NMR (565 MHz, CDCl3): IR (neat): 3070, 2941, 2834, 1597, 1488, 1446, 1328, 1251,
δ -78.1. IR (neat): 3048, 2927, 1591, 1489, 1449, 1259, 1221, 1160, 1137, 1026, 795, 750, 690, 635. HRMS: calculated for
1189, 1149, 1076, 1028, 810, 754, 700, 636. HRMS: calculated C19H17OS+([M-TfO-]+): 293.1000; found: 293.0989.
for C22H23S+([M-TfO-]+): 319.1521; found: 319.1518.
(3-methoxyphenyl)di-p-tolylsulfonium
trifluoromethane
(3,4-dimethylphenyl)bis(4-methoxyphenyl)sulfonium
sulfonate (3db). Yellow oil, 135.5 mg, 96% yield. (Rf = 0.30,
1
trifluoromethanesulfonate (3bc). Yellow oil, 121.6 mg, 81% eluent: DCM/MeOH = 15/1). H NMR (600 MHz, CDCl3): δ 7.57
yield. (Rf = 0.30, eluent: DCM/MeOH = 15/1). 1H NMR (600 – 7.51 (m, 5H), 7.46-7.44 (m, 4H), 7.22 – 7.16 (m, 2H), 7.08 –
MHz, CDCl3): δ 7.60 – 7.56 (m, 4H), 7.36 (d, J = 8.2 Hz, 1H), 7.30 7.04 (m, 1H), 3.80 (s, 3H), 2.42 (s, 6H). 13C NMR (151 MHz,
(d, J = 1.9 Hz, 1H), 7.23 (dd, J = 8.1, 2.2 Hz, 1H), 7.15 – 7.12 (m, CDCl3): δ 161.3, 146.1, 132.3, 132.2, 130.8, 125.8, 122.0, 120.8
4H), 3.84 (s, 6H), 2.29 (s, 3H), 2.27 (s, 3H). 13C NMR (151 MHz, (q, J = 320.1 Hz, TfO-), 120.6, 120.3, 115.6, 56.0, 21.5. 19F NMR
CDCl3): δ 164.2, 144.2, 140.8, 132.7, 132.3, 130.4, 127.3, 122.2, (565 MHz, CDCl3): δ -78.2. IR (neat): 3070, 2964, 1592, 1485,
120.8 (q, J = 321.6 Hz, TfO-), 117.0, 114.3, 55.9, 19.8. 19F NMR 1451, 1251, 1222, 1151, 1027, 754, 695, 636. HRMS: calculated
(565 MHz, CDCl3): δ -78.1. IR (neat): 3017, 2928, 2844, 2357, for C21H21OS+([M-TfO-]+): 321.1313; found: 321.1307.
1590, 1497, 1257, 1231, 1170, 1034, 834, 766, 631. HRMS:
C22H23O2S+([M-TfO-]+):351.1419;
(3-methoxyphenyl)bis(4-methoxyphenyl)sulfonium
calculated
351.1417.
for
found: trifluoromethanesulfonate (3dc). Yellow oil, 141.7 mg, 94%
yield. (Rf = 0.30, eluent: DCM/MeOH = 15/1). 1H NMR (600
benzo[d][1,3]dioxol-5-yldiphenylsulfonium
trifluoro MHz, CDCl3): δ 7.65 – 7.62 (m, 4H), 7.54 – 7.52 (m, 1H), 7.20 –
methanesulfonate (3ca). Yellow oil, 83.5 mg, 61% yield. (Rf = 7.14 (m, 5H), 7.11 – 7.10 (m, 1H), 7.03 (dd, J = 7.9, 1.3 Hz, 1H),
0.30, eluent: DCM/MeOH = 15/1). 1H NMR (600 MHz, CDCl3): δ 3.87 (s, 6H), 3.81 (s, 3H). 13C NMR (151 MHz, CDCl3): δ 164.5,
7.75 – 7.70 (m, 2H), 7.69 – 7.63 (m, 8H), 7.37 (dd, J = 8.3, 2.1 161.3, 133.1, 132.2, 127.2, 121.5, 120.8 (q, J = 320.9 Hz, TfO-),
Hz, 1H), 7.02 (d, J = 8.3 Hz, 1H), 6.99 (d, J = 2.1 Hz, 1H), 6.12 (s, 119.9, 117.2, 115.1, 113.9, 56.1, 56.0. 19F NMR (565 MHz,
2H). 13C NMR (151 MHz, CDCl3): δ 153.6, 150.4, 134.4, 131.5, CDCl3): δ -78.2. IR (neat): 3093, 2945, 2843, 1588, 1494, 1255,
130.5, 128.5, 124.9, 120.8 (q, J = 320.1 Hz, TfO-), 114.4, 110.6, 1152, 1074, 1028, 833, 798, 680, 637. HRMS: calculated for
109.7, 103.4. 19F NMR (565 MHz, CDCl3): δ -78.1. IR (neat): C21H21O3S+([M-TfO-]+): 353.1211; found: 353.1200.
3070, 2918, 1600, 1477, 1446, 1250, 1140, 1026, 924, 747,
(3-bromophenyl)diphenylsulfonium
trifluoromethane
685, 634. HRMS: calculated for C19H15O2S+([M-TfO-]+): sulfonate (3ea). Yellow oil, 98.7 mg, 67% yield. (Rf = 0.30,
307.0793; found: 307.0787.
eluent: DCM/MeOH = 15/1).1H NMR (600 MHz, CDCl3): δ 7.87
– 7.84 (m, 1H), 7.80 – 7.76 (m, 2H), 7.76 – 7.70 (m, 10H), 7.62 –
benzo[d][1,3]dioxol-5-yldi-p-tolylsulfoniumtrifluoro
methanesulfonate (3cb). Yellow oil, 107.6 mg, 74% yield. (Rf = 7.59 (m, 1H). 13C NMR (151 MHz, CDCl3): δ 137.6, 135.0, 133.1,
6 | J. Name., 2012, 00, 1-3
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132.9, 131.8, 131.2, 129.9, 126.3, 125.0, 123.6, 120.8 (q, J = P.B. is grateful for the financial support from Zhejiang Normal
321.6 Hz, TfO-). 19F NMR (565 MHz, CDCl3): δ -78.1. IR (neat): University, the National Natural Science Foundation of China
3093, 3063, 1476, 1447, 1251, 1223, 1151, 1027,995, 747, 683, (Grant 21502171) and the State Key Laboratory of Fine
634, 496. HRMS: calculated for C18H14BrS+([M-TfO-]+): Chemicals (KF 1512). Z L. acknowledges support from the
340.9994; found: 340.9991.
Natural Science Foundation of Zhejiang Province
(3-bromophenyl)di-p-tolylsulfonium
trifluoromethane (LY16B020002).
sulfonate (3eb). Yellow oil, 134.0 mg, 86% yield. (Rf = 0.30,
eluent: DCM/MeOH = 15/1).1H NMR (600 MHz, CDCl3): δ 7.82-
7.80 (m, 1H), 7.68 – 7.67 (m, 1H), 7.64 – 7.62 (m, 1H), 7.61 –
7.56 (m, 5H), 7.48 (d, J = 8.3 Hz, 4H), 2.44 (s, 6H). 13C NMR
(151 MHz, CDCl3): δ 146.6, 137.4, 132.9, 132.5, 132.4, 131.1,
129.4, 127.1, 124.8, 120.1, 120.8 (q, J = 320.1 Hz, TfO-), 21.6.
19F NMR (565 MHz, CDCl3): δ -78.1. IR (neat): 3088, 2921, 2850,
1719, 1589, 1461, 1403, 1255, 1222, 1150, 1026, 806, 753,
672, 636, 501. HRMS: calculated for C20H18BrS+([M-TfO-]+):
369.0307; found: 369.0306.
Notes and references
1
For selected reviews on aryne chemistry, see: (a) H. H. Wenk,
M. Winkler and W. Sander, Angew. Chem., Int. Ed., 2003, 42
,
502; (b) A. Bhunia, S. R. Yetra and A. T. Biju, Chem. Soc. Rev.,
2012, 41, 3140; (c) C. Wu and F. Shi, Asian J. Org. Chem.,
2013, 2, 116; (d) A. V. Dubrovskiy, N. A. Markina and R. C.
Larock, Org. Biomol. Chem., 2013, 11, 191; (e) S. Yoshida and
T. Hosoya, Chem. Lett., 2015, 44, 1450; (f) S. S. Bhojgude, A.
Bhunia and A. T. Biju, Acc. Chem. Res., 2016, 49, 1658.
2
3
For reviews regarding to the synthetic applications of arynes,
see: (a) H. Pellissier and M. Santelli, Tetrahedron, 2003, 59
(3-bromophenyl)bis(4-methoxyphenyl)sulfonium
,
trifluoromethanesulfonate (3ec). Yellow oil, 155.5 mg, 94%
yield. (Rf = 0.30, eluent: DCM/MeOH = 15/1).1H NMR (600
MHz, CDCl3): δ 7.80 – 7.76 (m, 1H), 7.71 – 7.67 (m, 4H), 7.61 –
7.60 (m, 1H), 7.56 – 7.53 (m, 2H), 7.19 – 7.14 (m, 4H), 3.86 (s,
6H). 13C NMR (151 MHz, CDCl3): δ 164.7, 136.9, 133.3, 132.7,
131.9, 128.6, 128.5, 124.7, 117.3, 113.3, 120.8 (q, J = 321.6 Hz,
TfO-), 56.1. 19F NMR (565 MHz, CDCl3): δ -78.1. IR (neat): 3081,
2932, 2843, 1586, 1474, 1438, 1342, 1195, 1116, 1072, 1061,
835, 772, 724, 618, 588, 512. HRMS: calculated for
C20H18BrO2S+([M-TfO-]+): 401.0205; found: 401.0206.
701; (b) R. Sanz, Org. Prep. Proced. Int., 2008, 40, 215; (c) P.
M. Tadross and B. M. Stoltz, Chem. Rev., 2012, 112, 3550; (d)
C. M. Gampe and E. M. Carreira, Angew. Chem., Int. Ed.,
2012, 51, 3766; (e) A. E. Goetz, T. K. Shah and N. K. Garg,
Chem. Commun., 2015, 51, 34.
(a) J. G. Radziszewski, B. A. J. Hess and R. Zahradnik, J. Am.
Chem. Soc., 1992, 114, 52; (b) P. Godfrey, Aust. J. Chem.,
2010, 63, 1061; (c) A. E. Goetz, S. M. Bronner, J. D. Cisneros,
J. M. Melamed, R. S. Paton, K. N. Houk and N. K. Garg,
Angew. Chem., Int. Ed., 2012, 51, 2758; (d) J. M. Medina, T.
C. McMahon, G. Jiménez-Osés, K. N. Houk and N. K. Garg, J.
Am. Chem. Soc., 2014, 136, 14706; (e) N. F. Fine Nathel, L. A.
(3,4-difluorophenyl)di-p-tolylsulfonium trifluoromethane
sulfonate (3fb). Yellow oil, 61.5 mg, 43% yield. (Rf = 0.31,
1
eluent: DCM/MeOH = 15/1). H NMR (600 MHz, CDCl3): δ 7.63
Morrill, H. Mayr and N. K. Garg, J. Am. Chem. Soc., 2016, 138
10402.
(a) Z.-J. Liu and R. C. Larock, Org. Lett., 2003, 5, 4673; (b) Z.-J.
,
4
Liu and R. C. Larock, J. Am. Chem. Soc., 2005, 127, 13112; (c)
Z.-J. Liu and R. C. Larock, J. Org. Chem., 2006, 71, 3198; (d) A.
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6H). 13C NMR (151 MHz, CDCl3): δ154.0 (dd, J = 262.7 Hz, 12.1
Hz), 151.3 (dd, J = 258.2 Hz, 14.3 Hz), 146.6, 132.5, 131.0,
128.69 (dd, J = 7.6 Hz, 3.8Hz), 121.3 (m), 120.8 (d, J = 19.6 Hz),
120.7 (q, J = 320.1 Hz, TfO-), 120.4 (d, J = 21.1 Hz), 120.3, 21.6.
19F NMR (565 MHz, CDCl3): δ -78.2 (s), -125.4 (d, J = 21.0 Hz), -
129.1 (d, J = 21.0 Hz). IR (neat): 3086, 3050, 2926, 1591, 1507,
1489, 1252, 1224, 1155, 1028, 809, 777, 637. HRMS: calculated
for C20H17F2S+([M-TfO-]+): 327.1019; found: 327.1010.
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triphenylselenonium
Following the general procedure in which diphenylselane
was used instead of diarylsulfide , the title compound was
trifluoromethanesulfonate
(5).
4
2
obtained as a yellow oil, 42.7 mg, 31% yield. (Rf = 0.34, eluent:
1
DCM/MeOH = 15/1). H NMR (600 MHz, CDCl3) δ: 7.72 – 7.68
(m, 3H), 7.67 – 7.56 (m, 12H). 13C NMR (151 MHz, CDCl3) δ:
133.7, 131.6, 131.1, 126.3. 120.6 (q, J = 320.1 Hz, TfO-). 19F
NMR (565 MHz, CDCl3): δ -78.2. IR (neat): 3088, 3062, 1474,
1446, 1258, 1149, 1065, 996, 839, 1029, 754, 635. Compound
5
5
is a known compound 13e
.
Conflict of interest
There are no conflicts to declare.
6
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Acknowledgements
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8 | J. Name., 2012, 00, 1-3
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