Pd-catalyzed Suzuki–Miyaura cross-coupling of [Ph2SR][OTf] with arylboronic acids

Article abstract of DOI:10.1016/j.tet.2016.10.018

The Pd-catalyzed Suzuki–Miyaura cross-coupling of alkyl- and fluoroalkyl(diphenyl)sulfonium triflates with arylboronic acids was compared. The fluorine substitution on the alkyl groups of [Ph₂SR][OTf] had a big influence on the reaction. Perfluoroalkyl(diphenyl)sulfonium triflates (2b–d) were unsuccessful participants in the Pd-catalyzed phenylation of arylboronic acid under the standard conditions because of the strong electronegativity of the long-chain perfluoroalkyl groups, which underwent S[sbnd]R_fnbond cleavage instead. Polyfluoroalkyl(diphenyl)sulfonium triflates (2f–h) reacted with arylboronic acid to afford the phenylation product in very low yields due to the tendency of deprotonation and β-F elimination of the sulfonium salts. Eventually, (2,2,2-trifluoroethyl)diphenylsulfonium triflate (2e), methyl- or ethyl(diphenyl)sulfonium triflate (2i or 2j), and triphenylsulfonium triflate (2m) were found to be more effective reagents than other tested phenylsulfounium salts for Pd-catalyzed phenylation, which provided much higher yields of the desired products under mild conditions.

Full text of DOI:10.1016/j.tet.2016.10.018

Tetrahedron xxx (2016) 1e7
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Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Pd-catalyzed SuzukieMiyaura cross-coupling of [Ph2SR][OTf] with
arylboronic acids
Xiao-Yan Wang, Hai-Xia Song, Shi-Meng Wang, Jing Yang, Hua-Li Qin, Xin Jiang,
*
Cheng-Pan Zhang
School of Chemistry, Chemical Engineering and Life Science, Wuhan University of Technology, 205 Luoshi Road, Wuhan, 430070, China
a r t i c l e i n f o
a b s t r a c t
Article history:
The Pd-catalyzed SuzukieMiyaura cross-coupling of alkyl- and fluoroalkyl(diphenyl)sulfonium triflates
with arylboronic acids was compared. The fluorine substitution on the alkyl groups of [Ph2SR][OTf] had
a big influence on the reaction. Perfluoroalkyl(diphenyl)sulfonium triflates (2bed) were unsuccessful
participants in the Pd-catalyzed phenylation of arylboronic acid under the standard conditions because
of the strong electronegativity of the long-chain perfluoroalkyl groups, which underwent SeRfn bond
cleavage instead. Polyfluoroalkyl(diphenyl)sulfonium triflates (2feh) reacted with arylboronic acid to
Received 19 August 2016
Received in revised form 6 October 2016
Accepted 9 October 2016
Available online xxx
Keywords:
Palladium
Fluorine
Sulfonium salts
Arylboronic acids
afford the phenylation product in very low yields due to the tendency of deprotonation and b-F elimi-
nation of the sulfonium salts. Eventually, (2,2,2-trifluoroethyl)diphenylsulfonium triflate (2e), methyl- or
ethyl(diphenyl)sulfonium triflate (2i or 2j), and triphenylsulfonium triflate (2m) were found to be more
effective reagents than other tested phenylsulfounium salts for Pd-catalyzed phenylation, which pro-
vided much higher yields of the desired products under mild conditions.
Ó 2016 Elsevier Ltd. All rights reserved.
1. Introduction
yielded (perfluoroalkyl)diphenylsulfonium salts, which are effec-
tive electrophilic perfluoroalkylation reagents (e.g., Yagupolskii-
Arylsulfonium salts have gained great interest in areas of
chemistry and materials science in the past several decades.1 They
can be readily reduced by pulse radiolytic, chemical, photochemi-
cal, and electrochemical methods via single electron transfer pro-
cesses.2 This intriguing property has led to triarylsulfonium salts as
important photoinitiators in cationic polymerization reactions and
as excellent photoacid generators capable of releasing protons
under irradiation, which have been widely used in the fields of
coatings, adhesives, photoresists, microfabrication, and pattern-
ing.3 The aryl radicals derived from triarylsulfonium salts under
photocatalytic conditions have accomplished the carbonecarbon
bond formation with allyl sulfones and activated olefins.4 The
conjugate addition of nucleophiles to vinyl(diphenyl)sulfonium
salts in situ forms sulfur ylides, which have been successfully uti-
lized in a variety of cyclization reactions.5,6
eUmemoto reagents) to perfluoroalkylate various nucleophiles
under mild reaction conditions, showing much different re-
activities from the non-fluorinated (alkyl)diphenylsulfonium ana-
logs.8 (Trifluoromethyl)diphenylsulfoniums, the fluorinated
version of (methyl)diphenylsulfoniums, are also effective CF3
transfer sources in the reductive trifluoromethylation reactions
towards a wide range of substrates, initiated by copper, photoredox
catalysts, and other reductants.9 Moreover, (2,2,2-trifluoroethyl)
diphenylsulfonium triflate, a partially fluorinated version of (ethyl)
diphenylsulfonium triflate, is an efficient ylide reagent and tri-
fluoromethylcarbene source to successfully afford a large number
of trifluoromethyl cyclopropanes and their derivatives.10
Recently, we found that (trifluoromethyl)diarylsulfonium tri-
flates could be used as cross-coupling partners in Pd-catalyzed
SuzukieMiyaura reaction with arylboronic acids.11 The use of 1-
aryl(tetrahydro)thiophenium salts as cross-coupling agents in the
similar reaction was also reported.12 Since the fluorine substitution
often significantly alters the properties of molecules, we speculated
that phenylsulfonium salts bearing fluoroalkyl groups might have
distinctive reaction profiles compared to the non-fluorinated ana-
logs in the Pd-catalyzed SuzukieMiyaura cross-couplings. To un-
derstand the ‘fluorine effects’ and to determine the efficient cross-
coupling partners in this type of transformation, we further studied
It has been well known that the introduction of fluorine atoms
into organic compounds can dramatically change their physical,
chemical, and biological properties.7 The incorporation of per-
fluoroalkyl groups into diphenylsulfoniums at the sulfur center has
* Corresponding author. E-mail addresses: cpzhang@whut.edu.cn,
zhangchengpan1982@hotmail.com (C.-P. Zhang).
http://dx.doi.org/10.1016/j.tet.2016.10.018
0040-4020/Ó 2016 Elsevier Ltd. All rights reserved.
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2
X.-Y. Wang et al. / Tetrahedron xxx (2016) 1e7
the reactions of arylboronic acids with a family of phenylsulfonium
salts bearing either fluoroalkyl or alkyl moieties on the sulfur
atoms.
triflate (2l) with 1a provided 3a in 56% yield, which was approxi-
mate to those using other aryl(tetrahydro)thiopheniums as the
cross-coupling partners in SuzukieMiyaura reactions with orga-
noboron reagents.12 These results implied that the non-fluorinated
alkyl diphenylsulfonium triflates were more effective participants
than the non-fluorinated dialkyl phenylsulfonium compounds in
the Pd-catalyzed SuzukieMiyaura cross-couplings. In addition, the
reaction of 1a with triphenylsulfonium triflate (2m), a well-known
photoacid generator, could give 3a in 92% yield under the standard
reaction conditions, the yield of which was nearly equal to those
using 2e, 2i, and 2j (Table 1).
To shed more light on this transformation, we monitored the
reactions of several representative phenylsulfonium triflates by
HPLC (Fig. 1). It was found that the Pd-catalyzed reactions of 1a with
2e, 2i, and 2j exhibited similar reactivity profiles, which were almost
completed in 3 h and gave comparable yields of 3a after 6 h. Fur-
thermore, the cross-coupling of 2a with 1a proceeded fast at the
beginning of the reaction and 1 h later it slowed down, which finally
provided 3a in moderate yield. Likewise, a fast formation of 3a was
observed in the cases of 2g and 2h during the first 40e60 min of the
reactions and later the transformation shut down. We suggested
2. Results and discussion
Initially, the reaction of (trifluoromethyl)diphenylsulfonium tri-
flate (2a,1.5 equiv) with [1,10-biphenyl]-4-ylboronic acid (1a) in DMF
in the presence of Pd[P(t-Bu)3]2 (5 mol %) and NaHCO3 (2 equiv) at
60 ꢀC for 6 h provided 1,10:40,100-terphenyl (3a) in 53% yield (Table 1)
(For reaction condition optimization see Electronic Supplementary
Information (ESI)). When (perfluoroethyl)diphenylsulfonium (2b),
(perfluorobutyl)diphenylsulfonium (2c), or (perfluorooctyl)diphe-
nylsulfonium triflate (2d) was used instead of 2a in the same re-
action, 3a was obtained in trace amount (Table 1). This phenomenon
may be attributed to the stronger electronegativity of the long-chain
perfluoroalkyl groups of [Ph2SRfn][OTf] than the CF3 moiety, which
preferentially underwent the SeRfn bond cleavage of [Ph2SRfn] cat-
ions in the reaction (see ESI). Interestingly, if (2,2,2-trifluoroethyl)
diphenylsulfonium triflate (2e) was treated with 1a under the
standard conditions, 3a was formed in 94% yield (Table 1). Never-
theless, treatment of (2,2,3,3,3-pentafluoropropyl)diphenylsulfo-
nium triflate (2f) with 1a, 3a was prepared in 10% yield. Similarly, the
reaction of (2,2-difluoroethyl)diphenylsulfonium triflate (2g) or (2-
fluoroethyl)diphenylsulfonium triflate (2h) with 1a gave 3a in 19%
or 23% yield, respectively. The 19F NMR analysis of the reaction
mixtures indicated that 2feh decomposed in the reaction, which
might cause the poor yields of 3a.
that the cleavage of the SeRfn bonds of [Ph2SRfn][OTf] and the b-F
elimination of the CH2Rfn groups of [Ph2SCH2Rfn][OTf] might hap-
pen in these reactions (according to 19F NMR analysis of the reaction
mixtures, see ESI),13 which ceased the SuzukieMiyaura cross-
coupling once the sulfonium salts were completely consumed.
This trend could be strengthened with the elongation of per-
fluoroalkyl chains of [Ph2SRfn][OTf] (e.g., 2bed), which led to the
Table 1
Pd-catalyzed SuzukieMiyaura cross-coupling of [Ph2SR][OTf] with [1,1ʹ-biphenyl]-4-ylboronic acid (1a)a
a Reaction conditions: 1a (0.1 mmol)/2 (0.15 mmol)/Pd[P(t-Bu)3]2 (0.005 mmol, 5 mol %)/NaHCO3 (0.2 mmol)/DMF (2 mL)/N2/60 ꢀC/6 h. Yields of 3a were determined by HLPC
using 1,10:40,100-terphenyl as the external standard (tR¼6.145 min, lmax¼278.3 nm, CH3OH/H2O¼90:10 (v/v)). Isolated yield is depicted in the parentheses.
The non-fluorinated phenylsulfonium salts were also in-
vestigated in the reaction (Table 1). (Ethyl)diphenylsulfonium tri-
flate (2i) and (methyl)diphenylsulfonium triflate (2j) reacted with
1a under the standard reaction conditions to supply 3a in 95% and
92% yield, respectively. These yields were comparable to that of 2e
and higher than that of 2a. Moreover, reaction of (dimethyl)phe-
nylsulfonium triflate (2k) with 1a under the standard conditions
gave 3a in 73% yield. Treatment of phenyl(tetrahydro)thiophenium
failure of the conversions. Since 2e has more steric hindrance than
2g and 2h (because of the shielding of -fluorine atoms), the
deprotonation of 2e followed by -F elimination is to some extent
prohibited (see ESI). Increasing the length of perfluoroalkyl groups
of [Ph2SCH2Rfn][OTf], however, the deprotonation and -F elimina-
tion became predominant due to the strong electron-withdrawing
power of Rfn moiety, which counteracted the steric effects, thus
leading to serious inhibition of the phenylation (e.g., 2f).
b
b
b
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X.-Y. Wang et al. / Tetrahedron xxx (2016) 1e7
3
with 2e (or 2i) to give the corresponding phenylation products
(3bej) in high yields (Table 2). The position of substituents on the
phenyl rings of arylboronic acids had little impact on the reaction.
Treatment of [1,10-biphenyl]-3-ylboronic acid (1b) with 2e (or 2i)
provided 3b in 98% (or 93%) yield. When [1,10-biphenyl]-2-ylboronic
acid (1c) reacted with 2e (or 2i), 3c was formed in 95% (or 91%) yield.
The unprotected hydroxyl group of (4-hydroxyphenyl)boronic acid
(1f) was tolerated in the reaction, which gave 3f in 93% (or 96%) yield.
Heteroaryl boronic acids such as benzofuran-2-ylboronic acid (1k),
benzothiophen-2-ylboronic acid (1l), (1-(tert-butoxycarbonyl)-1H-
indol-2-yl)boronic acid (1m), dibenzofuran-4-ylboronic acid (1o),
and dibenzothiophen-4-ylboronic acid (1p) reacted with 2e (or 2i)
under the standard conditions to furnish 3k, 3l, 3m, 3o, and 3p in
excellent yields. Reactions of naphthalen-1-ylboronic acid (1q) and
naphthalen-2-ylboronic acid (1r) with 2e (or 2i) at 60 ꢀC for 6 h
supplied 3q and 3r in good yields. Moreover, (E)-(4-methoxystyryl)
boronic acid (1s) was smoothly converted in the reaction, affording
3s in almost quantitative yield. These results suggested that the
Pd-catalyzed SuzukieMiyaura reaction of 2e (or 2i) is much more
efficient than that of 2a with arylboronic acids in the previous
report.11 Besides, ((8R,9S,13S,14S)-13-methyl-17-oxo-7,8,9,11,12,13,
14,15,16,17-decahydro-6H-cyclopentaphenanthren-3-yl)boronic acid
(1t) was also suitable substrate in the reaction, providing 3t in 77%
yield and indicating good availability of the reaction.
Fig. 1. Reaction conditions: 1a (0.4 mmol)/2a, 2b, 2e, 2g, 2h, 2i, or 2j (0.6 mmol)/Pd
[P(t-Bu)3]2 (0.02 mmol)/NaHCO3 (0.8 mmol)/DMF (10 mL)/N2/60 ꢀC. 100 uL of aliquot
from the reaction mixture was quenched and measured by HPLC at 0, 20, 40, 60, 80,
100, 120, 150, 180, and 360 min for each sulfonium salt. Yields of 3a were determined
by HLPC using 1,1ʹ:40,100-terphenyl as the external standard (tR¼6.145 min,
lmax¼278.3 nm, CH3OH/H2O¼90: 10 (v/v)).
In view of the easy accessibility and the higher yields of 3a ob-
tained than other sulfonium triflates, 2e and 2i (or 2j) were thought
to be the most promising cross-coupling participants among all
tested phenylsulfonium salts in the Pd-catalyzed SuzukieMiyaura
reaction with arylboronic acids. Indeed, arylboronic acids (1bej)
bearing either electron-donating or -withdrawing groups reacted
3. Conclusions
In conclusion, we have found that alkyl- or fluoroalkyl(diphenyl)
sulfonium salts and triphenylsulfonium triflate could be utilized as
Table 2
Pd-catalyzed SuzukieMiyaura cross-coupling of 2e (or 2i) with a variety of arylboronic acidsa
a Reaction conditions: 1 (0.1 or 0.3 mmol)/2 (0.15 or 0.45 mmol)/Pd[P(t-Bu)3]2 (0.005 or 0.015 mmol, 5 mol %)/NaHCO3 (0.2 or 0.6 mmol)/DMF (2 or 4 mL)/N2/60 ꢀC/6 h. Isolated
yield.
b 2e (R¼CH2CF3) was used.
c 2i (R¼CH2CH3) was used.
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4
X.-Y. Wang et al. / Tetrahedron xxx (2016) 1e7
a new class of cross-coupling participants in Pd-catalyzed Suzu-
kieMiyaura reaction, alike the commonly used aryl halides and
pseudo halides (e.g., triflates, tosylates, carboxylates, diazoniums,
iodoniums, and (tetrahydro)thiopheniums).14 The fluorine sub-
stitution on the alkyl groups of alkyl diphenylsulfonium triflates
had a big impact on the reaction. Since the long-chain per-
fluoroalkyl groups have much powerful electronegativity, per-
fluoroalkyl(diphenyl)sulfonium triflates (2bed) failed to
functionalize arylboronic acid under the standard reaction condi-
tions, which might preferentially undergo SeRfn bond cleavage.
Moreover, polyfluoroalkyl(diphenyl)sulfonium triflates (2feh)
reacted with arylboronic acid to provide the phenylation product in
J¼320.4 Hz), 116.8 (s). IR (KBr): 3106, 1450, 1349, 1144, 1109, 1032,
996, 813, 786, 757, 725, 687, 640, 574 cmꢁ1. ESI-MS (m/z): 405.0
([M]þ). Anal. Calcd for C17H10F12O3S2$1.5H2O: C 35.12, H 2.25;
Found: C 35.08, H 2.01.
[Ph2SC2F5][OTf] (2b):9b white solid (4.1 g from 68.4 mmol of
C2F5SO2Na, 9.05 mmol, total yield based on C2F5SO2Na is 13%). 1H
NMR (400 MHz, CDCl3)
d
8.39 (d, J¼8.0 Hz, 4H), 7.94 (t, J¼7.5 Hz,
2H), 7.84 (t, J¼7.8 Hz, 4H). 19F NMR (376 MHz, CDCl3)
d
ꢁ77.6 (t,
J¼1.9 Hz, 3F), ꢁ78.4 (s, 3F), ꢁ96.2 (m, 2F). 13C NMR (126 MHz,
CDCl3)
d
137.5 (s), 134.0 (s), 132.4 (s), 120.9 (q, J¼320.4 Hz), 116.4 (s).
[Ph2SC8F17][OTf] (2d): white solid (2.7 g from 20.0 mmol of
C8F17SO2Na, 3.59 mmol, total yield based on C8F17SO2Na is 18%). Mp
very poor yields for that the deprotonation and
b
-F elimination of
64e65 ꢀC. 1H NMR (400 MHz, CDCl3)
d
8.35 (d, J¼8.0 Hz, 4H), 7.95 (t,
these salts might happen in the reaction. Finally, (2,2,2-
trifluoroethyl)diphenylsulfonium triflate (2e), methyl- or ethyl(-
diphenyl)sulfonium triflate (2i or 2j), and triphenylsulfonium tri-
flate (2m) were found to be more effective cross-coupling partners
than other tested phenylsulfounium salts in Pd-catalyzed Suzu-
kieMiyaura reaction with arylboronic acids. This reaction demon-
J¼7.5 Hz, 2H), 7.85 (t, J¼7.9 Hz, 4H). 19F NMR (376 MHz, CDCl3)
d
ꢁ78.5 (s, 3F), ꢁ80.7 (t, J¼9.8 Hz, 3F), ꢁ90.7 (t, J¼14.6 Hz, 2F), ꢁ115.6
(m, 2F), ꢁ120.9 (m, 2F), ꢁ121.4 (m, 2F), ꢁ121.8 (m, 2F), ꢁ122.6 (m,
2F), ꢁ126.1 (m, 2F). 13C NMR (100 MHz, CDCl3)
d 137.4 (s), 134.0 (s),
132.3 (s), 116.8 (s). IR (KBr): 3097, 1450, 1368, 1256, 1223, 1152, 1103,
1031, 996, 923, 845, 812, 724, 708, 681, 639, 573 cmꢁ1. ESI-MS (m/z):
753.0 ([M]þ). Anal. Calcd for C21H10F20O3S2$H2O: C 32.65, H 1.57;
Found: C 32.72, H 1.59.
strates
a wide range of phenylsulfonium salts as efficient
phenylation reagents in SuzukieMiyaura cross-coupling.
4. Experimental section
4.1.2. Procedure B. A mixture of TfOCH2CF3 (3.0 g, 12.9 mmol) and
diphenyl sulfide (14.4 g, 77.4 mmol) was placed in a closed Schlenk
flask under a N2 atmosphere with stirring. The mixture was heated
at 150 ꢀC for 48 h, cooled to room temperature, and washed with
diethyl ether (till the excess sulfide was completely removed). The
resulting solid was then dried in vacuum to give 2.5 g of
[Ph2SCH2CF3][OTf] (2e)10,15b as a white solid (6.0 mmol, 47%). 1H
All reactions were carried out under a nitrogen or argon atmo-
sphere. Unless otherwise specified, NMR spectra were recorded in
CDCl3 on a 500 or 400 MHz (for 1H), 471 or 376 MHz (for 19F), and 126
or 100 MHz (for 13C) spectrometer. All chemical shifts were reported
in ppm relative to TMS (1H NMR, 0 ppm) and PhCF3 19F NMR,
(
ꢁ63.0 ppm) as an internal orexternal standard. Melting points of the
products were measured and uncorrected. The HPLC experiments
were carried out on a Waters e2695 instrument (column: J&K, RP-
NMR (500 MHz, CD3CN)
d
8.04 (d, J¼7.9 Hz, 4H), 7.87 (t, J¼7.3 Hz,
2H), 7.77 (t, J¼7.7 Hz, 4H), 5.14 (q, J¼8.6 Hz, 2H). 19F NMR (471 MHz,
CD3CN)
d
ꢁ61.4 (t, J¼8.6 Hz, 3F), ꢁ79.3 (s, 3F). 13C NMR (126 MHz,
C18, 5
m
m, 4.6ꢂ150 mm), and the HPLC yields of the product were
CD3CN) d 135.0 (s), 131.3 (s), 130.7 (s), 124.5 (s), 122.5 (q,
determined by using the corresponding pure compound as the ex-
ternal standard. Alkyl and fluoroalkyl phenylsulfonium salts like
2a,15a 2b,9b 2c,9b 2d,9b 2e,10,15b 2f,10 2g,10 2h,10 2i,15c 2j,15c 2k,15d 2l,12c
and 2m15e were synthesized by modified procedures according to
the literatures. Solvents were dried before use according to the lit-
erature.16 Other reagents were purchased from commercial sources
and used without further purification.
J¼278.8 Hz), 120.6 (q, J¼322.3 Hz), 43.7 (q, J¼33.1 Hz).
A mixture of TfOCH2CF2CF3 (9.0 g, 31.9 mmol) and diphenyl
sulfide (35.6 g, 191.4 mmol) reacted at 150 ꢀC for 72 h to give 1.0 g of
[Ph2SCH2C2F5][OTf] (2f) as a white solid (2.1 mmol, 7%). Mp
94e96 ꢀC. 1H NMR (500 MHz, CDCl3)
d
8.21 (d, J¼8.1 Hz, 4H), 7.77 (t,
J¼7.4 Hz, 2H), 7.71 (t, J¼7.6 Hz, 4H), 5.31 (t, J¼15.1 Hz, 2H). 19F NMR
(471 MHz, CDCl3)
d
ꢁ78.6 (s, 3F), ꢁ84.0 (s, 3F), ꢁ111.4 (t, J¼15.1 Hz,
2F). 13C NMR (126 MHz, CDCl3)
d 135.5 (s), 131.8 (s), 131.0 (s), 123.8
4.1. Typical procedures for the synthesis of phenylsulfonium
triflates
(s), 120.6 (q, J¼319.9 Hz), 44.9 (t, J¼21.8 Hz). IR (KBr): 3066, 2981,
2921, 1481, 1449, 1351, 1250, 1197, 1161, 1093, 1030, 998, 751, 685,
638, 574, 517 cmꢁ1. HRMS-ESI (m/z) calcd for C15H12F5Sþ ([M]þ):
319.0574; Found: 319.0576. Anal. Calcd for C16H12F8O3S2: C 41.03, H
2.58; Found: C 40.57, H 2.67.
A mixture of TfOCH2CF2H (2.1 g,10.0 mmol) and diphenyl sulfide
(5.5 g, 30.0 mmol) reacted at 120 ꢀC for 48 h to give 3.6 g of
[Ph2SCH2CF2H][OTf] (2g) as a white solid (9.0 mmol, 90%). Mp
4.1.1. Procedure A. Under an Ar atmosphere, a round bottom flask
was charged with C4F9SO2Na (10.0 g, 32.7 mmol) and tri-
fluoromethanesulfonate acid (17.2 mL, 190 mmol) with vigorous
stirring. After 5 min, benzene (4.4 mL, 47.5 mmol) was added. After
48 h at room temperature, the resulting mixture was quenched by
ice-water, neutralized with NaHCO3, and extracted with dichloro-
methane (3ꢂ100 mL). The combined organic layers were dried over
anhydrous Na2SO4 and concentrated to dryness under reduced
pressure to afford 2.3 g of ((perfluorobutyl)sulfinyl)benzene as
a white solid (6.69 mmol, 20%). Then Tf2O (5.5 mL, 33.6 mmol) was
added into a mixture of ((perfluorobutyl)sulfinyl)benzene (2.3 g)
and benzene (18 mL) at 0 ꢀC under an Ar atmosphere with stirring.
After 1 h, the mixture was warmed at room temperature for an-
other 48 h. The solvent was removed and the residue was purified
by column chromatography on silica gel using dichloromethane/
acetonitrile¼4: 1 (v/v) as eluents to give 2.2 g of [Ph2SC4F9][OTf]
(2c) as a white solid (3.98 mmol, 60%; total yield based on
C4F9SO2Na is 12%). Mp 127e129 ꢀC. 1H NMR (500 MHz, CDCl3)
82e83 ꢀC. 1H NMR (500 MHz, CDCl3)
d
8.06 (d, J¼7.7 Hz, 4H), 7.75 (t,
J¼7.4 Hz, 2H), 7.69 (t, J¼7.6 Hz, 4H), 6.51 (t, J¼53.7 Hz, 1H), 4.96 (t,
J¼15.3 Hz, 2H). 19F NMR (376 MHz, CDCl3)
ꢁ78.5 (s, 3F), ꢁ114.2 (dt,
d
J¼53.8, 15.0 Hz, 2F). 13C NMR (126 MHz, CDCl3)
d 135.0 (s), 131.7 (s),
130.6 (s), 124.4 (s), 120.7 (q, J¼320.0 Hz), 111.7 (t, J¼244.8 Hz), 47.4
(t, J¼23.6 Hz). IR (KBr): 3066, 3001, 2921, 2850, 1480, 1449, 1410,
1370, 1225, 1158, 1110, 1074, 1029, 998, 744, 638, 574, 516 cmꢁ1. ESI-
MS (m/z): 251.1 ([M]þ). Anal. Calcd for C15H13F5O3S2: C 45.00, H
3.27; Found: C 45.14, H 3.34.
A mixture of TfOCH2CH2F (16.4 g, 83.9 mmol) and diphenyl
sulfide (23.4 g, 125.8 mmol) reacted at 60 ꢀC for 15 h to give 26.8 g
of [Ph2SCH2CH2F][OTf] (2h) as a light gray solid (70.2 mmol, 84%).
Mp 60e62 ꢀC. 1H NMR (500 MHz, CDCl3)
d
8.05 (d, J¼7.1 Hz, 4H),
d
8.38 (d, J¼7.9 Hz, 4H), 7.93 (t, J¼7.4 Hz, 2H), 7.83 (t, J¼7.4 Hz, 4H).
7.75 (d, J¼7.3 Hz, 2H), 7.70 (t, J¼7.0 Hz, 4H), 4.88 (d, J¼46.7 Hz, 2H),
19F NMR (471 MHz, CDCl3)
d
ꢁ78.4 (s, 3F), ꢁ80.4 (t, J¼9.3 Hz, 3F),
4.74 (d, J¼23.7 Hz, 2H). 19F NMR (471 MHz, CDCl3)
d
ꢁ78.4 (s, 3F),
ꢁ91.0 (t, J¼13.6 Hz, 2F), ꢁ116.8 (m, 2F), ꢁ125.3 (t, J¼12.4 Hz, 2F). 13
C
ꢁ218.8 (m,1F). 13C NMR (100 MHz, CDCl3)
d 135.0 (s),131.7 (s),130.9
(s), 123.6 (s), 120.7 (q, J¼320.0 Hz), 77.5 (d, J¼173.2 Hz), 46.3 (d,
NMR (126 MHz, CDCl3)
d
137.5 (s), 134.1 (s), 132.4 (s), 120.9 (q,
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X.-Y. Wang et al. / Tetrahedron xxx (2016) 1e7
5
J¼18.1 Hz). IR (KBr): 3096, 3002, 2962, 1583, 1479, 1448, 1254, 1225,
1158, 1062, 1029, 998, 799, 748, 684, 638, 574, 517 cmꢁ1. ESI-MS (m/
z): 233.1 ([M]þ). Anal. Calcd for C15H14F4O3S2: C 47.11, H 3.69;
Found: C 46.81, H 3.75.
pressure. The residue was purified by column chromatography on
silica gel using petroleum ether or a mixture of petroleum ether and
ethyl acetate as eluents to give the desired product (3). In the cases of
3d, 3e, and 3f, a solution of m-CPBA (0.6 mmol) in DMF (1 mL) was
added into the reaction mixture before the extraction step to oxidize
the small amounts of the side products (sulfides) at room temper-
ature for 2 h in order to successfully purify the desired products.
4.1.3. Procedure C. To a mixture of diphenyl sulfide (1.86 g,
10.0 mmol) and ethyl formate (1.48 g, 20.0 mmol) was added tri-
fluoromethanesulfonic acid (5.0 mL) at 0 ꢀC with vigorous stirring.
The resulting mixture was warmed to room temperature for 10 h,
poured into water (100 mL), and extracted with dichloromethane
(3ꢂ100 mL). The combined organic layers were concentrated to
5 mL and diethyl ether (200 mL) was added. The precipitates were
collected, washed with ether, and dried in a vacuum to give 2.83 g
of [Ph2SCH2CH3][OTf] (2i)15c (7.77 mmol, 78% yield) as a white
4.2.1. 1,10:40,100-Terphenyl (3a).17a White solid (66.1 mg from 2e, 96%;
65.2 mg from 2i, 94%), petroleum ether as eluent for column chro-
matography.1H NMR (500 MHz, CDCl3)
d
7.68 (s, 4H), 7.65 (d, J¼7.8 Hz,
4H), 7.46 (t, J¼7.8 Hz, 4H), 7.36 (t, J¼7.2 Hz, 2H). 13C NMR (126 MHz,
CDCl3) d 140.8 (s), 140.2 (s), 128.9 (s), 127.5 (s), 127.4 (s), 127.1 (s).
powder. 1H NMR (500 MHz, CDCl3)
d
7.99 (d, J¼7.5 Hz, 4H),
4.2.2. 1,10:30,100-Terphenyl (3b).17a White solid (67.6 mg from 2e,
98%; 63.4 mg from 2i, 93%), petroleum ether as eluent for column
7.72e7.68 (m, 6H), 4.27 (q, J¼7.1 Hz, 2H), 1.47 (t, J¼7.1 Hz, 3H). 19
F
NMR (471 MHz, CDCl3)
d
ꢁ78.2 (s, 3F). 13C NMR (126 MHz, CDCl3)
chromatography. 1H NMR (400 MHz, CDCl3)
d 7.80 (s, 1H), 7.64 (d,
d
134.6 (s), 131.5 (s), 130.7 (s), 124.2 (s), 120.9 (q, J¼321.4 Hz), 40.2
J¼7.3 Hz, 4H), 7.58e7.56 (m, 2H), 7.50 (dd, J¼8.7, 6.5 Hz, 1H), 7.45 (t,
(s), 9.6 (s).
[Ph2SCH3][OTf] (2j):15c white solid (2.87 g from 10 mmol of
diphenyl sulfide, 8.22 mmol, 82% yield). 1H NMR (500 MHz, CDCl3)
J¼7.7 Hz, 4H), 7.36 (t, J¼7.3 Hz, 2H). 13C NMR (126 MHz, CDCl3)
d
141.8 (s), 141.2 (s), 129.2 (s), 128.8 (s), 127.4 (s), 127.3 (s), 126.2 (s),
126.2 (s).
d
7.92 (d, J¼7.8 Hz, 4H), 7.70 (t, J¼7.38 Hz, 2H), 7.65 (t, J¼7.5 Hz, 4H),
3.71 (s, 3H). 19F NMR (471 MHz, CDCl3)
(126 MHz, CDCl3)
d
ꢁ78.3 (s, 3F). 13C NMR
4.2.3. 1,10:20,100-Terphenyl (3c).17b Colorless liquid (65.5 mg from 2e,
95%; 62.9 mg from 2i, 91%), petroleum ether as eluent for column
d
134.5 (s), 131.4 (s), 130.0 (s), 125.8 (s), 120.8 (q,
J¼319.5 Hz), 28.4 (s).
chromatography. 1H NMR (500 MHz, CDCl3)
d
7.54e7.52 (m, 4H),
d 141.7 (s), 140.7 (s),
7.32e7.27 (m, 10H). 13C NMR (126 MHz, CDCl3)
4.1.4. Procedure D. Thiophenol (1.0 g, 9.1 mmol) was added to
a solution of NaOH (0.36 g, 9.1 mmol) in a mixture solvent of EtOH
and H2O (1: 1 (v/v), 65 mL) with vigorous stirring. After 10 min, 1-
bromo-4-chlorobutane (1.15 mL, 10.0 mmol) was added and the
mixture was reacted at room temperature for 8 h. The volatile
species were removed under reduced pressure. The residue was
then extracted with Et2O (3ꢂ20 mL) and the combined organic
layers were dried over anhydrous Na2SO4 and concentrated to
dryness to give 1.5 g of (4-chlorobutylsulfanyl)benzene as a yellow
oil (7.5 mmol, 82%). Next, AgOTf (1.8 g, 7.0 mmol) was added to
a solution of (4-chlorobutylsulfanyl)benzene (1.4 g, 7.0 mmol) in
ClCH2CH2Cl (30 mL) and reacted at room temperature in the
darkness for 8 h. The gray precipitates were removed and the so-
lution was treated with anhydrous Na2SO4 and filtered. The filter
cake was washed by ClCH2CH2Cl (3ꢂ5 mL). The combined filtrates
were concentrated under reduced pressure to give a viscous yellow
oil, which was further washed by Et2O to provide 2.1 g of
[PhS(CH2)4][OTf] (2l) as a white solid (6.7 mmol, 96%). Mp
130.7 (s), 130.0 (s), 128.0 (s), 127.6 (s), 126.6 (s).
4.2.4. 4-Methoxy-1,10-biphenyl (3d).17a White solid (51.2 mg from
2e, 93%; 51.4 mg from 2i, 93%), petroleum ether/ethyl acetate¼10: 1
(v/v) as eluents for column chromatography. 1H NMR (400 MHz,
CDCl3)
d
7.56e7.51 (m, 4H), 7.42 (t, J¼7.6 Hz, 2H), 7.30 (t, J¼7.4 Hz,
1H), 6.98 (d, J¼8.8 Hz, 2H), 3.85 (s, 3H). 13C NMR (100 MHz, CDCl3)
d
158.1 (s), 139.8 (s), 132.8 (s), 127.7 (s), 127.1 (s), 125.7 (s), 125.6 (s),
113.2 (s), 54.3 (s).
4.2.5. 4-(Benzyloxy)-1,10-biphenyl (3e).17c White solid (71.8 mg
from 2e, 92%; 70.2 mg from 2i, 90%), petroleum ether as eluent for
column chromatography. 1H NMR (400 MHz, CDCl3)
d 7.56e7.51 (m,
4H), 7.45 (d, J¼7.2 Hz, 2H), 7.43e7.38 (m, 4H), 7.35e7.28 (m, 2H),
7.05 (d, J¼8.7 Hz, 2H), 5.10 (s, 2H). 13C NMR (126 MHz, CDCl3)
d
158.4 (s), 140.8 (s), 137.0 (s), 134.1 (s), 128.8 (s), 128.7 (s),128.2 (s),
128.0 (s), 127.5 (s), 126.8 (s), 126.7 (s), 115.2 (s), 70.1 (s).
44e45 ꢀC. 1H NMR (400 MHz, CDCl3)
7.72e7.63 (m, 3H), 4.20 (dt, J¼13.4, 7.0 Hz, 2H), 3.69 (dt, J¼12.3,
6.1 Hz, 2H), 2.59e2.52 (m, 4H). 19F NMR (376 MHz, CDCl3)
ꢁ78.3
(s, 3F). 13C NMR (126 MHz, CDCl3)
134.1 (s), 131.3 (s), 129.8 (s),
d
7.80 (dm, J¼7.1 Hz, 2H),
4.2.6. [1,10-Biphenyl]-4-ol (3f).17a White solid (47.2 mg from 2e,
93%; 48.8 mg from 2i, 96%), petroleum ether/ethyl acetate¼5: 1 (v/
v) as eluents for column chromatography. 1H NMR (400 MHz,
d
d
CDCl3)
J¼7.6 Hz, 2H), 7.30 (t, J¼7.3 Hz, 1H), 6.90 (d, J¼8.8 Hz, 2H), 4.98 (s,
1H). 13C NMR (126 MHz, (CD3)2SO)
157.6 (s), 140.7 (s), 131.4 (s),
d
7.54 (d, J¼7.2 Hz, 2H), 7.48 (d, J¼8.6 Hz, 2H), 7.41 (t,
125.9 (s), 120.7 (q, J¼320.3 Hz), 48.5 (s), 29.1 (s). IR (KBr): 3093,
3015, 2957, 2878, 2287, 1582, 1484, 1447, 1423, 1266, 1223, 1160,
1078, 1030, 1001, 894, 876, 749, 686, 638, 573, 517 cmꢁ1. ESI-MS (m/
z): 165.1 ([M]þ). Anal. Calcd for C11H13F3O3S2$0.5H2O: C 40.86, H
4.36; Found: C 40.60, H 4.45.
d
129.3 (s), 128.2 (s), 126.8 (s), 126.4 (s), 116.2 (s).
4.2.7. 4-(Tert-butyl)-1,10-biphenyl (3g).17d White solid (55.6 mg
from 2e, 88%), petroleum ether as eluent for column chromatog-
4.2. General procedure for Pd-catalyzed phenylation of ar-
ylboronic acids with phenylsulfonium salts
raphy. 1H NMR (400 MHz, CDCl3)
d
7.58 (d, J¼7.2 Hz, 2H), 7.54 (d,
J¼8.5 Hz, 2H), 7.46 (d, J¼8.5 Hz, 2H), 7.42 (t, J¼7.4 Hz, 2H), 7.31 (t,
J¼7.4 Hz, 1H), 1.36 (s, 9H). 13C NMR (100 MHz, CDCl3)
d 150.3 (s),
A sealed tube was charged with arylboronic acid (1, 0.1 or
0.3 mmol), [Ph2SCH2CF3]þ[OTf]ꢁ (2e) or [Ph2SCH2CH3]þ[OTf]ꢁ (2i)
(0.15 or 0.45 mmol), Pd[P(t-Bu)3]2 (0.005 or 0.015 mmol, 5 mol %),
NaHCO3 (0.2 or 0.6 mmol), and DMF (2 or 4 mL) in a nitrogen-filled
glovebox with vigorous stirring. The mixture was reacted at 60 ꢀC for
6 h, cooled to room temperature, and extracted with dichloro-
methane (3ꢂ20 mL). The extracts were washed with water, dried
over anhydrous Na2SO4, and concentrated to dryness under reduced
141.1 (s), 138.4 (s), 128.7 (s), 127.0 (s), 127.0 (s), 126.8 (s), 125.7 (s),
34.6 (s), 31.4 (s).
4.2.8. Methyl [1,10-biphenyl]-4-carboxylate (3h).17a White solid
(63.0 mg from 2e, 99%; 61.6 mg from 2i, 97%), petroleum ether/
ethyl acetate¼10: 1 (v/v) as eluents for column chromatography. 1H
NMR (400 MHz, CDCl3)
2H), 7.62 (d, J¼7.3 Hz, 2H), 7.46 (t, J¼7.7 Hz, 2H), 7.39 (t, J¼7.3 Hz,
d
8.11 (d, J¼8.3 Hz, 2H), 7.66 (d, J¼8.4 Hz,
Please cite this article in press as: Wang, X.-Y.; et al., Tetrahedron (2016), http://dx.doi.org/10.1016/j.tet.2016.10.018

6
X.-Y. Wang et al. / Tetrahedron xxx (2016) 1e7
1H), 3.94 (s, 3H). 13C NMR (100 MHz, CDCl3)
d
171.4 (s), 167.0 (s),
eluent for column chromatography. 1H NMR (500 MHz, CDCl3)
145.7 (s), 140.0 (s), 130.1 (s), 128.9 (s), 128.2 (s), 127.3 (s), 127.1 (s),
52.1 (s).
d
8.15 (d, J¼6.0 Hz, 1H), 8.11 (d, J¼7.7 Hz, 1H), 7.79 (d, J¼5.9 Hz, 1H),
7.72 (d, J¼7.3 Hz, 2H), 7.53e7.41 (m, 7H). 13C NMR (126 MHz, CDCl3)
d
140.7 (s), 139.7 (s), 138.7 (s), 137.1 (s), 136.3 (s), 135.9 (s), 128.9 (s),
4.2.9. [1,10-Biphenyl]-4-carbaldehyde (3i).17a White solid (52.8 mg
from 2e, 97%; 51.9 mg from 2i, 95%), petroleum ether/ethyl
acetate¼10: 1 (v/v) as eluents for column chromatography. 1H NMR
128.3 (s), 128.1 (s), 127.0 (s), 126.8 (s), 125.2 (s), 124.4 (s), 122.7 (s),
121.8 (s), 120.5 (s).
(500 MHz, CDCl3)
d
10.06 (s, 1H), 7.95 (d, J¼8.1 Hz, 2H), 7.75 (d,
4.2.17. 1-Phenylnaphthalene (3q).17a White solid (49.3 mg from 2e,
81%; 54.9 mg from 2i, 90%), petroleum ether as eluent for column
J¼8.1 Hz, 2H), 7.64 (d, J¼7.6 Hz, 2H), 7.48 (t, J¼7.5 Hz, 2H), 7.42 (t,
J¼7.3 Hz, 1H). 13C NMR (126 MHz, CDCl3)
d
191.9 (s), 147.2 (s), 139.8
chromatography. 1H NMR (400 MHz, CDCl3)
d
7.89 (d, J¼7.6 Hz, 2H),
(s), 135.3 (s), 130.3(s), 129.0 (s), 128.5 (s), 127.7(s), 127.4 (s).
7.85 (d, J¼8.2 Hz, 1H), 7.53e7.46 (m, 6H), 7.43e7.39 (m, 3H). 13C
NMR (100 MHz, CDCl3) d 140.8 (s), 140.3 (s), 133.9 (s), 131.7 (s), 130.1
4.2.10. 4-Nitro-1,10-biphenyl (3j).17a Light yellow solid (54.8 mg
from 2e, 92%; 50.6 mg from 2i, 85%), petroleum ether/ethyl
acetate¼10: 1 (v/v) as eluents for column chromatography. 1H NMR
(s), 128.3 (s), 127.7 (s), 127.3 (s), 127.0 (s), 126.1 (s), 126.1 (s), 125.8
(s), 125.4 (s).
(400 MHz, CDCl3)
d
8.29 (d, J¼8.7 Hz, 2H), 7.73 (d, J¼8.8 Hz, 2H),
4.2.18. 2-Phenylnaphthalene (3r).17a White solid (54.3 mg, 89%),
7.63 (d, J¼6.9 Hz, 2H), 7.50 (t, J¼7.5 Hz, 2H), 7.44 (t, J¼7.2 Hz,1H). 13
C
petroleum ether as eluent for column chromatography. 1H NMR
NMR (126 MHz, CDCl3)
d
147.7 (s), 147.1 (s), 138.8 (s), 129.2 (s), 128.9
(400 MHz, CDCl3) d 8.03 (s, 1H), 7.91e7.83 (m, 3H), 7.75e7.70 (m,
(s), 127.8 (s), 127.4 (s), 124.1 (s).
3H), 7.49e7.45 (m, 4H), 7.36 (t, J¼7.4 Hz, 1H). 13C NMR (100 MHz,
CDCl3)
d 141.1 (s), 138.6 (s), 133.7 (s), 132.6 (s), 128.9 (s), 128.4 (s),
4.2.11. 2-Phenylbenzofuran (3k).17e White solid (57.2 mg from 2e,
98%; 55.3 mg from 2i, 95%), petroleum ether as eluent for column
128.2 (s), 127.7 (s), 127.4 (s), 127.4 (s),126.3 (s), 125.9 (s), 125.8
(s),125.6 (s).
chromatography. 1H NMR (400 MHz, CDCl3)
d
7.86 (d, J¼7.4 Hz, 2H),
7.57 (d, J¼7.4 Hz, 1H), 7.52 (d, J¼8.0 Hz, 1H), 7.43 (t, J¼7.6 Hz, 2H),
7.34 (t, J¼7.4 Hz,1H), 7.27 (t, J¼7.3 Hz,1H), 7.22 (t, J¼7.4 Hz,1H), 7.00
4.2.19. (E)-1-Methoxy-4-styrylbenzene (3s).17k White solid (62.4 mg
from 2e, 99%; 61.8 mg from 2i, 98%), petroleum ether as eluent for
(s, 1H). 13C NMR (100 MHz, CDCl3)
d
156.0 (s), 154.9 (s), 130.5 (s),
column chromatography. 1H NMR (400 MHz, CDCl3)
d 7.49 (d,
129.2 (s), 128.8 (s), 128.6 (s), 125.0 (s), 124.3 (s), 123.0 (s), 120.9 (s),
111.2 (s), 101.3 (s).
J¼7.0 Hz, 2H), 7.45 (d, J¼9.0 Hz, 2H), 7.34 (t, J¼7.6 Hz, 2H), 7.23 (t,
J¼7.3 Hz, 1H), 7.02 (AB peak, J¼38.2, 16.3 Hz, 2H), 6.90 (d, J¼8.7 Hz,
2H), 3.82 (s, 3H). 13C NMR (126 MHz, CDCl3)
d 159.4 (s), 137.7 (s),
4.2.12. 2-Phenylbenzo[b]thiophene (3l).17f White solid (56.8 mg
from 2e, 90%; 53.3 mg from 2i, 85%), petroleum ether as eluent for
130.2 (s), 128.7 (s), 128.3 (s), 127.8 (s), 127.2 (s), 126.7 (s), 126.3 (s),
114.2 (s), 55.4 (s).
column chromatography. 1H NMR (400 MHz, CDCl3)
d 7.83 (d,
J¼7.7 Hz, 1H), 7.77 (d, J¼7.3 Hz, 1H), 7.72 (d, J¼7.2 Hz, 2H), 7.55 (s,
4.2.20. (8R,9S,13S,14S)-13-Methyl-3-phenyl-7,8,9,11,12,13,15,16-octa-
hydro-6H-cyclopenta[a]phenanthren-17(14H)-one
1H), 7.43 (t, J¼7.5 Hz, 2H), 7.37e7.29 (m, 3H). 13C NMR (126 MHz,
(3t).17l White
CDCl3)
d
144.3 (s), 140.7 (s), 139.5 (s), 134.3 (s), 129.0 (s), 128.3 (s),
solid (25.4 mg from 2i and 0.1 mmol of 1t, 77%), petroleum ether/
126.5 (s), 124.5 (s), 124.3 (s), 123.6 (s), 122.3 (s), 119.5 (s).
ethyl acetate¼5: 1 (v/v) as eluents for column chromatography. 1H
NMR (500 MHz, CDCl3)
d
7.58 (d, J¼7.1 Hz, 2H), 7.43e7.31 (m, 6H),
4.2.13. Tert-butyl 2-phenyl-1H-indole-1-carboxylate (3m).17g Light
yellow solid (81.6 mg from 2e, 93%; 84.2 mg from 2i, 96%), petro-
leum ether/ethyl acetate¼10: 1 (v/v) as eluents for column chro-
3.00 (d, J¼7.6 Hz, 2H), 2.54e2.46 (m, 2H), 2.36 (t, J¼11.5 Hz, 1H),
2.19e2.05 (m, 3H), 1.99 (d, J¼12.2 Hz, 1H), 1.67e1.49 (m, 6H), 0.93
(s, 3H). 13C NMR (126 MHz, CDCl3)
d 220.9 (s), 141.0 (s), 138.9 (s),
matography. 1H NMR (500 MHz, CDCl3)
d
8.22 (d, J¼8.0 Hz,1H), 7.55
138.8 (s), 136.9 (s), 128.7 (s), 127.8 (s), 127.1 (s),127.0 (s), 125.9 (s),
124.6 (s), 50.6 (s), 48.0 (s), 44.4 (s), 38.2 (s), 35.9 (s), 31.7 (s), 29.6 (s),
26.6 (s), 25.8 (s), 21.6 (s), 13.9 (s).
(d, J¼7.2 Hz, 1H), 7.40e7.31 (m, 6H), 7.24 (t, J¼7.4 Hz, 1H), 6.55 (s,
1H), 1.30 (s, 9H). 13C NMR (126 MHz, CDCl3)
d
150.3 (s), 140.5 (s),
137.5 (s), 135.1 (s), 129.3 (s), 128.8 (s), 127.8 (s), 127.6 (s), 124.3 (s),
123.0 (s), 120.5 (s), 115.2 (s), 109.9 (s), 83.4 (s), 27.6 (s).
Acknowledgements
4.2.14. 6-Phenyl-2,3-dihydrobenzo[b][1,4]dioxine (3n).17h Light yel-
low solid (61.2 mg from 2e, 96%; 63.0 mg from 2i, 99%), petroleum
ether as eluent for column chromatography. 1H NMR (400 MHz,
We thank Wuhan University of Technology, the Natural Science
Foundation of Hubei Province (China) (2015CFB176), the ‘Chutian
Scholar’ Program from Department of Education of Hubei Province
(China), and the ‘Hundred Talent’ Program of Hubei Province for
financial support.
CDCl3)
d
7.53 (d, J¼7.2 Hz, 2H), 7.39 (t, J¼7.6 Hz, 2H), 7.28 (t,
J¼7.3 Hz, 1H), 7.12 (d, J¼2.1 Hz, 1H), 7.07 (dd, J¼8.3, 2.1 Hz, 1H), 6.92
(d, J¼8.3 Hz, 1H), 4.26 (s, 4H). 13C NMR (126 MHz, CDCl3)
d 143.8 (s),
143.2 (s), 140.7 (s), 134.9 (s), 128.8 (s), 126.9 (s), 126.8 (s), 120.2 (s),
117.6 (s), 115.9 (s), 64.5 (s), 64.5 (s).
Supplementary data
Supplementary data (including additional experimental and
copies of NMR spectra of the products) associated with this article
can be found in the online version, at http://dx.doi.org/10.1016/
j.tet.2016.10.018.
4.2.15. 4-Phenyldibenzo[b,d]furan (3o).17i Colorless liquid (66.6 mg
from 2e, 91%; 67.1 mg from 2i, 92%), petroleum ether as eluent for
column chromatography. 1H NMR (500 MHz, CDCl3)
d 7.94 (d,
J¼7.6 Hz, 1H), 7.90e7.89 (m, 3H), 7.57 (d, J¼7.8 Hz, 2H), 7.51 (t,
J¼7.2 Hz, 2H), 7.44e7.37 (m, 3H), 7.32 (t, J¼7.4 Hz, 1H). 13C NMR
References and notes
(126 MHz, CDCl3) d 156.3 (s), 153.5 (s), 136.6 (s), 128.9 (s), 128.8 (s),
127.9 (s), 127.3 (s), 127.0 (s), 126.0 (s), 125.0 (s), 124.3 (s), 123.3 (s),
122.9 (s), 120.8 (s), 119.8 (s), 111.9 (s).
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(3p).17j Colorless
liquid
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Please cite this article in press as: Wang, X.-Y.; et al., Tetrahedron (2016), http://dx.doi.org/10.1016/j.tet.2016.10.018