A general procedure for the regioselective synthesis of aryl thioethers and aryl selenides through C-H activation of arenes

Article abstract of DOI:10.1002/ejoc.201300248

A general procedure for the synthesis of aryl thioethers and aryl selenides in one-pot through sequential iridium-catalyzed C-H borylation and copper-promoted C-S and C-Se bond formation is described. Functional groups including chloro, nitro, fluoro, trifluoromethyl, and nitrogen-containing heterocycles were all tolerated under the reaction conditions. Importantly, not only aryl thiols and selenides but also their alkyl analogs were suitable coupling partners, and the products were obtained in good yields with high meta regioselectivity. Aryl thioethers and selenides were prepared in good yields with high meta regioselectivity through sequential Ir-catalyzed C-H borylation and Cu-promoted C-S and C-Se bond formation in one pot. A wide range of functional groups were tolerated under the reaction conditions. In addition to aryl thiols and selenides, alkyl thiols and selenides were also suitable coupling partners in this reaction. Copyright

Full text of DOI:10.1002/ejoc.201300248

FULL PAPER
DOI: 10.1002/ejoc.201300248
A General Procedure for the Regioselective Synthesis of Aryl Thioethers and
Aryl Selenides Through C–H Activation of Arenes
Chih-Lun Yi,[a] Tsung-Jui Liu,[a] Jun-Hao Cheng,[a] and Chin-Fa Lee*[a]
Dedicated to Professor Teruaki Mukaiyama[‡]
Keywords: Sulfur / Selenide / C–H activation / Arenes / Iridium / Copper
A general procedure for the synthesis of aryl thioethers and
aryl selenides in one-pot through sequential iridium-cata-
lyzed C–H borylation and copper-promoted C–S and C–Se
bond formation is described. Functional groups including
chloro, nitro, fluoro, trifluoromethyl, and nitrogen-containing
heterocycles were all tolerated under the reaction conditions.
Importantly, not only aryl thiols and selenides but also their
alkyl analogs were suitable coupling partners, and the prod-
ucts were obtained in good yields with high meta regioselec-
tivity.
catalyzed coupling of arylsulfonyl cyanides with simple ar-
enes to give the diaryl thioethers in moderate yields.[16]
However, some drawbacks remain with this system and
need to be addressed. First, this system employs trifluoro-
acetic acid as a solvent, and acid-sensitive functional groups
may not survive under these conditions. Second, mixtures
of ortho- and para-arythiolated products were observed in
most cases. Third, the substrates are limited to electron-rich
arenes. Notably, the above-mentioned protocols prefer ortho
and para C–S formation rather than meta C–S formation.
In 2011, Frost reported the first meta sulfonation of 2-phen-
ylpyridines with sulfonyl chlorides through ruthenium ca-
talysis. However, this catalytic system again requires pyr-
idine as a directing group.[17] Recently, we communicated
the one-pot meta C–H thioetherification of simple arenes
in the absence of a directing group through iridium-cata-
Introduction
Transition-metal-catalyzed direct C–H functionalization
is an important strategy for the construction of C–C,[1] C–
N,[2] and other C–heteroatom bonds[3] from the viewpoint
of atom economy.[4] Many elegant studies have reported the
synthesis of a C–C bond through C–H activation. Aryl
thioethers are important skeletons found in biology,[5] and
many methods have been reported for the preparation of
such molecules.[6–12] Among the reactions leading to C–het-
eroatom bond formation, investigation of C–S bond forma-
tion through C–H activation is less studied.[13–17] 2-Phenyl-
pyridine has been reported to couple with thiophenols and
methyl disulfide in the presence of a copper catalyst to pro-
vide the products with high ortho selectivity.[13] Dong et al.
demonstrated the palladium-catalyzed ortho-sulfonylation
of 2-phenylpyridine with ArSO2Cl.[14] Although high re-
gioselectivity for ortho C–S bond formation was achieved
by these two protocols, pyridine is required as a directing
group for this transformation. Recently, Cheng et al. re-
ported the copper-catalyzed direct C–H thioetherification
of arenes; however, the starting material is limited to very
electron-rich arenes such as 1,3,5-trimethoxybenzene and
1,2,4-trimethoxybenzene, which resulted in the formation of
the corresponding aryl thioethers in low to moderate
yields.[15] Very recently, Beller et al. reported the palladium-
Table 1. Optimization of the reaction conditions.[a]
Entry
Temp. [°C]
Time [h]
Yield [%][b]
1
2
3
4
5
155
155
155
120
110
3
trace[c]
45[c]
53
91
27
24
24
24
24
[a] Department of Chemistry, National Chung Hsing University,
Taichung, Taiwan 402, Republic of China
Fax: +886-4-2286-2547
E-mail: cfalee@dragon.nchu.edu.tw
[a] Reaction conditions: Cu(OAc)2 (0.75 mmol), pyridine
(1.5 mmol), 3,5-dimethylphenyl boronic ester (1 mmol), and 1-do-
decanethiol (0.5 mmol) in DMF (2 mL) under an argon atmo-
sphere; Bpin = pinacolboryl. [b] Isolated yield. [c] Molecular sieves
(3 Å) were added.
Homepage: http://www.nchu.edu.tw/~chem/cflee.htm
[‡] On the occasion of the 40th anniversary of the Mukaiyama
aldol reaction
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201300248.
3910
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2013, 3910–3918

Regioselective Synthesis of Aryl Thioethers and Aryl Selenides
Table 2. Tandem iridium-catalyzed borylation and copper-promoted C–S bond formation.[a]
[a] Reaction conditions unless otherwise stated: arene (1.0 mmol), [Ir(cod)OMe]2 (0.0015 mol, 0.15 mol-%; cod = 1,5-cyclooctadiene), di-
tert-butyl bipyridine (dtbpy; 0.003 mmol, 0.3 mol-%) in THF (1.5 mL) for the first step; Cu(OAc)2 (0.75 mmol, 1.5 equiv.), pyridine
(1.5 mmol, 3 equiv.), thiol (0.5 mmol) in DMF (2 mL) under an argon atmosphere for the second step. [b] Borylation with [Ir(cod)-
OMe]2 (1.5 mol-%) and dtbpy (3.0 mol-%). [c] Borylation with [Ir(cod)OMe]2 (0.1 mol-%) and dtbpy (0.2 mol-%). [d] Borylation with
[Ir(cod)OMe]2 (3.0 mol-%) and dtbpy (6.0 mol-%). [e] 135 °C.
Eur. J. Org. Chem. 2013, 3910–3918
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
3911

C.-L. Yi, T.-J. Liu, J.-H. Cheng, C.-F. Lee
FULL PAPER
lyzed C–H borylation[18] followed by copper-catalyzed C–S Table 3. Synthesis of aryl alkyl and diaryl selenides through tandem
bond formation.[19] Although good results were obtained
iridium-catalyzed borylation and copper-promoted C–Se bond for-
mation.[a]
for reactions of aryl disulfides, alkyl disulfides were not
suitable as coupling partners for the synthesis of aryl alkyl
thioethers under the reaction conditions.[19] Therefore, it is
necessary to develop a general method to overcome this
difficulty. Herein, we report that the combination of
Cu(OAc)2 and pyridine could be applied to promote the C–
S and C–Se cross-coupling reaction step. Thus, the aryl
alkyl thioethers and selenides could be prepared through
sequential iridium-catalyzed meta C–H borylation and cop-
per-promoted C–S and C–Se bond formations in one pot.
Results and Discussion
Initially, (3,5-dimethylphenyl)boronic ester and 1-do-
decanethiol were chosen as substrates to determine the opti-
mal reaction conditions. When the reaction was carried out
with DMF as the solvent in the presence of Cu(OAc)2 and
pyridine (3 equiv.) at 155 °C for 3 h,[20] only a trace amount
of the product was detected by GC–MS (Table 1, entry 1).
The product yield could be raised to 45% if the reaction
time was extended to 24 h (Table 1, entry 2). A better result
was obtained when the reaction was performed without
molecular sieves (Table 1, entry 3). To our surprise, a 91%
yield was achieved after 24 h at 120 °C (Table 1, entry 4).
However, only 27% of the product was formed at 110 °C
(Table 1, entry 5).
With the optimized reaction conditions for the copper-
promoted C–S bond-formation reaction in hand, we then
examined the scope of the tandem iridium-catalyzed bo-
rylation and copper-promoted C–S bond-coupling reaction
through a one-pot procedure. 1,3-Disubstituted arenes re-
acted smoothly with pin2B2 [bis(pinacolato)diboron] in the
presence of an iridium catalyst to afford the arylboronates.
After removing the volatile residues by vacuum, the re-
sulting arylboronates were treated with alkyl thiols includ-
ing dodecanethiol (Table 2, entries 1, 3, 6, 9, and 14), 2-
methy-1-butanethiol (Table 2, entries 2, 4, 7, 10, 12, and
15), cyclohexanethiol (Table 2, entries 5, 11, and 13), and
benzyl mercaptan (Table 2, entry 8) in the presence of
Cu(OAc)2 to give the corresponding aryl alkyl thioethers in
moderate to good yields (Table 2, entries 1–15). Moreover,
this methodology could be applied to the formation of di-
aryl thioethers (Table 2, entries 16–26). Functional groups
including chloro (Table 2, entries 3–5, 9–13, 18–26), trifluo-
romethyl (Table 2, entries 6–8, 16, and 17), pyridine
(Table 2, entries 14 and 15), fluoro (Table 2, entry 25), and
nitro (Table 2, entry 26) were all tolerated under the reac-
tion conditions.
To explore the scope of this method for the synthesis of
[a] Reaction conditions unless otherwise stated: arene (1.0 mmol),
aryl selenides, we then investigated diaryl diselenides as the
coupling partners (Table 3). Aryl alkyl selenides (Table 3,
entries 1–5) and diaryl selenides (Table 3, entries 6–10) were
formed in moderate to good yields. Functional groups such
as chloro (Table 3, entries 1, 3, 4, 6, 8, and 9), trifluoro-
methyl (Table 3, entries 2 and 7), and pyridine (Table 3, en-
[Ir(cod)OMe]2 (0.0015 mol, 0.15 mol-%), dtbpy (0.003 mmol,
0.3 mol-%) in THF (1.5 mL) for the first step; Cu(OAc)2
(0.75 mmol, 1.25 equiv.), pyridine (1.5 mmol, 2.5 equiv.), diselenide
(0.6 mmol) in DMF (2 mL) under an argon atmosphere for the
second step. [b] Borylation with [Ir(cod)OMe]2 (0.1 mol-%) and
dtbpy (0.2 mol-%). [c] Borylation with [Ir(cod)OMe]2 (3.0 mol-%)
and dtbpy (6.0 mol-%).
3912
www.eurjoc.org
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2013, 3910–3918

Regioselective Synthesis of Aryl Thioethers and Aryl Selenides
a rubber septum and removed from the glove box. Under a nitrogen
atmosphere, arene (1.0 mmol) and THF (1.5 mL) were added by
syringe, and the Schlenk tube was heated at 80 °C in an oil bath.
After stirring at this temperature for 24 h, the heterogeneous mix-
ture was cooled to room temperature, after removal of the volatile
components under vacuum. This Schlenk tube was returned to the
glove box, Cu(OAc)2 (0.136 g, 0.75 mmol) was added, and the
Schlenk tube was covered with a rubber septum and removed from
the glove box. Under an argon atmosphere, thiol (0.5 mmol), pyr-
idine (0.123 mL, 1.5 mmol), and DMF (2.0 mL) were added by sy-
ringe, and the Schlenk tube was connected to an argon-filled bal-
loon and heated at 120 °C in an oil bath. After stirring at this
temperature for 24 h, the heterogeneous mixture was cooled to
room temperature and diluted with ethyl acetate (20 mL). The re-
sulting solution was directly filtered through a pad of silica gel and
then washed with ethyl acetate (20 mL) and concentrated to give
the crude material, which was then purified by column chromatog-
raphy (SiO2, hexane) to yield 3.
tries 5 and 10) were also tolerated under these reaction con-
ditions.
Conclusions
In conclusion, we have reported a general and convenient
procedure for the synthesis of aryl alkyl and diaryl thio-
ethers and selenides through iridium-catalyzed meta bor-
ylation followed by copper-promoted C–S and C–Se cross-
coupling reactions from simple arenes in one pot. Func-
tional groups including chloro, trifluoromethyl, pyridine,
fluoro, and nitro were all tolerated under the reaction con-
ditions. Screening the biological activities of these mole-
cules is underway in our laboratory.
Experimental Section
3,5-Dimethylphenyl Dodecyl Sulfide (3a): Following the general
procedure for Table 2, [Ir(OCH3)(C8H12)]2 (9.9 mg, 0.015 mmol),
4,4Ј-di-tert-butyl-2,2Ј-bipyridyl (8.2 mg, 0.03 mmol), pin2B2
(0.189 g, 0.73 mmol), and 1,3-dimethylbenzene (0.125 mL,
1.0 mmol) in THF (1.5 mL). After removal of the volatile compo-
nents under vacuum, Cu(OAc)2 (0.1362 g, 0.75 mmol), 1-dodecane-
thiol (0.123 mL, 0.5 mmol), pyridine (0.123 mL, 1.5 mmol), and
DMF (2.0 mL). Purification provided 3a (Table 2, entry 1) as a col-
General Information: All chemicals were purchased from commer-
cial suppliers and used without further purification. DMF was
dried with CaH2 and stored in the presence of activated molecular
sieves. All reactions were carried out under an inert atmosphere.
Flash chromatography was performed on silica gel 60 (230–
400 mesh). NMR spectra were recorded by using CDCl3 as the
solvent. Chemical shifts are referenced to the residual solvent reso-
nance. Standard abbreviations indicating multiplicity were used as
follows: s = singlet, d = doublet, t = triplet, dd = doublet of dou-
blets, q = quartet, m = multiplet, br. = broad. Melting points (m.p.)
were determined by using a Büchi 535 apparatus and are reported
uncorrected. High-resolution mass spectra (HRMS) were per-
formed with an electron ionization time-of-flight (EI-TOF) mass
spectrometer.
1
orless oil (0.101 g, 66% yield). H NMR (400 MHz, CDCl3): δ =
0.88 (t, J = 6.6 Hz, 3 H), 1.26–1.43 (m, 18 H), 1.60–1.67 (m, J =
7.5 Hz, 2 H), 2.28 (s, 6 H), 2.89 (t, J = 7.4 Hz, 2 H), 6.78 (s, 1 H),
6.94 (s, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 14.1, 21.2,
22.7, 28.8, 29.1, 29.3, 29.5, 29.6, 29.6, 29.6, 31.9, 33.5, 126.4, 127.5,
136.5, 138.3 ppm. HRMS (EI): calcd. for C20H34S 306.2381; found
306.2391.
3,5-Dimethylphenyl 2-Methyl-1-butyl Sulfide (3b): Following the
general procedure for Table 2, [Ir(OCH3)(C8H12)]2 (9.9 mg,
0.015 mmol), 4,4Ј-di-tert-butyl-2,2Ј-bipyridyl (8.2 mg, 0.03 mmol),
pin2B2 (0.189 g, 0.73 mmol), and 1,3-dimethylbenzene (0.125 mL,
1.0 mmol) in THF (1.5 mL). After removal of the volatile compo-
nents under vacuum, Cu(OAc)2 (0.136 g, 0.75 mmol), 2-methyl-1-
butanethiol (0.065 mL, 0.5 mmol), and DMF (2.0 mL). Purifica-
tion provided 3b (Table 2, entry 2) as a colorless oil (0.070 g, 67%
General Procedure for Reaction in Table 1: A Schlenk tube equipped
with a magnetic stirring bar was charged with (3,5-dimethylphen-
yl)boronic ester (1.0 mmol), copper salt (0.75 mmol), and thiol
(0.5 mmol) in a nitrogen-filled glove box. The Schlenk tube was
then covered with a rubber septum and removed from the glove
box. Under an argon atmosphere, solvent (2.0 mL) was added by
syringe, and the Schlenk tube was connected to an argon-filled bal-
loon and heated at 120 °C in an oil bath. After stirring at this
temperature for 24 h, the heterogeneous mixture was cooled to
room temperature and diluted with ethyl acetate (20 mL). The re-
sulting solution was directly filtered through a pad of silica gel then
washed with ethyl acetate (20 mL) and concentrated to give the
crude material, which was then purified by column chromatog-
raphy (SiO2, hexane) to yield 3a.
1
yield). H NMR (400 MHz, CDCl3): δ = 0.91 (t, J = 7.4 Hz, 3 H),
1.02 (d, J = 6.8 Hz, 3 H), 1.23–1.30 (m, 1 H), 1.50–1.57 (m, 1 H),
1.63–1.68 (m, 1 H), 2.27 (s, 6 H), 2.73 (dd, J = 7.2, 12.4 Hz, 1 H),
2.93 (dd, J = 5.8, 12.2 Hz, 1 H), 6.78 (s, 1 H), 6.94 (s, 2 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 11.2, 19.0, 21.2, 28.8, 34.5, 40.6,
126.3, 127.4, 137.0, 138.3 ppm. HRMS (EI): calcd. for C13H20S:
208.1286; found 208.1288.
3,5-Dimethylphenyl Dodecyl Sulfide (3a): Following the general
procedure for Table 1, Cu(OAc)2 (0.136 g, 0.75 mmol) and 1-do-
decanethiol (0.123 mL, 0.5 mmol) in DMF (2.0 mL). Purification
provided 3a (Table 1, entry 4) as a colorless oil (0.139 g, 91% yield).
1H NMR (400 MHz, CDCl3): δ = 0.88 (t, J = 6.6 Hz, 3 H), 1.26–
1.43 (m, 18 H), 1.60–1.67 (m, J = 7.5 Hz, 2 H), 2.28 (s, 6 H), 2.89
(t, J = 7.4 Hz, 2 H), 6.78 (s, 1 H), 6.94 (s, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 14.1, 21.2, 22.7, 28.8, 29.1, 29.3, 29.5, 29.6,
29.6, 29.6, 31.9, 33.5, 126.4, 127.5, 136.5, 138.3 ppm. HRMS (EI):
calcd. for C20H34S 306.2381; found 306.2391.
3-Chloro-5-methylphenyl Dodecyl Sulfide (3c): Following the gene-
ral procedure for Table 2, [Ir(OCH3)(C8H12)]2 (1.0 mg,
0.0015 mmol),
4,4Ј-di-tert-butyl-2,2Ј-bipyridyl
(0.8 mg,
0.003 mmol), pin2B2 (0.189 g, 0.73 mmol), and 3-chlorotoluene
(0.123 mL, 1.0 mmol) in THF (1.5 mL). After removal of the vola-
tile components under vacuum, Cu(OAc)2 (0.136 g, 0.75 mmol), 1-
dodecanethiol (0.123 mL, 0.5 mmol), and DMF (2.0 mL). Purifica-
tion provided 3c (Table 2, entry 3) as a colorless oil (0.128 g, 78%
1
yield). H NMR (400 MHz, CDCl3): δ = 0.88 (t, J = 6.8 Hz, 3 H),
1.26–1.43 (m, 18 H), 1.60–1.67 (m, J = 7.3 Hz, 2 H), 2.28 (s, 3 H),
2.89 (t, J = 7.2 Hz, 2 H), 6.94 (s, 1 H), 6.97 (s, 1 H), 7.07 (s, 1 H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 14.1, 21.1, 22.7, 28.8, 28.9,
General Procedure for Reactions in Table 2: A Schlenk tube
equipped with
a magnetic stirring bar was charged with
[Ir(OCH3)(C8H12)]2 (1.0 mg, 0.0015 mmol), 4,4Ј-di-tert-butyl-2,2Ј- 29.1, 29.3, 29.5, 29.6, 29.6, 29.6, 31.9, 33.2, 124.8, 126.3, 127.1,
bipyridyl (0.8 mg, 0.003 mmol), and pin2B2 (0.189 g, 0.73 mmol) in
a nitrogen-filled glove box. The Schlenk tube was then covered with
134.3, 138.9, 140.0 ppm. HRMS (EI): calcd. for C19H31ClS
326.1835; found 326.1843.
Eur. J. Org. Chem. 2013, 3910–3918
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
3913

C.-L. Yi, T.-J. Liu, J.-H. Cheng, C.-F. Lee
FULL PAPER
3-Chloro-5-methylphenyl 2-Methyl-1-butyl Sulfide (3d): Following 3,5-Bis(trifluoromethyl)phenyl Benzyl Sulfide (3h): Following the ge-
the general procedure for Table 2, [Ir(OCH3)(C8H12)]2 (1.0 mg, neral procedure for Table 2, [Ir(OCH3)(C8H12)]2 (0.7 mg,
0.0015 mmol), 4,4Ј-di-tert-butyl-2,2Ј-bipyridyl (0.8 mg, 0.001 mmol), 4,4Ј-di-tert-butyl-2,2Ј-bipyridyl (0.5 mg,
0.003 mmol), pin2B2 (0.189 g, 0.73 mmol), and 3-chlorotoluene
(0.123 mL, 1.0 mmol) in THF (1.5 mL). After removal of the vola-
tile components under vacuum, Cu(OAc)2 (0.136 g, 0.75 mmol), 2-
0.002 mmol), pin2B2 (0.189 g, 0.73 mmol), and 1,3-bis(trifluorome-
thyl)benzene (0.160 mL, 1.0 mmol) in THF (1.5 mL). After re-
moval of the volatile components under vacuum, Cu(OAc)2
methyl-1-butanethiol (0.065 mL, 0.5 mmol), and DMF (2.0 mL). (0.136 g, 0.75 mmol), phenylmethanethiol (0.060 mL, 0.5 mmol),
Purification provided 3d (Table 2, entry 4) as a colorless oil
(0.094 g, 82% yield). H NMR (400 MHz, CDCl3): δ = 0.91 (t, J
= 7.4 Hz, 3 H), 1.02 (d, J = 6.8 Hz, 3 H), 1.24–1.31 (m, 1 H), 1.49–
1.56 (m, 1 H), 1.64–1.69 (m, 1 H), 2.28 (s, 3 H), 2.73 (dd, J = 7.6,
and DMF (2.0 mL). Purification provided 3h (Table 2, entry 8) as
1
1
a colorless oil (0.079 g, 47% yield). H NMR (600 MHz, CDCl3):
δ = 4.19 (s, 2 H), 7.27–2.31 (m, 5 H), 7.63–7.64 (m, 3 H) ppm. 13C
NMR (125 MHz, CDCl3): δ = 38.3, 119.6, 119.6, 119.6, 123.0 (q,
12.4 Hz, 1 H), 2.92 (dd, J = 6.0, 12.4 Hz, 1 H), 6.93 (s, 1 H), 6.98 J = 226.3 Hz), 127.8, 128.6, 128.8, 128.8, 131.9 (q, J = 27.6 Hz),
(s, 1 H), 7.07 (s, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
11.2, 18.9, 21.1, 28.8, 34.4, 40.2, 124.8, 126.2, 127.1, 134.2, 139.4,
135.0 ppm. HRMS (EI): calcd. for C12H17ClS 228.0739; found
228.0735.
135.6, 140.1 ppm. 19F NMR (376 MHz, CDCl3): δ = –64.6 (s) ppm.
HRMS (EI): calcd. for C15H10F6S 336.0407; found 336.0414.
3-Chloro-5-methoxyphenyl Dodecyl Sulfide (3i): Following the gene-
ral procedure for Table 2, [Ir(OCH3)(C8H12)]2 (1.0 mg,
3-Chloro-5-methylphenyl Cyclohexyl Sulfide (3e): Following the ge-
neral procedure for Table 2, [Ir(OCH3)(C8H12)]2 (1.0 mg,
0.0015 mmol),
4,4Ј-di-tert-butyl-2,2Ј-bipyridyl
(0.8 mg,
0.003 mmol), pin2B2 (0.189 g, 0.73 mmol), and 3-chloroanisole
(0.125 mL, 1.0 mmol) in THF (1.5 mL). After removal of the vola-
tile components under vacuum, Cu(OAc)2 (0.136 g, 0.75 mmol), 1-
dodecanethiol (0.123 mL, 0.5 mmol), and DMF (2.0 mL). Purifica-
tion provided 3i (Table 2, entry 9) as a colorless oil (0.154 g, 90%
0.0015 mmol),
4,4Ј-di-tert-butyl-2,2Ј-bipyridyl
(0.8 mg,
0.003 mmol), pin2B2 (0.189 g, 0.73 mmol), and 3-chlorotoluene
(0.123 mL, 1.0 mmol) in THF (1.5 mL). After removal of the vola-
tile components under vacuum, Cu(OAc)2 (0.136 g, 0.75 mmol), cy-
clohexanethiol (0.065 mL, 0.5 mmol), and DMF (2.0 mL). Purifi-
cation provided 3e (Table 2, entry 5) as a colorless oil (0.096 g, 80%
yield). 1H NMR (400 MHz, CDCl3): δ = 1.24–1.38 (m, 5 H), 1.60–
1.63 (m, 1 H), 1.76–1.79 (m, 2 H), 1.96–1.99 (m, 2 H), 2.29 (s, 3
H), 3.09–3.14 (m, 1 H), 6.99 (s, 1 H), 7.06 (s, 1 H), 7.16 (s, 1 H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 21.1, 25.7, 25.9, 33.2, 46.4,
127.3, 127.8, 130.1, 134.1, 137.0, 140.0 ppm. HRMS (EI): calcd.
for C13H17ClS 240.0739; found 240.0737.
1
yield). H NMR (400 MHz, CDCl3): δ = 0.88 (t, J = 6.8 Hz, 3 H),
1.25–1.44 (m, 18 H), 1.57–1.67 (m, 2 H), 2.90 (t, J = 7.4 Hz, 2 H),
3.77 (s, 3 H), 6.67 (t, J = 2.0 Hz, 1 H), 6.71 (t, J = 2.0 Hz, 1 H),
6.85 (t, J = 1.6 Hz, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
14.1, 22.7, 28.8, 28.8, 29.1, 29.3, 29.5, 29.6, 29.6, 29.6, 31.9, 33.0,
111.4, 112.1, 119.9, 135.0, 140.2, 160.2 ppm. HRMS (EI): calcd.
for C19H31ClOS 342.1784; found 342.1780.
3-Chloro-5-methoxyphenyl 2-Methyl-1-butyl Sulfide (3j): Following
the general procedure for Table 2, [Ir(OCH3)(C8H12)]2 (1.0 mg,
3,5-Bis(trifluoromethyl)phenyl Dodecyl Sulfide (3f): Following the
general procedure for Table 2, [Ir(OCH3)(C8H12)]2 (0.7 mg,
0.0015 mmol),
4,4Ј-di-tert-butyl-2,2Ј-bipyridyl
(0.8 mg,
0.001 mmol),
4,4Ј-di-tert-butyl-2,2Ј-bipyridyl
(0.5 mg,
0.003 mmol), pin2B2 (0.189 g, 0.73 mmol), and 3-chloroanisole
(0.125 mL, 1.0 mmol) in THF (1.5 mL). After removal of the vola-
tile components under vacuum, Cu(OAc)2 (0.136 g, 0.75 mmol), 2-
methyl-1-butanethiol (0.065 mL, 0.5 mmol), and DMF (2.0 mL).
Purification provided 3j (Table 2, entry 10) as a colorless oil
0.002 mmol), pin2B2 (0.189 g, 0.73 mmol), and 1,3-bis(trifluoro-
methyl)benzene (0.160 mL, 1.0 mmol) in THF (1.5 mL). After re-
moval of the volatile components under vacuum, Cu(OAc)2
(0.136 g, 0.75 mmol), 1-dodecanethiol (0.123 mL, 0.5 mmol), and
DMF (2.0 mL). Purification provided 3f (Table 2, entry 6) as a col-
1
(0.093 g, 76% yield). H NMR (400 MHz, CDCl3): δ = 0.91 (t, J
1
orless oil (0.1224 g, 59% yield). H NMR (600 MHz, CDCl3): δ =
= 7.4 Hz, 3 H), 1.02 (d, J = 6.8 Hz, 3 H), 1.23–1.31 (m, 1 H), 1.49–
1.57 (m, 1 H), 1.64–1.70 (m, 1 H), 2.73 (dd, J = 7.2, 12.4 Hz, 1 H),
2.93 (dd, J = 6.0, 12.4 Hz, 1 H), 3.77 (s, 3 H), 6.66 (t, J = 2.0 Hz,
1 H), 6.71 (t, J = 1.0 Hz, 1 H), 6.85 (t, J = 1.8 Hz, 1 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 11.2, 18.9, 28.8 34.4, 40.0, 55.5,
111.3, 112.0, 119.9, 135.0, 140.6, 160.2 ppm. HRMS (EI): calcd.
for C12H17ClOS 244.0689; found 244.0684.
0.88 (t, J = 6.9 Hz, 3 H), 1.26–1.48 (m, 18 H), 1.67–1.72 (m, 2 H),
3.00 (t, J = 7.2 Hz, 2 H), 7.61 (s, 1 H), 7.65 (s, 2 H) ppm. 13C
NMR (125 MHz, CDCl3): δ = 14.1, 22.7, 28.5, 28.8, 29.1, 29.3,
29.4, 29.5, 29.6, 31.9, 32.8, 118.7, 123.1 (q, J = 226.0 Hz), 127.1,
132.0 (q, J = 27.5 Hz), 141.4 ppm. 19F NMR (376 MHz, CDCl3):
δ = –64.7 (s) ppm. HRMS (EI): calcd. for C20H28F6S 414.1816;
found 414.1812.
3-Chloro-5-methoxyphenyl Cyclohexyl Sulfide (3k): Following the
general procedure for Table 2, [Ir(OCH3)(C8H12)]2 (1.0 mg,
3,5-Bis(trifluoromethyl)phenyl 2-Methyl-l-butyl Sulfide (3g): Fol-
lowing the general procedure for Table 2, [Ir(OCH3)(C8H12)]2
(0.7 mg, 0.001 mmol), 4,4Ј-di-tert-butyl-2,2Ј-bipyridyl (0.5 mg,
0.002 mmol), pin2B2 (0.189 g, 0.73 mmol), and 1,3-bis(trifluoro-
methyl)benzene (0.160 mL, 1.0 mmol) in THF (1.5 mL). After re-
moval of the volatile components under vacuum, Cu(OAc)2
0.0015 mmol),
4,4Ј-di-tert-butyl-2,2Ј-bipyridyl
(0.8 mg,
0.003 mmol), pin2B2 (0.189 g, 0.73 mmol), and 3-chloroanisole
(0.125 mL, 1.0 mmol) in THF (1.5 mL). After removal of the vola-
tile components under vacuum, Cu(OAc)2 (0.136 g, 0.75 mmol), cy-
clohexanethiol (0.065 mL, 0.5 mmol), and DMF (2.0 mL). Purifi-
cation provided 3k (Table 2, entry 11) as a colorless oil (0.091 g,
(0.136 g,
0.75 mmol),
2-methyl-1-butanethiol
(0.065 mL,
0.5 mmol), and DMF (2.0 mL). Purification provided 3g (Table 2,
entry 7) as a colorless oil (0.083 g, 53% yield). 1H NMR (600 MHz,
CDCl3): δ = 0.95 (t, J = 7.5 Hz, 3 H), 1.06 (d, J = 6.6 Hz, 3 H),
1.31–1.35 (m, 1 H), 1.53–1.57 (m, 1 H), 1.70–1.73 (m, 1 H), 2.83
(dd, J = 7.8, 12.6 Hz, 1 H), 3.04 (dd, J = 5.7, 12.3 Hz, 1 H), 7.60
(s, 1 H), 7.66 (s, 2 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 11.2,
19.0, 28.8, 34.3, 39.7, 118.6, 123.1 (q, J = 226.0 Hz), 127.0, 132.0
(q, J = 27.7 Hz), 141.8 ppm. 19F NMR (376 MHz, CDCl3): δ =
–64.7 (s) ppm. HRMS (EI): calcd. for C13H14F6S 316.0720; found
316.0725.
1
71% yield). H NMR (400 MHz, CDCl3): δ = 1.23–1.25 (m, 5 H),
1.60–1.64 (m, 1 H), 1.76–1.79 (m, 2 H), 1.98–2.01 (m, 2 H), 3.13–
3.17 (m, 1 H), 3.77 (s, 3 H), 6.72 (t, J = 2.0 Hz, 1 H), 6.79 (t, J =
1.8 Hz, 1 H), 6.94 (t, J = 1.6 Hz, 1 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 25.6, 25.9, 33.1, 46.2, 55.5, 112.2, 114.8, 122.6, 134.8,
138.3, 160.1 ppm. HRMS (EI): calcd. for C13H17ClOS 256.0689;
found 256.0681.
3,5-Dichlorophenyl 2-Methyl-1-butyl Sulfide (3l): Following the ge-
neral procedure for Table 2, [Ir(OCH3)(C8H12)]2 (1.0 mg,
3914
www.eurjoc.org
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2013, 3910–3918

Regioselective Synthesis of Aryl Thioethers and Aryl Selenides
0.0015 mmol), 4,4Ј-di-tert-butyl-2,2Ј-bipyridyl (0.8 mg, (0.136 g, 0.75 mmol), 4-methoxythiophenol (0.063 mL, 0.5 mmol),
0.003 mmol), pin2B2 (0.189 g, 0.73 mmol), and 1,3-dichlorobenzene
(0.115 mL, 1.0 mmol) in THF (1.5 mL). After removal of the vola-
tile components under vacuum, Cu(OAc)2 (0.136 g, 0.75 mmol), 2-
and DMF (2.0 mL). Purification provided 3p (Table 2, entry 16) as
a white solid (0.097 g, 55% yield), m.p. 54–55 °C (ref.[19] 54–55 °C).
1H NMR (600 MHz, CDCl3): δ = 3.76 (s, 3 H), 6.88 (dd, J = 1.8,
methyl-1-butanethiol (0.065 mL, 0.5 mmol), and DMF (2.0 mL). 6.6 Hz, 2 H), 7.36 (s, 2 H), 7.38 (dd, J = 2.4, 6.6 Hz, 2 H), 7.47 (s,
Purification provided 3l (Table 2, entry 12) as a colorless oil
(0.071 g, 57% yield). H NMR (400 MHz, CDCl3): δ = 0.92 (t, J 118.7, 118.7, 118.8, 118.8, 120.3, 123.1 (q, J = 226.1 Hz), 126.1,
1 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 55.4, 115.7, 118.7,
1
= 7.4 Hz, 3 H), 1.01 (d, J = 4.4 Hz, 3 H), 1.24–1.32 (m, 1 H), 1.47–
1.56 (m, 1 H), 1.63–1.70 (m, 1 H), 2.74 (dd, J = 7.6, 12.4 Hz, 1 H),
2.93 (dd, J = 5.8, 12.4 Hz, 1 H), 7.09–7.13 (m, 3 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 11.2, 18.9, 28.8, 34.3, 40.0, 125.2, 125.6,
135.1, 141.7 ppm. HRMS (EI): calcd. for C11H14Cl2S 248.0193;
found 248.0186.
126.1, 132.0 (q, J = 27.6 Hz), 136.8, 143.6, 161.0 ppm. 19F NMR
(376 MHz, CDCl3): δ = –64.6 (s) ppm.
3,5-Bis(trifluoromethyl)phenyl 2-Naphthyl Sulfide (3q): Following
the general procedure for Table 2, [Ir(OCH3)(C8H12)]2 (0.7 mg,
0.001 mmol),
4,4Ј-di-tert-butyl-2,2Ј-bipyridyl
(0.5 mg,
0.002 mmol), pin2B2 (0.189 g, 0.73 mmol), and 1,3-bis(trifluoro-
methyl)benzene (0.160 mL, 1.0 mmol) in THF (1.5 mL). After re-
moval of the volatile components under vacuum, Cu(OAc)2
(0.136 g, 0.75 mmol), 2-naphthalenethiol (0.081 g, 0.5 mmol), and
DMF (2.0 mL). Purification provided 3q (Table 2, entry 17) as a
3,5-Dichlorophenyl Cyclohexyl Sulfide (3m): Following the general
procedure for Table 2, [Ir(OCH3)(C8H12)]2 (1.0 mg, 0.0015 mmol),
4,4Ј-di-tert-butyl-2,2Ј-bipyridyl (0.8 mg, 0.003 mmol), pin2B2
(0.189 g, 0.73 mmol), and 1,3-dichlorobenzene (0.115 mL,
1.0 mmol) in THF (1.5 mL). After removal of the volatile compo-
1
colorless oil (0.101 g, 55% yield). H NMR (600 MHz, CDCl3): δ
nents under vacuum, Cu(OAc)2 (0.136 g, 0.75 mmol), cyclohex- = 7.44 (dd, J = 1.8, 8.4 Hz, 1 H), 7.52–7.55 (m, 2 H), 7.62 (s, 2 H),
anethiol (0.065 mL, 0.5 mmol), and DMF (2.0 mL). Purification
7.65 (s, 1 H), 7.80–7.81 (m, 1 H), 7.84–7.86 (m, 2 H), 8.04 (s, 1 H)
provided 3m (Table 2, entry 13) as a colorless oil (0.068 g, 52%
ppm. 13C NMR (125 MHz, CDCl3): δ = 119.7, 119.7, 119.7, 123.0
yield). 1H NMR (400 MHz, CDCl3): δ = 1.20–1.43 (m, 5 H), 1.59– (q, J = 226.3 Hz), 127.1, 127.3, 128.0, 128.0, 128.0, 128.3, 129.8,
1.64 (m, 1 H), 1.74–1.86 (m, 2 H), 1.92–2.04 (m, 2 H), 3.10–3.22
129.9, 132.3 (q, J = 27.8 Hz), 133.2, 133.5, 133.9, 141.6 ppm. 19F
NMR (376 MHz, CDCl3): δ = –64.6 (s) ppm. HRMS (EI): calcd.
(m, 1 H), 7.17 (t, J = 2.0 Hz, 1 H), 7.21 (d, J = 2.0 Hz, 2 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 25.6, 25.9, 33.1, 46.3, 126.3, for C18H10F6S 372.0407; found 372.0399.
128.4, 134.9, 139.4 ppm. HRMS (EI): calcd. for C12H14Cl2S
260.0193; found 260.0190.
3-Chloro-5-methoxyphenyl Phenyl Sulfide (3r):[19] Following the ge-
neral procedure for Table 2, [Ir(OCH3)(C8H12)]2 (1.0 mg,
0.0015 mmol), 4,4Ј-di-tert-butyl-2,2Ј-bipyridyl (0.8 mg,
0.003 mmol), pin2B2 (0.189 g, 0.73 mmol), and 3-chloroanisole
(0.125 mL, 1.0 mmol) in THF (1.5 mL). After removal of the vola-
2,6-Di-tert-butyl-4-pyridyl Dodecyl Sulfide (3n): Following the gene-
ral procedure for Table 2, [Ir(OCH3)(C8H12)]2 (19.9 mg,
0.03 mmol), 4,4Ј-di-tert-butyl-2,2Ј-bipyridyl (16.4 mg, 0.06 mmol),
pin2B2 (0.189 g, 0.73 mmol), and 2,6-di-tert-butylpyridine tile components under vacuum, Cu(OAc)2 (0.136 g, 0.75 mmol),
(0.232 mL, 1.0 mmol) in THF (1.5 mL). After removal of the vola-
tile components under vacuum, Cu(OAc)2 (0.1362 g, 0.75 mmol),
1-dodecanethiol (0.123 mL, 0.5 mmol), and DMF (2.0 mL). Purifi-
thiophenol (0.053 mL, 0.5 mmol), and DMF (2.0 mL). Purification
provided 3r (Table 2, entry 18) as a colorless oil (0.078 g, 62%
1
yield). H NMR (400 MHz, CDCl3): δ = 3.73 (s, 3 H), 6.68 (t, J =
cation provided 3n (Table 2, entry 14) as a colorless oil (0.103 g,
2 Hz, 1 H), 6.72 (t, J = 2.2 Hz, 1 H), 6.81 (t, J = 1.6 Hz, 1 H),
1
53% yield). H NMR (400 MHz, CDCl3): δ = 0.87 (t, J = 6.0 Hz, 7.30–7.39 (m, 3 H), 7.40–7.46 (m, 2 H) ppm. 13C NMR (100 MHz,
3 H), 1.26–1.32 (m, 34 H), 1.42–1.47 (m, 2 H), 1.69–1.72 (m, 2 H), CDCl3): δ = 55.5, 112.5, 113.4, 121.4, 128.1, 129.5, 132.6, 133.4,
2.95 (t, J = 7.2 Hz, 2 H), 6.93 (s, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 14.1, 22.7, 28.8, 29.0, 29.2, 29.3, 29.5, 29.6, 29.6, 30.0,
30.8, 31.9, 37.6, 112.7, 148.1, 167.4 ppm. HRMS (EI): calcd. for
C25H45NS 391.3273; found 391.3279.
135.3, 139.7, 160.4 ppm.
3-Chloro-5-methoxyphenyl 4-Methoxyphenyl Sulfide (3s): Following
the general procedure for Table 2, [Ir(OCH3)(C8H12)]2 (1.0 mg,
0.0015 mmol),
4,4Ј-di-tert-butyl-2,2Ј-bipyridyl
(0.8 mg,
2,6-Di-tert-butyl-4-pyridyl 2-Methyl-1-butyl Sulfide (3o): Following 0.003 mmol), pin2B2 (0.189 g, 0.73 mmol), and 3-chloroanisole
the general procedure for Table 2, [Ir(OCH3)(C8H12)]2 (19.9 mg,
0.03 mmol), 4,4Ј-di-tert-butyl-2,2Ј-bipyridyl (16.4 mg, 0.06 mmol),
(0.125 mL, 1.0 mmol) in THF (1.5 mL). After removal of the vola-
tile components under vacuum, Cu(OAc)2 (0.136 g, 0.75 mmol), 4-
pin2B2 (0.189 g, 0.73 mmol), and 2,6-di-tert-butylpyridine methoxythiophenol (0.063 mL, 0.5 mmol), and DMF (2.0 mL). Pu-
(0.232 mL, 1.0 mmol) in THF (1.5 mL). After removal of the vola-
tile components under vacuum, Cu(OAc)2 (0.136 g, 0.75 mmol), 2-
rification provided 3s (Table 2, entry 19) as a yellow oil (0.079 g,
56% yield). H NMR (400 MHz, CDCl3): δ = 3.72 (s, 3 H), 3.84
1
methyl-1-butanethiol (0.065 mL, 0.5 mmol), and DMF (2.0 mL). (s, 3 H), 6.53 (t, J = 1.8 Hz, 1 H), 6.64 (t, J = 1.4 Hz, 2 H), 6.92
Purification provided 3o (Table 2, entry 15) as a colorless oil
(0.106 g, 72% yield). H NMR (400 MHz, CDCl3): δ = 0.95 (t, J
(dd, J = 2.2, 6.6 Hz, 2 H), 7.44 (dd, J = 2.2, 7.0 Hz, 2 H) ppm. 13
NMR (100 MHz, CDCl3): δ = 55.4, 55.5, 111.2, 111.4, 115.2, 119.2,
C
1
= 67.4 Hz, 3 H), 1.05 (d, J = 6.8 Hz, 3 H), 1.26–1.37 (m, 19 H), 122.3, 135.2, 136.3, 142.2, 160.3, 160.4 ppm. HRMS (EI): calcd.
1.48–1.58 (m, 1 H), 1.71–1.76 (m, 1 H), 2.75 (dd, J = 7.6, 12.4 Hz,
1 H), 3.01 (dd, J = 5.8, 12.6 Hz, 1 H), 6.93 (s, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 11.4, 19.1, 29.0, 30.3, 34.5, 37.7, 37.7,
112.7, 148.4, 167.4 ppm. HRMS (EI): calcd. for C18H31NS
293.2177; found 293.2170.
for C14H13ClO2S 280.0325; found 280.0335.
3-Chloro-5-methoxyphenyl 4-Chlorophenyl Sulfide (3t):[19] Following
the general procedure for Table 2, [Ir(OCH3)(C8H12)]2 (1.0 mg,
0.0015 mmol),
4,4Ј-di-tert-butyl-2,2Ј-bipyridyl
(0.8 mg,
0.003 mmol), pin2B2 (0.189 g, 0.73 mmol), and 3-chloroanisole
(0.125 mL, 1.0 mmol) in THF (1.5 mL). After removal of the vola-
tile components under vacuum, Cu(OAc)2 (0.136 g, 0.75 mmol), 4-
chlorothiophenol (0.074 g, 0.5 mmol), and DMF (2.0 mL). Purifi-
cation provided 3t (Table 2, entry 20) as a colorless oil (0.086 g,
3,5-Bis(trifluoromethyl)phenyl 4-Methoxyphenyl Sulfide (3p):[19]
Following the general procedure for Table 2, [Ir(OCH3)(C8H12)]2
(0.7 mg, 0.001 mmol), 4,4Ј-di-tert-butyl-2,2Ј-bipyridyl (0.5 mg,
0.002 mmol), pin2B2 (0.189 g, 0.73 mmol), and 1,3-bis(trifluoro-
methyl)benzene (0.160 mL, 1.0 mmol) in THF (1.5 mL). After re-
moval of the volatile components under vacuum, Cu(OAc)2
1
60% yield). H NMR (400 MHz, CDCl3): δ = 3.73 (s, 3 H), 6.67
(t, J = 1.8 Hz, 1 H), 6.73 (t, J = 2.0 Hz, 1 H), 6.80 (t, J = 1.6 Hz,
Eur. J. Org. Chem. 2013, 3910–3918
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
3915

C.-L. Yi, T.-J. Liu, J.-H. Cheng, C.-F. Lee
1 H), 7.30–7.32 (m, 4 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 51% yield). H NMR (600 MHz, CDCl3): δ = 2.26 (s, 3 H), 6.91
FULL PAPER
1
55.6, 112.9, 113.8, 121.7, 129.6, 132.3, 133.6, 134.2, 135.4, 138.9,
160.5 ppm.
3-Chloro-5-methylphenyl Phenyl Sulfide (3u):[19] Following the gene-
(s, 1 H), 6.95 (s, 1 H), 6.98 (s, 1 H), 7.04–7.07 (m, 2 H), 7.40–7.42
(m, 2 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 21.1, 116.6,
116.7, 125.7, 127.3, 127.8, 128.7, 128.7, 134.6, 135.0, 135.0, 138.8,
140.5, 161.9, 163.6 ppm. 19F NMR (376 MHz, CDCl3): δ = –114.3
(s) ppm. HRMS (EI): calcd. for C13H10ClFS 252.0176; found
252.0171.
ral procedure for Table 2, [Ir(OCH3)(C8H12)]2 (1.0 mg,
0.0015 mmol),
4,4Ј-di-tert-butyl-2,2Ј-bipyridyl
(0.8 mg,
0.003 mmol), pin2B2 (0.189 g, 0.73 mmol), and 3-chlorotoluene
(0.123 mL, 1.0 mmol) in THF (1.5 mL). After removal of the vola-
tile components under vacuum, Cu(OAc)2 (0.136 g, 0.75 mmol),
thiophenol (0.053 mL, 0.5 mmol), and DMF (2.0 mL). Purification
provided 3u (Table 2, entry 21) as a colorless oil (0.078 g, 67%
yield). 1H NMR (400 MHz, CDCl3): δ = 2.26 (s, 3 H), 6.99 (s, 2
H), 7.04 (s, 1 H), 7,28–7.39 (m, 5 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 21.0, 126.8, 127.6, 127.7, 128.8, 129.4, 132.0, 134.2,
134.5, 138.1, 140.4 ppm.
3-Chloro-5-methylphenyl 4-Nitrophenyl Sulfide (3z): Following the
general procedure for Table 2, [Ir(OCH3)(C8H12)]2 (1.0 mg,
0.0015 mmol),
4,4Ј-di-tert-butyl-2,2Ј-bipyridyl
(0.8 mg,
0.003 mmol), pin2B2 (0.1891 g, 0.73 mmol), and 3-chlorotoluene
(0.123 mL, 1.0 mmol) in THF (1.5 mL). After removal of the vola-
tile components under vacuum, Cu(OAc)2 (0.136 g, 0.75 mmol), 4-
nitrothiophenol (0.097 g, 0.5 mmol), and DMF (2.0 mL). Purifica-
tion provided 3z (Table 2, entry 26) as a yellow oil (0.064 g, 46%
yield). 1H NMR (400 MHz, CDCl3): δ = 2.36 (s, 3 H), 7.22–7.24
(m, 4 H), 7.32 (s, 1 H), 8.10 (d, J = 9.2 Hz, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 21.1, 124.1, 127.4, 130.4, 130.8, 132.3,
132.9, 135.2, 141.6, 145.7, 147.1 ppm. HRMS (EI): calcd. for
C13H10ClNO2S 279.0121; found 279.0114.
3-Chloro-5-methylphenyl 4-Methoxyphenyl Sulfide (3v):[19] Follow-
ing the general procedure for Table 2, [Ir(OCH3)(C8H12)]2 (1.0 mg,
0.0015 mmol),
4,4Ј-di-tert-butyl-2,2Ј-bipyridyl
(0.8 mg,
0.003 mmol), pin2B2 (0.189 g, 0.73 mmol), and 3-chlorotoluene
(0.123 mL, 1.0 mmol) in THF (1.5 mL). After removal of the vola-
tile components under vacuum, Cu(OAc)2 (0.136 g, 0.75 mmol), 4-
methoxythiophenol (0.063 mL, 0.5 mmol), and DMF (2.0 mL). Pu-
rification provided 4h (Table 2, entry 22) as a colorless oil (0.075 g,
56% yield). 1H NMR (400 MHz, CDCl3): δ = 2.23 (s, 3 H), 3.82
(s, 3 H), 6.85 (d, J = 7.6 Hz, 2 H), 6.91 (dd, J = 2.0, 6.8 Hz, 3 H),
7.42 (dd, J = 2.0, 6.8 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 21.1, 55.3, 115.1, 122.9, 124.3, 126.3, 126.4, 134.4, 135.9, 140.2,
140.7, 160.2 ppm.
General Procedure for Reactions in Table 3: A Schlenk tube
equipped with
a magnetic stirring bar was charged with
[Ir(OCH3)(C8H12)]2 (1.0 mg, 0.0015 mmol), 4,4Ј-di-tert-butyl-2,2Ј-
bipyridyl (0.8 mg, 0.003 mmol), and pin2B2 (0.189 g, 0.73 mmol) in
a nitrogen-filled glove box. The Schlenk tube was then covered with
a rubber septum and removed from the glove box. Under a nitrogen
atmosphere, arene (1.0 mmol) and THF (1.5 mL) were added by
syringe, and the Schlenk tube was heated at 80 °C in an oil bath.
After stirring at this temperature for 24 h, the heterogeneous mix-
ture was cooled to room temperature, after removal of the volatile
components under vacuum. This Schlenk tube was returned to the
glove box, Cu(OAc)2 (0.136 g, 0.75 mmol) was added, and the
Schlenk tube was then covered with a rubber septum and removed
from the glove box. Under an argon atmosphere, diselenide
(0.6 mmol), pyridine (0.123 mL, 1.5 mmol), and DMF (2.0 mL)
were added by syringe, and the Schlenk tube was connected to an
argon-filled balloon and heated at 120 °C in an oil bath. After stir-
ring at this temperature for 24 h, the heterogeneous mixture was
cooled to room temperature and diluted with ethyl acetate (20 mL).
The resulting solution was directly filtered through a pad of silica
gel then washed with ethyl acetate (20 mL) and concentrated to
give the crude material, which was then purified by column
chromatography (SiO2, hexane) to yield 4.
3-Chloro-5-methylphenyl 4-Chlorophenyl Sulfide (3w):[19] Following
the general procedure for Table 2, [Ir(OCH3)(C8H12)]2 (1.0 mg,
0.0015 mmol),
4,4Ј-di-tert-butyl-2,2Ј-bipyridyl
(0.8 mg,
0.003 mmol), pin2B2 (0.189 g, 0.73 mmol), and 3-chlorotoluene
(0.123 mL, 1.0 mmol) in THF (1.5 mL). After removal of the vola-
tile components under vacuum, Cu(OAc)2 (0.136 g, 0.75 mmol), 4-
chlorothiophenol (0.074 g, 0.5 mmol), and DMF (2.0 mL). Purifi-
cation provided 3w (Table 2, entry 23) as a colorless oil (0.087 g,
65% yield). 1H NMR (400 MHz, CDCl3): δ = 2.27 (s, 3 H), 6.98
(s, 1 H), 7.03 (s, 1 H), 7.05 (s, 1 H), 7.29 (s, 4 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 21.1, 127.0, 128.0, 129.1, 129.5, 133.0,
133.1, 133.8, 134.6, 137.3, 140.7 ppm.
3-Chloro-5-methylphenyl 2-Naphthyl Sulfide (3x):[19] Following the
general procedure for Table 2, [Ir(OCH3)(C8H12)]2 (1.0 mg,
0.0015 mmol),
4,4Ј-di-tert-butyl-2,2Ј-bipyridyl
(0.8 mg,
3-Chloro-5-methylphenyl Methyl Selenide (4a): Following the gene-
ral procedure for Table 3, [Ir(OCH3)(C8H12)]2 (1.0 mg,
0.003 mmol), pin2B2 (0.189 g, 0.73 mmol), and 3-chlorotoluene
(0.123 mL, 1.0 mmol) in THF (1.5 mL). After removal of the vola-
tile components under vacuum, Cu(OAc)2 (0.1362 g, 0.75 mmol),
2-naphthalenethiol (0.081 g, 0.5 mmol), and DMF (2.0 mL). Purifi-
cation provided 3x (Table 2, entry 24) as a colorless oil (0.101 g,
0.0015 mmol),
4,4Ј-di-tert-butyl-2,2Ј-bipyridyl
(0.8 mg,
0.003 mmol), pin2B2 (0.189 g, 0.73 mmol), and 3-chlorotoluene
(0.123 mL, 1.0 mmol) in THF (1.5 mL). After removal of the vola-
tile components under vacuum, Cu(OAc)2 (0.136 g, 0.75 mmol), di-
methyl diselenide (0.060 mL, 0.6 mmol), and DMF (2.0 mL). Puri-
fication provided 4a (Table 3, entry 1) as a yellow oil (0.135 g, 61%
yield). 1H NMR (400 MHz, CDCl3): δ = 2.29 (s, 3 H), 2.34 (s, 3
H), 6.98 (s, 1 H), 7.09 (s, 1 H), 7.17 (s, 1 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 7.1, 21.0, 126.5, 126.9, 128.8, 133.3, 134.4,
140.2 ppm. HRMS (EI): calcd. for C8H9ClSe 219.9558; found
219.9563.
1
71% yield). H NMR (400 MHz, CDCl3): δ = 2.23 (s, 3 H), 7.0–
7.01 (m, 2 H), 7.08 (s, 1 H), 7.39 (d, J = 2.0 Hz, 1 H), 7.41–7.48
(m, 2 H), 7.73–7.81 (m, 3 H), 7.89 (s, 1 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 21.0, 126.5, 126.7, 126.7, 127.5, 127.6,
127.7, 128.7, 129.1, 129.3, 131.2, 131.4, 132.5, 133.7, 134.6, 138.1,
140.5 ppm.
3-Chloro-5-methylphenyl 4-Fluorophenyl Sulfide (3y): Following the
general procedure for Table 2, [Ir(OCH3)(C8H12)]2 (1.0 mg,
0.0015 mmol),
4,4Ј-di-tert-butyl-2,2Ј-bipyridyl
(0.8 mg, 3,5-Bis(trifluoromethyl)phenyl Methyl Selenide (4b): Following the
general procedure for Table 3, [Ir(OCH3)(C8H12)]2 (0.7 mg,
0.001 mmol), 4,4Ј-di-tert-butyl-2,2Ј-bipyridyl (0.5 mg,
0.003 mmol), pin2B2 (0.189 g, 0.73 mmol), and 3-chlorotoluene
(0.123 mL, 1.0 mmol) in THF (1.5 mL). After removal of the vola-
tile components under vacuum, Cu(OAc)2 (0.1362 g, 0.75 mmol),
4-fluorothiophenol (0.055 mL, 0.5 mmol), and DMF (2.0 mL). Pu-
rification provided 3y (Table 2, entry 25) as a colorless oil (0.064 g,
0.002 mmol), pin2B2 (0.189 g, 0.73 mmol), and 1,3-bis(trifluoro-
methyl)benzene (0.160 mL, 1.0 mmol) in THF (1.5 mL). After re-
moval of the volatile components under vacuum, Cu(OAc)2
3916
www.eurjoc.org
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2013, 3910–3918

Regioselective Synthesis of Aryl Thioethers and Aryl Selenides
(0.136 g, 0.75 mmol), dimethyl diselenide (0.060 mL, 0.6 mmol),
moval of the volatile components under vacuum, Cu(OAc)2
(0.1362 g, 0.75 mmol), diphenyl diselenide (0.1893 g, 0.6 mmol),
and DMF (2.0 mL). Purification provided 4b (Table 3, entry 2) as
1
a colorless oil (0.161 g, 52% yield). H NMR (600 MHz, CDCl3): and DMF (2.0 mL). Purification provided 4g (Table 3, entry 7) as
δ = 2.44 (s, 3 H), 7.65 (s, 1 H), 7.77 (s, 2 H) ppm. 13C NMR
(125 MHz, CDCl3): δ = 7.2, 119.6, 119.7, 119.7, 123.0 (q, J =
a yellow oil (0.232 g, 63% yield). H NMR (600 MHz, CDCl3): δ
1
= 7.40–7.44 (m, 3 H), 7.59–7.61 (m, 2 H), 7.69 (s, 1 H), 7.74 (s, 2
226.3 Hz), 129.3, 132.0 (q, J = 27.6 Hz), 135.3 ppm. 19F NMR H) ppm. 13C NMR (125 MHz, CDCl3): δ = 120.4, 120.4, 120.4,
(376 MHz, CDCl3): δ = –64.7 (s) ppm. HRMS (EI): calcd. for
C9H6F6Se 307.9539; found 307.9544.
122.9 (q, J = 227.9 Hz), 129.2, 130.0, 130.6, 130.6, 132.2 (q, J =
27.7 Hz), 135.0, 135.9 ppm. 19F NMR (376 MHz, CDCl3): δ =
–64.6 (s) ppm.
3-Chloro-5-methoxyphenyl Methyl Selenide (4c): Following the ge-
neral procedure for Table 3, [Ir(OCH3)(C8H12)]2 (1.0 mg,
3-Chloro-5-methoxyphenyl Phenyl Selenide (4h):[19] Following the
0.0015 mmol),
4,4Ј-di-tert-butyl-2,2Ј-bipyridyl
(0.8 mg,
general procedure for Table 3, [Ir(OCH3)(C8H12)]2 (1.0 mg,
0.003 mmol), pin2B2 (0.189 g, 0.73 mmol), and 3-chloroanisole
(0.125 mL, 1.0 mmol) in THF (1.5 mL). After removal of the vola-
tile components under vacuum, Cu(OAc)2 (0.136 g, 0.75 mmol), di-
methyl diselenide (0.060 mL, 0.6 mmol), and DMF (2.0 mL). Puri-
fication provided 4c (Table 3, entry 3) as a colorless oil (0.151 g,
0.0015 mmol),
4,4Ј-di-tert-butyl-2,2Ј-bipyridyl
(0.8 mg,
0.003 mmol), pin2B2 (0.189 g, 0.73 mmol), and 3-chloroanisole
(0.125 mL, 1.0 mmol) in THF (1.5 mL). After removal of the vola-
tile components under vacuum, Cu(OAc)2 (0.136 g, 0.75 mmol), di-
phenyl diselenide (0.189 g, 0.6 mmol), and DMF (2.0 mL). Purifi-
cation provided 4h (Table 3, entry 8) as a yellow oil (0.195 g, 66%
1
64% yield). H NMR (400 MHz, CDCl3): δ = 2.35 (s, 3 H), 3.78
(s, 3 H), 6.72 (s, 1 H), 6.82 (s, 1 H), 6.95 (s, 1 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 7.1, 55.5, 112.0, 114.0, 121.7, 134.3, 135.1,
160.2 ppm. HRMS (EI): calcd. for C8H9ClOSe 235.9507; found
235.9500.
1
yield). H NMR (400 MHz, CDCl3): δ = 3.73 (s, 3 H), 6.76 (t, J =
2.2 Hz, 1 H), 6.82 (dd, J = 1.4, 2.2 Hz, 1 H), 6.96 (t, J = 1.4 Hz, 1
H), 7.31–7.33 (m, 3 H), 7.52–7.54 (m, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 55.5, 113.1, 115.8, 123.7, 128.1, 129.4,
129.5, 134.0, 134.1, 135.3, 160.4 ppm.
3,5-Dichlorophenyl Methyl Selenide (4d): Following the general pro-
cedure for Table 3, [Ir(OCH3)(C8H12)]2 (1.0 mg, 0.0015 mmol),
4,4Ј-di-tert-butyl-2,2Ј-bipyridyl (0.8 mg, 0.003 mmol), pin2B2
(0.189 g, 0.73 mmol), and 1,3-dichlorobenzene (0.115 mL,
1.0 mmol) in THF (1.5 mL). After removal of the volatile compo-
nents under vacuum, Cu(OAc)2 (0.136 g, 0.75 mmol), dimethyl dis-
elenide (0.060 mL, 0.6 mmol), and DMF (2.0 mL). Purification
provided 4d (Table 3, entry 4) as a colorless oil (0.123 g, 52% yield).
1H NMR (400 MHz, CDCl3): δ = 2.37 (s, 3 H), 7.17 (s, 1 H), 7.24
(s, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 7.2, 126.0, 127.6,
135.2 ppm. HRMS (EI): calcd. for C7H6Cl2Se 239.9012; found
239.9014.
3,5-Dichlorophenyl Phenyl Selenide (4i):[19] Following the general
procedure for Table 3, [Ir(OCH3)(C8H12)]2 (1.0 mg, 0.0015 mmol),
4,4Ј-di-tert-butyl-2,2Ј-bipyridyl (0.8 mg, 0.003 mmol), pin2B2
(0.189 g, 0.73 mmol), and 1,3-dichlorobenzene (0.115 mL,
1.0 mmol) in THF (1.5 mL). After removal of the volatile compo-
nents under vacuum, Cu(OAc)2 (0.136 g, 0.75 mmol), diphenyl dis-
elenide (0.1893 g, 0.6 mmol), and DMF (2.0 mL). Purification pro-
1
vided 4i (Table 3, entry 9) as a yellow oil (0.227 g, 75% yield). H
NMR (400 MHz, CDCl3): δ = 7.18–7.21 (m, 3 H), 7.33–7.38 (m, 3
H), 7.54–7.56 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
126.9, 128.4, 128.7, 129.1, 129.8, 134.7, 135.4 ppm.
2,6-Di-tert-butyl-4-pyridyl Methyl Selenide (3e): Following the ge-
neral procedure for Table 3, [Ir(OCH3)(C8H12)]2 (19.9 mg,
0.03 mmol), 4,4Ј-di-tert-butyl-2,2Ј-bipyridyl (16.4 mg, 0.06 mmol),
pin2B2 (0.1891 g, 0.73 mmol), and 2,6-di-tert-butylpyridine
(0.232 mL, 1.0 mmol) in THF (1.5 mL). After removal of the vola-
tile components under vacuum, Cu(OAc)2 (0.136 g, 0.75 mmol), di-
methyl diselenide (0.060 mL, 0.6 mmol), and DMF (2.0 mL). Puri-
fication provided 3e (Table 3, entry 5) as a yellow oil (0.150 g, 53%
2,6-Di-tert-butyl-4-pyridyl Phenyl Selenide (4j): Following the gene-
ral procedure for Table 3, [Ir(OCH3)(C8H12)]2 (19.9 mg,
0.03 mmol), 4,4Ј-di-tert-butyl-2,2Ј-bipyridyl (16.4 mg, 0.06 mmol),
pin2B2 (0.189 g, 0.73 mmol), and 2,6-di-tert-butylpyridine
(0.232 mL, 1.0 mmol) in THF (1.5 mL). After removal of the vola-
tile components under vacuum, Cu(OAc)2 (0.136 g, 0.75 mmol), di-
phenyl diselenide (0.189 g, 0.6 mmol), and DMF (2.0 mL). Purifi-
cation provided 4j (Table 3, entry 10) as a yellow oil (0.230 g, 66%
1
1
yield). H NMR (400 MHz, CDCl3): δ = 1.33 (s, 18 H), 2.37 (s, 3
yield). H NMR (400 MHz, CDCl3): δ = 1.26 (s, 18 H), 6.97 (s, 2
H), 7.07 (s, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 5.5, 30.0,
37.7, 115.4, 143.2, 167.5 ppm. HRMS (EI): calcd. for C14H23NSe
285.0996; found 285.1001.
H), 7.36–7.38 (m, 3 H), 7.60–7.62 (m, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 30.0, 37.6, 116.3, 127.5, 128.6, 129.6, 135.5,
143.9, 167.8 ppm. HRMS (EI): calcd. for C19H25NSe 347.1152;
found 347.1144.
3-Chloro-5-methylphenyl Phenyl Selenide (4f):[19] Following the
general procedure for Table 3, [Ir(OCH3)(C8H12)]2 (1.0 mg,
Supporting Information (see footnote on the first page of this arti-
cle): Copies of the NMR spectra for all products.
0.0015 mmol),
4,4Ј-di-tert-butyl-2,2Ј-bipyridyl
(0.8 mg,
0.003 mmol), pin2B2 (0.189 g, 0.73 mmol), and 3-chlorotoluene
(0.123 mL, 1.0 mmol) in THF (1.5 mL). After removal of the vola-
tile components under vacuum, Cu(OAc)2 (0.136 g, 0.75 mmol), di-
phenyl diselenide (0.189 g, 0.6 mmol), and DMF (2.0 mL). Purifi-
cation provided 4f (Table 3, entry 6) as a colorless oil (0.183 g, 65%
yield). 1H NMR (400 MHz, CDCl3): δ = 2.26 (s, 3 H), 7.03 (s, 1
H), 7.13 (s, 1 H), 7.19 (s, 1 H), 7.28–7.30 (m, 3 H), 7.48–7.50 (m,
2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 21.0, 127.8, 128.0,
129.0, 129.5, 130.0, 131.1, 132.8, 133.6, 134.5, 140.6 ppm.
Acknowledgments
The National Science Council, Taiwan (grant number NSC 101-
2113-M-005-008-MY3), the National Chung Hsing University and
the Center of Nanoscience and Nanotechnology (NCHU) are
gratefully acknowledged for financial support. The authors thank
Prof. Fung-E. Hong (NCHU) for sharing his GC–MS instruments.
C.-F. L. is a Golden-Jade Fellow of Kenda Foundation, Taiwan.
3,5-Bis(trifluoromethyl)phenyl Phenyl Selenide (4g):[19] Following
the general procedure for Table 3, [Ir(OCH3)(C8H12)]2 (0.7 mg,
0.001 mmol),
4,4Ј-di-tert-butyl-2,2Ј-bipyridyl
(0.5 mg,
[1] a) P. Fang, M. Li, H. Ge, J. Am. Chem. Soc. 2010, 132, 11898–
11899; b) J. Norinder, A. Matsumoto, N. Yoshikai, E. Naka-
mura, J. Am. Chem. Soc. 2008, 130, 5858–5859; c) G. Deng, L.
0.002 mmol), pin2B2 (0.189 g, 0.73 mmol), and 1,3-bis(trifluoro-
methyl)benzene (0.160 mL, 1.0 mmol) in THF (1.5 mL). After re-
Eur. J. Org. Chem. 2013, 3910–3918
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
3917

C.-L. Yi, T.-J. Liu, J.-H. Cheng, C.-F. Lee
FULL PAPER
Zhao, C.-J. Li, Angew. Chem. 2008, 120, 6374–6378; Angew.
Chem. Int. Ed. 2008, 47, 6278–6282; d) J. Wen, J. Zhang, S.-Y.
Chen, J. Li, X.-Q. Yu, Angew. Chem. 2008, 120, 9029–9032;
Angew. Chem. Int. Ed. 2008, 47, 8897–8900; e) I. Ban, T. Sudo,
T. Taniguchi, K. Itami, Org. Lett. 2008, 10, 3607–3609; f) J.
Ryu, S. H. Cho, S. Chang, Angew. Chem. 2012, 124, 3737–3741;
Angew. Chem. Int. Ed. 2012, 51, 3677–3681.
[8] For cobalt-catalyzed C–S bond formation, see: Y.-C. Wong,
T. T. Jayanth, C.-H. Cheng, Org. Lett. 2006, 8, 5613–5616.
[9] For indium-catalyzed C–S bond formation, see: a) V. P. Reddy,
K. Swapna, A. V. Kumar, K. R. Rao, J. Org. Chem. 2009, 74,
3189–3191; b) V. P. Reddy, A. V. Kumar, K. Swapna, K. Rao,
Org. Lett. 2009, 11, 1697–1700.
[10] For iron-catalyzed C–S bond formation, see: a) Y.-Y. Lin, Y.-J.
Wang, C.-H. Lin, J.-H. Cheng, C.-F. Lee, J. Org. Chem. 2012,
77, 6100–6106; b) J.-R. Wu, C.-H. Lin, C.-F. Lee, Chem. Com-
mun. 2009, 4450–4452; c) J.-W. Qiu, X.-G. Zhang, R.-Y. Tang,
P. Zhong, J.-H. Lia, Adv. Synth. Catal. 2009, 351, 2319–2323;
d) A. Correa, M. Carril, C. Bolm, Angew. Chem. 2008, 120,
2922–2925; Angew. Chem. Int. Ed. 2008, 47, 2880–2883.
[11] For rhodium-catalyzed C–S bond formation, see: a) M. Aris-
awa, T. Suzuki, T. Ishikawa, M. Yamaguchi, J. Am. Chem. Soc.
2008, 130, 12214–12215; b) K. Ajiki, M. Hirano, K. Tanaka,
Org. Lett. 2005, 7, 4193–4195; c) C.-S. Lai, H.-L. Kao, Y.-J.
Wang, C.-F. Lee, Tetrahedron Lett. 2012, 53, 4365–4367; d) M.
Arisawa, T. Ichikawa, M. Yamaguchi, Org. Lett. 2012, 14,
5318–5321.
[2] a) Z. Li, D. A. Capretto, R. O. Rahaman, C. He, J. Am. Chem.
Soc. 2007, 129, 12058–12059; b) Z. Shi, Y. Cui, N. Jiao, Org.
Lett. 2010, 12, 2908–2911; c) H.-Y. Thu, W.-Y. Yu, C.-M. Che,
J. Am. Chem. Soc. 2006, 128, 9048–9049; d) B.-J. Li, H.-Y.
Wang, Q.-L. Zhu, Z.-J. Shi, Angew. Chem. 2012, 124, 4014–
4018; Angew. Chem. Int. Ed. 2012, 51, 3948–3952.
[3] a) R. Giri, X. Chen, J.-Q. Yu, Angew. Chem. 2005, 117, 2150–
2153; Angew. Chem. Int. Ed. 2005, 44, 2112–2115; b) T.-S. Mei,
D.-H. Wang, J.-Q. Yu, Org. Lett. 2010, 12, 3140–3143; c) A. R.
Dick, K. L. Hull, M. S. Sanford, J. Am. Chem. Soc. 2004, 126,
2300–2301; d) K. L. Hull, W. Q. Anani, M. S. Sanford, J. Am.
Chem. Soc. 2006, 128, 7134–7135.
[4] For representative reviews, see: a) S. Murai, Activation of Unre-
active Bonds and Organic Synthesis Springer, Berlin, 1999, p.
48; b) G. Dyker, Handbook of C–H Transformations: Applica-
tions in Organic Synthesis Wiley-VCH, Weinheim, Germany,
2005; c) I. A. Mkhalid, J. H. Barnard, T. B. Marder, J. M. Mur-
phy, J. F. Hartwig, Chem. Rev. 2010, 110, 890–931; d) T. W.
Lyons, M. S. Sanford, Chem. Rev. 2010, 110, 1147–1169; e) J. C.
Lewis, R. G. Bergman, J. A. Ellman, Acc. Chem. Res. 2008, 41,
1013–1025; f) Y. J. Park, J. W. Park, C. H. Jun, Acc. Chem. Res.
2008, 41, 222–234; g) M. M. Díaz-Requejo, P. J. Pérez, Chem.
Rev. 2008, 108, 3379–3394; h) D. A. Colby, R. G. Bergman,
J. A. Ellman, Chem. Rev. 2010, 110, 624–655.
[12] C.-H. Cheng, C. Ramesh, H.-L. Kao, Y.-J. Wang, C.-C. Chan,
C.-F. Lee, J. Org. Chem. 2012, 77, 10369–10374.
[13] X. Chen, S.-S. Hao, C. E. Goodhue, J.-Q. Yu, J. Am. Chem.
Soc. 2006, 128, 6790–6791.
[14] Z. Zhao, E. Dimitrijevic, V. M. Dong, J. Am. Chem. Soc. 2009,
131, 3466–3467.
[15] S. Zhang, P. Qian, M. Zhang, M. Hu, J. Cheng, J. Org. Chem.
2010, 75, 6732–6735.
[16] P. Anbarasan, H. Neumann, M. Beller, Chem. Commun. 2011,
47, 3233–3235.
[17] O. Saidi, J. Marafie, A. E. W. Ledger, P. M. Liu, M. F. Mahon,
G. Kociok-Köhn, M. K. Whittlesey, C. G. Frost, J. Am. Chem.
Soc. 2011, 133, 19298–19301.
[5] For representative examples of palladium-catalyzed C–S bond
formation, see: a) T. Migita, T. Shimizu, Y. Asami, J. Shiobara,
Y. Kato, M. Kosugi, Bull. Chem. Soc. Jpn. 1980, 53, 1385– [18] For selected examples, see: a) H. Y. Chen, S. Schlecht, T. C.
1389; b) M. A. Fernández-Rodríguez, Q. Shen, J. F. Hartwig,
J. Am. Chem. Soc. 2006, 128, 2180–2181; c) M. A. Fernández-
Rodríguez, Q. Shen, J. F. Hartwig, Chem. Eur. J. 2006, 12,
7782–7796; d) T. Itoh, T. Mase, Org. Lett. 2004, 6, 4587–4590;
e) M. Sayah, M. G. Organ, Chem. Eur. J. 2011, 17, 11719–
11722.
Semple, J. F. Hartwig, Science 2000, 287, 1995–1997; b) T. Ishi-
yama, J. Takagi, K. Ishida, N. Miyaura, N. Anastasi, J. F. Hart-
wig, J. Am. Chem. Soc. 2002, 124, 390–391; c) T. M. Boller,
J. M. Murphy, M. Hapke, T. Ishiyama, N. Miyaura, J. F. Hart-
wig, J. Am. Chem. Soc. 2005, 127, 14263–14278; d) J. Y. Cho,
C. N. Iverson, M. R. Smith, J. Am. Chem. Soc. 2000, 122,
12868–12869; e) J. Y. Cho, M. K. Tse, D. R. Holmes, E. Ma-
leczka, M. R. Smith, Science 2002, 295, 305–308; f) N. D. Lit-
vinas, P. S. Fier, J. F. Hartwig, Angew. Chem. 2012, 124, 551–
554; Angew. Chem. Int. Ed. 2012, 51, 536–539; g) T. Liu, X.
Shao, Y. Wu, Q. Shen, Angew. Chem. 2012, 124, 555–558; An-
gew. Chem. Int. Ed. 2012, 51, 540–543; h) A. G. Crawford, Z.
Liu, I. A. I. Mkhalid, M.-H. Thibault, N. Schwarz, G. Alcaraz,
A. Steffen, J. C. Collings, A. S. Batsanov, J. A. K. Howard,
T. B. Marder, Chem. Eur. J. 2012, 18, 5022–5035; i) C. W. Lis-
key, X. Liao, J. F. Hartwig, J. Am. Chem. Soc. 2010, 132,
11389–11391; j) T. A. Boebel, J. F. Hartwig, Tetrahedron 2008,
64, 6824–6830.
[6] For representative examples of copper-catalyzed C–S bond for-
mation, see: a) H.-L. Kao, C.-K. Chen, Y.-J. Wang, C.-F. Lee,
Eur. J. Org. Chem. 2011, 1776–1781; b) H.-L. Kao, C.-F. Lee,
Org. Lett. 2011, 13, 5204–5207; c) K. Sahoo, L. Jamir, S. Guin,
B. K. Patei, Adv. Synth. Catal. 2010, 352, 2538–2548; d) C.-
K. Chen, Y.-W. Chen, C.-H. Lin, H.-P. Lin, C.-F. Lee, Chem.
Commun. 2010, 46, 282–284; e) P.-F. Larsson, A. Correa, M.
Carril, P.-O. Norrby, C. Bolm, Angew. Chem. 2009, 121, 5801–
5803; Angew. Chem. Int. Ed. 2009, 48, 5691–5693; f) A. K.
Verma, J. Singh, R. Chaudhary, Tetrahedron Lett. 2007, 48,
7199–7202; g) F. Y. Kwong, S. L. Buchwald, Org. Lett. 2002,
4, 3517–3520; h) C. G. Bates, P. Saejueng, M. Q. Doherty, D.
Venkataraman, Org. Lett. 2004, 6, 5005–5008.
[19] J.-H. Cheng, C.-L. Yi, T.-J. Liu, C.-F. Lee, Chem. Commun.
2012, 48, 8440–8442.
[20] P. S. Herradura, K. A. Pendola, R. K. Guy, Org. Lett. 2000, 2,
2019–2022.
[7] For representative examples of nickel-catalyzed C–S bond for-
mation, see: a) Y. Zhang, K. N. Ngeow, J. Ying, Org. Lett.
2007, 9, 3495–3498; b) V. Percec, J.-Y. Bae, D. H. Hill, J. Org.
Chem. 1995, 60, 6895–6903; c) C. G. Screttas, I. C. Smonou, J.
Organomet. Chem. 1988, 342, 143–152.
Received: February 16, 2013
Published Online: April 18, 2013
3918
www.eurjoc.org
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2013, 3910–3918