A mild and facile synthesis of aryl and alkenyl sulfides via copper-catalyzed deborylthiolation of organoborons with thiosulfonates

Article abstract of DOI:10.1039/c5cc07463k

An efficient deborylthiolation of aryl- and alkenylborons with thiosulfonates has been achieved under mild conditions using a copper catalyst. All steps of the experimental process were free from unpleasant odors. The mild reaction conditions as well as ready availability of boron compounds and thiosulfonates enabled easy access to an array of sulfides, including those bearing sensitive functional groups.

Full text of DOI:10.1039/c5cc07463k

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A mild and facile synthesis of aryl and alkenyl sulfides
via copper-catalyzed deborylthiolation of organoborons
with thiosulfonates
Cite this: DOI: 10.1039/x0xx00000x
Suguru Yoshida,*,a Yasuyuki Sugimura,b Yuki Hazama,a Yoshitake Nishiyama,a
Takahisa Yano,a Shigeomi Shimizu,b and Takamitsu Hosoya*,a
Received 00th xxxxx 201x,
Accepted 00th xxxxx 201x
DOI: 10.1039/x0xx00000x
www.rsc.org/
In the course of our recent studies on aryne chemistry,6 we faced
An efficient deborylthiolation of aryl- and alkenylborons with
thiosulfonates has been achieved under mild conditions using a
copper catalyst. All steps of the experimental process were free
from unpleasant odors. The mild reaction conditions as well as
ready availability of boron compounds and thiosulfonates
enabled easy access to an array of sulfides, including those
bearing sensitive functional groups.
the limitation of the conventional methods for transition-metal-
catalyzed deborylthiolation. For example, an attempt to transform
arylboronic ester 16i,7 to sulfide 2, which we designed as a precursor
of thiolated aryne 3, via the Chan–Lam–Evans-type thiolation5e with
p-toluenethiol resulted in a low efficiency, and desilylated side
products, such as 4 and 5, were also obtained (Scheme 1).
Furthermore, an attempt to prepare 2 via the copper-catalyzed
deborylthiolation of 1 with N-p-tolylthiosuccinimide5a also failed
without producing any of the desired product. These unfavorable
results motivated us to develop a novel method with higher
functional group tolerance that is applicable to the synthesis of a
wider range of sulfides.
Aromatic sulfur compounds are widely used in a variety of
disciplines, including materials science and pharmaceutical
chemistry.1–3 The most popular methods for preparing aromatic
sulfides include the nucleophilic displacement of disulfides with
carbon nucleophiles, such as aryl Grignard reagents, and transition-
metal-catalyzed coupling reactions of aryl halides or boronic acids
with thiols or disulfides.4,5 Although numerous alternative methods
for sulfide synthesis have been developed, reliable aromatic C–S
bond forming reactions are still limited, particularly those applicable
to the synthesis of sulfides bearing sensitive functional groups and
free from unpleasant organosulfurous odors. Here we report an
odorless copper-catalyzed thiolation of boronic acid derivatives with
readily available thiosulfonates that allows for the facile preparation
of diverse sulfides under mild conditions.
We focused on thiosulfonate 66c,8,9 as a readily available, odorless
electrophilic sulfur source to provide sulfides by reaction with
carbon nucleophiles accompanied by the liberation of an odorless
and water-soluble sulfinate (Scheme 2). Considering the good
leaving ability of the sulfonyl group,10 we designed a catalytic
thiolation reaction of boronic acids 7 using thiosulfonate 6. The
hypothetical catalytic cycle included a formal substitution reaction
between thiosulfonate 6 and organometallic species generated from
boronic acid 7 via a metal exchange reaction with or without a base,
affording the desired sulfide 8 and regenerating the catalyst.
Scheme 2 Design of catalytic thiolation of arylboronic acids 7 using
thiosulfonate 6.
After extensive screening of the reaction conditions, we found that
a copper salt in the presence of a weak base efficiently catalyzed the
thiolation of phenylboronic acid (7a) with S-p-tolyl p-
toluenethiosulfonate (6a) at room temperature to afford sulfide 8a
(Table 1). Initial screening for the metal salt indicated that copper
salts, including copper sulfate, were most suitable for the desired
Scheme 1 The Chan–Lam–Evans-type thiolation of arylboronic ester
1.
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DOI: 10.1039/C5CC07463K
transformation (entries 1–5). Further studies showed that addition of Table 2 Thiolations of various boronic acids 7 with thiosulfonate 6aa
a base was quite effective (entries 6–10). In particular, the use of a
weak base, such as sodium bicarbonate or cesium fluoride, in
combination with copper sulfate dramatically improved the reaction
efficiencies to afford 8a in excellent yields (entries 9 and 10). On the
other hand, reactions in the presence of potassium tert-butoxide or
potassium carbonate resulted in low efficiencies at room tem-
perature (entries 6 and 7), while heating at 50 °C moderately
improved the yield of 8a for the latter case (entry 8). It is worth
noting that the thiolation was achieved free from unpleasant odors
during all steps of the experimental process.
CuSO4 (5 mol %)
NaHCO3 (2.0 equiv)
p-tol
p-tol
S
S
R
p-tol
RB(OH)2
+
S
8
MeOH
rt, 24 h
O
7
O
(1.5 equiv)
6a
MeO2C
MeO
Br
p-tol
p-tol
p-tol
S
S
S
83%, 8b
98% (94%)b, 8c
95%, 8d
OH
OMe
S
p-tol
p-tol
p-tol
S
OHC
S
S
Table 1 Optimization of the reaction conditions
73%, 8ec
93%, 8fc
74%, 8g
p-tol
catalyst (5 mol %)
additive (2.0 equiv)
Me
S
S
Boc
N
+
O
p-tol
MeOH
rt, 24 h
B(OH)2
S
O
p-tol
p-tol
Me
p-tol
S
S
S
7a
6a
8a
97%, 8hc
85%, 8ic
0%, 8j
(1.5 equiv)
aIsolated yields. bA yield when the reaction was performed using 10 mmol of
6a (2.8 g) and 15 mmol of 7c (2.7 g) in parentheses. cK2CO3 (2.0 equiv) was
used instead of NaHCO3, and the reaction was performed at 50 °C for 24 h.
Entry
1
Catalyst
Pd(OAc)2
Additive
––
Yield of 8a (%)a
2
Ni(OAc)2
CuOAc
––
––
0
16
2
3
Cu(OAc)2
CuSO4
CuSO4
CuSO4
CuSO4
CuSO4
CuSO4
––
––
KOt-Bu
K2CO3
K2CO3
NaHCO3
CsF
17
16
11
4
5
6
7
7
8b
9
53
quantc
98
10
Scheme 3 Copper-catalyzed deborythiolation of arylboronic ester 1
with thiosulfonate 6a.
aYields were determined based on GC analyses unless otherwise noted.
bThe reaction was performed at 50 °C. cIsolated yield.
The optimized conditions were applicable to thiolations of a broad
range of boronic acids 7 using thiosulfonate 6a, with a slight
modification of the conditions depending on the substrates (Table 2).
Thiolations of para-substituted phenyl boronic acid bearing an
electron-donating methoxy group or an electron-withdrawing ester
moiety proceeded efficiently to afford sulfide 8b or 8c, respectively,
in high yields. Furthermore, the reaction was scalable, as
successfully demonstrated in the gram-scale synthesis of sulfide 8c
without exposure to unpleasant odors during the synthetic process.
ortho-Bromophenylboronic acid was also thiolated efficiently with
6a to yield sulfide 8d without diminishing the bromo group. Sulfide
8e having an unprotected phenolic hydroxy group was obtained in
high yield from 2-hydroxyphenylboronic acid using potassium
carbonate instead of sodium bicarbonate and heating at 50 °C, which
effectively suppressed undesired deborylprotonation of the boronic
acid. Thiolation of borylbenzaldehyde also proceeded efficiently to
afford sulfide 8f, leaving the electrophilic formyl group untouched.
Heteroaromatic boronic acids also served as good substrates to
provide thienyl or indolyl sulfides 8g or 8h in high yields. While
alkenylboronic acid was thiolated smoothly to afford alkenyl sulfide
8i, thiolation of methylboronic acid did not proceed under any of the
conditions examined. The mild reaction conditions also enabled the
deborylthiolation of borylated aryne precursor 1 to afford desired 2
in an excellent yield without producing desilylated side products
(Scheme 3). These results clearly demonstrated the high functional
group tolerance of this method.
Table 3 Thiolations of boronic acid 7c with various thiosulfonates 6
CuSO4 (5 mol %)
NaHCO3 (2.0 equiv)
R
S
Ar
R
ArB(OH)2
+
S
8
S
MeOH
rt, 24 h
O
R
7c
O
(1.5 equiv)
6
Ar = 4-(MeO2C)C6H4
Entry
Thiosulfonate 6
Product 8
Yield (%)a
82
OMe
Cl
OMe
O
O
S
1
Ar
S
S
8k
MeO
Cl
6b
Cl
O
O
O
S
Ar
2
3
4
93
94
S
S
8l
6c
BzHN
O
S
Ar
S
S
NHBz
NHBz
6d
8m
Me
O
Me
O
S
O
Ar
93
93
S
O
S
S
8n
O
6e
Me
O
O
Ar
Ph
Ph
S
5
S
Ph
8o
6f
aIsolated yield.
The ready availability of various thiosulfonates also gives the
method a distinctive advantage. For example, thiosulfonates such as
6b–6f, which were easily prepared by selective oxidation of
symmetric disulfides, were applicable to the thiolation, as
demonstrated in the reaction with boronic acid 7c (Table 3). para-
Methoxyphenyl- and para-chlorophenylthiolated products 8k and 8l
were obtained in high yields using thiosulfonates 6b and 6c,
respectively (entries 1 and 2). The reaction with ortho-substituted
substrate 6d also proceeded smoothly to afford sulfide 8m in an
excellent yield (entry 3). Furyl- and benzylthiolation using
2 | Chem. Commun., 201x, 00, 1-4
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thiosulfonates 6e and 6f efficiently afforded sulfides 8n and 8o, re-
spectively, showing the broad scope of the method (entries 4 and 5).
Table 4 Sulfide syntheses from alkyl halides 9, potassium thiosulfonate 10,
and boronic acid 7c
Yield
(%)a
Yield
(%)a
Entry
1
9
11
8
94
86
77
97
2
3b
83
82
4
5
6
7
88
70
95
88
89
94
99
91
Scheme 4 Formal C–H thiolation of aryl esters 12a–12c. Yields are
those of isolated products. aL = Silica-SMAP. bSee, ref. 15a.
The combined use of the methods developed in this study and a
multi-component coupling based on the aryne chemistry17 enabled
the facile and efficient preparation of sulfides that were previously
difficult to access. For example, the sequential assembly of various
modules, such as iodomethane-d3 (9j), potassium thiosulfonate (10),
borylated aryne precursor 1,6i and morpholine, allowed to furnish
1,3,5-trisubstituted aryl sulfide 15 in high efficiency (Scheme 5).
The thiolated aryne precursors, such as 16, would serve as platform
molecules for preparing diverse highly functionalized aryl sulfides
through the generation of arynes, such as 17, and their reactions with
various arynophiles and nucleophiles.6,17
8
9
92
90
74
86
aIsolated yield. K2CO3 (2.0 equiv) was used instead of NaHCO3, and the
reaction was performed at 50 °C for 24 h.
b
The use of readily available alkyl thiosulfonates further expanded
the scope of the reaction. Nucleophilic substitution reactions of alkyl
halides 9a–9i with potassium p-toluenethiosulfonate (10)11
efficiently provided the corresponding alkyl thiosulfonates 11a–11i
in high yields (Table 4). Subsequent copper-catalyzed thiolation of
boronic acid 7c with these thiosulfonates also proceeded efficiently,
affording alkyl aryl sulfides 8p–8x in high yields. These results
clearly demonstrated the wide functional group tolerance of this two-
step transformation, as not only the simple alkyl halides 9a and 9b
but also the sterically-hindered secondary alkyl halide 9c and allyl
bromide (9d) participated in the sulfide synthesis (entries 1–4).
Alkyl halides bearing an unprotected hydroxy group (entry 5), other
halides (entries 6–9), or ether moieties (entries 8 and 9) also served
as good substrates, efficiently affording the corresponding alkyl aryl
sulfides without damaging these functionalities. It is worth noting
that the reagent 10 acted overall as a “+S–” equivalent in this
transformation.
Scheme 5 Synthesis of 1,3,5-trisubstituted aryl sulfide 15 via formal
C–H thiolation of aryne precursor 18. Yields are those of isolated
products. aSee, ref. 6i.
A formal C–H thiolation12,13 of simple aromatic compounds was
achieved via iridium-catalyzed C–H borylation of arenes,14,15
followed by the copper-catalyzed thiolation, enabling facile access to
an array of sulfides (Scheme 4). For example, ortho-selective
borylation of methyl benzoate (12a) using Ir–Silica-SMAP
catalyst15a and subsequent deborylthiolation with 6c afforded sulfide
In summary, we have developed a simple, efficient, and odorless
deborylthiolation method of organoboron compounds with
13a in high overall yield (Scheme 4A). Hydrolysis of 13a followed thiosulfonates catalyzed by copper. The ready availability of diverse
by acidic cyclization furnished thioxanthone 14, which is a key
intermediate for various antipsychotics.16 This approach enabled the
double thiolation of ortho- and meta-phthalate diester 12b and 12c,
boronic acid derivatives and thiosulfonates, as well as the mild
reaction conditions allowed us to prepare a variety of sulfides,
including those with sensitive functionalities. Further studies are
easily providing di(sulfanyl) diesters 13b or 13c, respectively currently underway in our laboratory.
(Schemes 4B and 4C).
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This work was supported by the Platform for Drug Discovery,
Informatics, and Structural Life Science from MEXT and AMED,
Japan; JSPS KAKENHI Grant Numbers 15H03118, 26560443 (T.H.),
and 26350971 (S.Y.).
7
8
Notes and references
aLaboratory of Chemical Bioscience, Institute of Biomaterials and
Bioengineering, Tokyo Medical and Dental University, 2-3-10 Kanda-
Surugadai, Chiyoda-ku, Tokyo 101-0062, Japan.
bDepartment of Pathological Cell Biology, Medical Research Institute,
Tokyo Medical and Dental University, 1-5-45 Yushima, Bunkyo-ku,
Tokyo 113-8510, Japan
9
*E-mail: s-yoshida.cb@tmd.ac.jp; thosoya.cb@tmd.ac.jp
†
Electronic Supplementary Information (ESI) available: Experimental
procedures and characterization data including copies of NMR spectra.
See DOI: 10.1039/c000000x/
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4 | Chem. Commun., 201x, 00, 1-4
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DOI: 10.1039/C5CC07463K
Graphical abstract for the contents page
xxx
A mild and facile synthesis of aryl and alkenyl
sulfides via copper-catalyzed deborylthiolation of
organoborons with thiosulfonates
Suguru Yoshida,* Yasuyuki Sugimura, Yuki Hazama,
Yoshitake Nishiyama, Takahisa Yano, Shigeomi
Shimizu and Takamitsu Hosoya*
A simple, efficient, and oderless deborylthiolation of aryl- and
alkenylborons with thiosulfonates has been achieved under mild
conditions using a copper catalyst.
This journal is © The Royal Society of Chemistry 201x
Chem. Commun., 201x, 00, 1-4 | 5