An odorless, one-pot synthesis of thioesters from organic halides, thiourea and benzoyl chlorides in water

Article abstract of DOI:10.1002/adsc.201201059

Thioesterification can be realized via an odorless, one-pot reaction through the in situ generation of S-alkylisothiouronium salts from organic halides and thiourea in aqueous Triton X-100 (TX100) micelles. The protocol is free of foul-smell thiols and or

Full text of DOI:10.1002/adsc.201201059

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DOI: 10.1002/adsc.201201059
An Odorless, One-Pot Synthesis of Thioesters from Organic
Halides, Thiourea and Benzoyl Chlorides in Water
Guo-ping Lua and Chun Caia,*
a
Chemical Engineering College, Nanjing University of Science & Technology, Nanjing, Jiangsu 210094, Peopleꢀs Republic
of China
Fax : (+86)-25-8431-5030; phone: (+86)-25-8431-5514; e-mail: c.cai@mail.njust.edu.cn
Received: December 8, 2012; Revised: March 3, 2013; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201201059.
Abstract: Thioesterification can be realized via an
odorless, one-pot reaction through the in situ gener-
ation of S-alkylisothiouronium salts from organic
halides and thiourea in aqueous Triton X-100
(TX100) micelles. The protocol is free of foul-smell
thiols and organic solvents, and operates under mild
conditions, thereby offering considerable potential
for applications in organic synthesis.
alent precursors can react with aldehydes by radical-
mediated couplings,[9] and thioesters can also be syn-
thesized via thioaroylate ions generated in situ from
acyloxyphosphonium salts and benzyltriethylammoni-
um tetrathiomolybdate.[10] Nevertheless, these odor-
less procedures also encounter disadvantages, such as
pre-preparation of disulfides from thiols, use of non-
commercial or high-cost reagents.
Recently, several attempts have also been made for
the formation of thioethers through the in situ genera-
tion of S-alkylisothiouronium salts in place of thiols
which are, in turn, formed from organic halides and
thiourea.[11] Ideally, the thioesterification reaction
would be carried out in water as the only medium by
an odorless method.[12] Along this line, we describe
here an odorless, one-pot process for the synthesis of
Keywords: S-alkylisothiouronium salts; green
chemistry; micelles; multicomponent reactions;
thioACHTUNGTRENNUNGesterification; water chemistry
Thioesters are a class of important synthetic inter- thioesters using thiourea as the sulfur source in water,
mediates in organic synthesis, that are applied for avoiding the pre-generation of thiols with thiourea
peptide coupling,[1] acyl transfer,[2] protecting groups and organic halides and the use of organic solvents as
for thiols,[3] and also as coupling partners in organo- in the previous literature[13] (Scheme 1).
metallic reactions.[4] They are also key intermediates
It is common knowledge that carboxylic acid hal-
in various biological systems,[5] and are widely present ides are quite water-sensitive (leading to rapid hydrol-
in a number of biologically active and medicinal ysis), so it seems virtually impossible to perform the
agents.[6] Traditionally, thiols[7] or thiocarboxylates[8] reactions of carboxylic acid halides in water. Adding
are required for the synthesis of such versatile com- surfactants in water to form micelles may decrease
pounds. These methodologies, however, suffer from the kinetics of hydrolysis by preventing and/or hinder-
limitations such as difficulties encountered in han- ing acyl halides from encountering the water mole-
dling the foul-smelling thiols and thioacids. In order cules.[14] As a starting point, we performed a test reac-
to eliminate these problems, several odorless proto- tion of thiourea, benzyl chloride and 4-toluoyl chlo-
cols have been reported. Disulfides as the thiol equiv- ride using K2CO3 as the base in 2 wt% SDS aqueous
Scheme 1. The synthesis of thioesters using thiourea as the sulfur source.
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Table 1. Optimization of the reaction conditions.[a]
chloride or benzyl chloride could go to completion at
308C to provide the desire products (1a–d). A slight
heating (608C) was required when benzyl halides with
electron-withdrawing groups were used (1e–h). Pri-
mary alkyl halides could also be applied to the reac-
tion successfully (1i–k). Ethyl bromoacetate and (E)-
1,3-dichloroprop-1-ene proved to be more efficient re-
actants than primary alkyl halides, so the final prod-
ucts (1l–n) could be formed at 308C.
2-Bromo-1,1-diethoxyethane could react with thio-
urea and benzoyl chloride to provide 1o with a moder-
ate yield under mild heating conditions. Likewise, the
reactions of thiourea, benzoyl chloride and dibro-
mides occurred to afford the corresponding dibenzo-
thioates (1p, 1q) under identical conditions. However,
more steric hindered alkyl bromides (such as cyclo-
hexyl bromide, tert-butyl bromide) failed to afford the
desired products. The hydrolysis rate of other acyl
chlorides (such as propionyl chloride, 2-chloroacetyl
chloride) in water is too fast for them to react with
the S-benzylisothiouronium salts formed in situ from
thiourea and benzyl chloride.
S-Prop-2-ynyl benzothioate 1r generated through
a one-pot process from 3-bromoprop-1-yne, thiourea
and benzoyl chloride, could be attached to a peptido-
mimetic by copper-catalyzed “click” reaction
(Scheme 2).[15] Furthermore, the thioester 3 could be
readily transformed into a more versatile SH group
under mild reaction conditions for the further struc-
ture modification.
To further highlight the potential of this methodol-
ogy, thioester 1t, a crucial intermediate en route to 4
which displays potent anti-HIV properties in human
macrophages, was synthesized by the one-pot, odor-
less procedure in water (Scheme 3), rather than by
use of the foul-smelling thiol and an organic solvent
as in the previous reports.[5c,d]
Entry
Surfactant
Base
Yield [%][b]
1
2
3
4
5
6
7
8
SDS[c]
SDS
–
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
NaOH
NEt3
98[d]
82
63
TX100[e]
CTAB[g]
Tween60[h]
Span80[i]
TPGS-750-M[j]
TX100
TX100
TX100
TX100
87 (78)[f]
79
71
75
80
74
9
10
11
12
78
–
n.r.
K2CO3
82[f,k]
[a]
Reaction conditions: 4-toluoyl chloride 0.5 mmol, thiour-
ea 1.0 mmol, benzyl chloride 1.0 mmol, K2CO3 1.5 mmol,
2 wt% solution of aqueous surfactant 1.0 mL, 4 h, 308C.
The yield is determined by GC.
Sodium dodecyl sulfate.
The reaction is carried out at 608C for 8 h.
t-Octylphenoxypolyethoxyethanol.
Isolated yield.
Cetyltrimethylammonium bromide.
Polyoxyethylene (20) sorbitan monostearate.
Sorbitane monooleate.
Polyethanyl-a-tocopherylsuccinate.
[b]
[c]
[d]
[e]
[f]
[g]
[h]
[i]
[j]
[k]
Reaction conditions: 4-toluoyl chloride 10 mmol, thiourea
20 mmol, 4-tolyl chloride 20 mmol, K2CO3 30 mmol, re-
action medium 10 mL, 8 h, 308C.
An initial attempt was also made to employ benzoic
solution at 608C for 8 h. The reaction proceeded well anhydride in the protocol. Although the desired thio-
and the desired thioester 1a was obtained in 98% esters were provided by the reaction of a variety of
yield (Table 1, entry 1). The yield is also satisfactory benzyl halides, thiourea and benzoic anhydride in
(82%) when the reaction is conducted at 308C for 4 h 2 wt% TX100/H2O at 808C for 8 h, low yields and un-
(entry 2). The use of surfactant is crucial for the reac- desired symmetrical thioethers were noted owing to
tion, and the yield dropped from 82% to 63% in the the lower reactivity of benzoic anhydride compared
absence of a surfactant (entry 2 vs. entry 3). After to benzoyl chloride. The reactions of benzyl chlorides,
screening the different surfactants and bases, the com- thiourea and benzenesulfonyl chloride were carried
bination of K2CO3 and 2 wt% TX100 aqueous solu- out under likewise identical conditions. Although two
tion emerged as the best selection (entry 4). No reac- S-benzyl benzenesulfonothioates (5a, 5b) were syn-
tion took place without a base (entry 11). In order to thesized successfully (Scheme 4), no desired product
show the possibility for large-scale operation, we also was obtained using benzyl chlorides with electron-
scaled up the reaction to 10 mmol, and the reaction withdrawing groups as the reactants.
proceeded well with 82% yield of the desired product
(entry 12).
Finally, a proposed mechanism for the reaction was
also illustrated in Scheme 5. We believe that this reac-
With the optimized conditions in hand, a series of tion proceeds by the in situ generation of an S-alkyli-
benzoyl chlorides and different benzyl chlorides were sothiouronium salt (not S-benzoylisothiouronium
chosen to establish the scope and generality of the salts[16]) which is hydrolyzed in the reaction mixture
method (Table 2). The reactions of 4-methylbenzyl to produce a thiolate moiety and urea.[11] Then the
2
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An Odorless, One-Pot Synthesis of Thioesters from Organic Halides, Thiourea and Benzoyl Chlorides
Table 2. The reactions of various organic halides, thiourea and benzoyl chlorides in water.[a,b]
[a]
Reaction conditions: organic halide 0.5 mmol, thiourea 1.0 mmol, benzoyl chloride 1.0 mmol, K2CO3 1.5 mmol, 2 wt%
TX100 aqueous solution 1.0 mL, 8 h.
Isolated yield.
Reaction conditions: dibromide compound 0.5 mmol, thiourea 2.0 mmol, benzoyl chloride 2.0 mmol, K2CO3 3.0 mmol,
[b]
[c]
2 wt% TX100 aqueous solution 1.5 mL, 8 h.
Scheme 2. The thioester 1r is attached to a peptidomimetic by a “click” reaction.
generated thiolate ion which is a synthetic equivalent
of thiol and an odorless moiety may react with benzo- performed in water through the one-pot, three-com-
yl chloride to form the final product. ponent reaction of organic halides, thiourea and ben-
In summary, the preparation of thioesters can be
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Scheme 3. A potential application of the protocol in organic synthesis.
Scheme 4. The reactions of benzyl chlorides, thiourea and benzenesulfonyl chloride in water.
Scheme 5. A proposed mechanism for the thioesterification resaction of organic halides, thiourea and benzoyl chlorides.
zoyl chlorides. The non-ionic surfactant Triton X-100 product. The extent of conversion was determined by GC.
Further column chromatography on silica gel afforded the
desired pure product.
that self-assembles in water to form micelles proves
to diminish the hydrolysis of benzoyl chlorides. The
newly developed procedure is free of organic solvents
and foul-smelling thiols during these reactions, and
work-up entails only an in-flask extraction with a mini-
mal amount of a single, recoverable organic solvent,
making it more environmentally friendly and suitable
General Procedure for the Synthesis of Thioesters
from Benzyl Halides, Thiourea and Benzoic
Anhydride or Benzenesulfonyl Chloride in Water
for large-scale operations. In addition, benzenesulfon- A mixture of benzyl halide (0.5 mmol), thiourea (1.0 mmol),
benzoic anhydride or benzenesulfonyl chloride (1.0 mmol)
and K2CO3 (1.5 mmol) in 2 wt% aqueous Triton X-100 solu-
tion (1.0 mL) was stirred at 808C for 8 h. Upon completion,
the reaction mixture was diluted with EtOAc (4.0 mL), fil-
tered through a bed of silica gel layered over Celite, The
volatiles were removed under vacuum to afford the crude
product. The extent of conversion was determined by GC.
Further column chromatography on silica gel afforded the
desired pure products.
yl chloride and benzoic anhydride in place of benzoyl
chlorides can also be applied in the protocol.
Experimental Section
General Procedure for the Synthesis of Thioesters
from Organic Halides, Thiourea and Benzoyl
Chlorides in Water
A
mixture of organic halide (0.5 mmol), thiourea
Characterization Data of New Compounds
(1.0 mmol), benzoyl chloride (1.0 mmol) and K2CO3
(1.5 mmol) in 2 wt% aqueous Triton X-100 solution
(1.0 mL) was stirred at 308C or 608C for 8 h. Upon comple-
tion, the reaction mixture was diluted with EtOAc (4.0 mL),
filtered through a bed of silica gel layered over Celite, The
volatiles were removed under vacuum to afford the crude
S-4-Fluorobenzyl benzothioate (1e): 1H NMR (500 MHz,
CDCl3): d=4.31 (s, 2H), 7.00–7.04 (m, 2H), 7.36–7.39 (dd,
J=8.5, 5.5 Hz, 2H), 7.46–7.49 (m, 2H), 7.58–7.61 (m, 1H),
7.98–8.00 (m, 2H); 13C NMR (125 MHz, CDCl3): d=31.6,
114.4, 114.6, 126.3, 127.7, 129.6, 129.7, 132.4, 132.6, 135.7,
4
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An Odorless, One-Pot Synthesis of Thioesters from Organic Halides, Thiourea and Benzoyl Chlorides
160.1, 162.0, 190.2; MS (ESI): m/z=246; anal. calcd. for
C14H11FOS: C 68.27, H 4.50%; found: C 68.51, H 4.73%.
S-4-Cyanobenzyl benzothioate (1f): 1H NMR (500 MHz,
CDCl3): d=4.34 (s, 2H), 7.46–7.52 (m, 4H), 7.59–7.63 (m,
3H), 7.61–7.98 (m, 2H); 13C NMR (125 MHz, CDCl3): d=
31.8, 110.2, 117.7, 126.4, 127.8, 128.7, 131.4, 132.8, 135.4,
142.5, 189.5; MS (ESI): m/z=253; anal. calcd. for
C15H11NOS: C 71.12, H 4.38, N 5.53%; found: C 70.91, H
4.73, N 5.23%.
C37H35N5O3S: C 70.56, H 5.60, N 11.12%; found: C 70.37, H
5.81, N 11.38%.
S-4-Methylbenzyl benzenesulfonothioate (5b): 1H NMR
(500 MHz, CDCl3): d=2.31 (s, 3H), 4.17 (s, 2H), 7.01 (d,
J=8.0 Hz, 2H), 7.07 (d, J=8.0 Hz, 2H), 7.48–7.51 (m, 2H),
7.57–7.61 (m, 1H), 7.90–7.92 (m, 2H); 13C NMR (125 MHz,
CDCl3): d=20.1, 34.4, 125.4, 127.8, 128.3, 131.4, 132.0, 136.4,
140.9, 167.3; MS (ESI): m/z=278; anal. calcd. for
C14H14O2S2: C 60.40, H 5.07%; Found: C 60.63, H 4.85%.
S-Cyclohexylmethyl
benzothioate
(1j):
1H NMR
(500 MHz, CDCl3): d=1.01–1.09 (m, 2H), 1.16–1.31 (m,
3H), 1.54–1.61 (m, 1H), 1.66–1.69 (m, 1H), 1.73–1.77 (m,
2H), 1.87–1.90 (m, 2H), 3.01 (d, J=6.5 Hz, 2H), 7.56–7.59
(t, J=7.5 Hz, 1H), 8.00 (dd, J=8.0, 1.0 Hz, 2H); 13C NMR
(125 MHz, CDCl3): d=25.0, 25.3, 31.6, 34.9, 37.1, 126.2,
127.6, 132.2, 136.3, 191.2; MS (ESI): m/z=234; anal. calcd.
for C14H18OS: C 71.75, H 7.74%; found: C 71.56, H 7.43%.
Acknowledgements
We thank the China North Industries Coporation (NORIN-
CO 00402040103) for financial support.
S-1H,1H,2H,2H-perfluorooctyl
benzothioate
(1k):
1H NMR (500 MHz, CDCl3): d=2.47–2.57 (m, 2H), 3.30–
3.33 (m, 2H), 7.48–7.51 (t, J=7.5 Hz, 2H), 7.60–7.64 (t, J=
7.5 Hz, 1H), 7.97–7.99 (dd, J=8.0, 1.0 Hz, 2H); 13C NMR
(125 MHz, CDCl3): d=19.1, 30.8, 126.3, 127.8, 132.8, 135.5,
189.8; 19F NMR (470 MHz, CDCl3): d=À126.2, À123.4,
À122.9, À121.9, À114.5, À80.9; MS (ESI): m/z=484; anal.
calcd. for C15H9F13OS: C 37.20, H 1.87%; found: C 36.98, H
1.78%.
References
[1] a) P. E. Dawson, T. W. Muir, C. I. Lewis, S. B. H. Kent,
Science 1994, 266, 776–779; b) C. Ozawa, H. Katayama,
H. Hojo, Y. Nakahara, Org. Lett. 2008, 10, 3531–3533;
c) R. M. Schmaltz, S. R. Hanson, C.-H. Wong, Chem.
Rev. 2011, 111, 4259–4307.
[2] a) T. Mukaiyama, M. Araki, H. Takei, J. Am. Chem.
Soc. 1973, 95, 4763–4765; b) R. J. Anderson, C. A. Hen-
rick, L. D. Rosenblum, J. Am. Chem. Soc. 1974, 96,
3654–3655.
[3] C. Fowelin, B. Schꢂpbach, A. Terfort, Eur. J. Org.
Chem. 2007, 1013–1017.
[4] a) J. M. Villalobos, J. Srogl, L. S. Liebeskind, J. Am.
Chem. Soc. 2007, 129, 15734–15735; b) K. Kunchi-
thapatham, C. C. Eichman, J. P. Stambuli, Chem.
Commun. 2011, 47, 12679–12681.
Ethyl 2-(2-fluorobenzoylthio)acetate (1m): 1H NMR
(500 MHz, CDCl3): d=1.31–1.34 (t, J=7.0 Hz, 3H), 3.90 (s,
2H), 4.23–4.28 (q, J=7.0 Hz, 2H), 7.18–7.22 (m, 1H), 7.25–
7.28 (m, 1H), 7.91–7.95 (td, J=7.5, 1.5 Hz, 1H); 13C NMR
(125 MHz, CDCl3): d=13.1, 30.8, 68.9, 116.1, 123.4, 128.9,
133.9, 158.7, 160.8, 167.6, 180.6; 19F NMR (470 MHz,
CDCl3): d=À109.7; MS (ESI): m/z=242; anal. calcd. for
C11H11FO3S: C 54.53, H 4.58%; found: C 54.76, H 4.69%.
(E)-S-3-Chloroallyl
benzothioate
(1n):
1H NMR
(500 MHz, CDCl3): d=3.73–3.75 (dd, J=7.5, 1.5 Hz, 2H),
5.99–6.04 (dt, J=13.0, 8.0 Hz, 1H), 6.31–6.34 (dt, J=13.5,
1.0 Hz, 1H), 7.46–7.50 (t, J=7.0 Hz, 2H), 7.59–7.62 (t, J=
7.5 Hz), 7.97 (d, J=7.5 Hz, 1H); 13C NMR (125 MHz,
CDCl3): d=28.0, 120.6, 126.3, 127.5, 127.7, 132.6, 135.7,
189.8; MS (ESI): m/z=212; anal. calcd. for C10H9ClOS: C
56.47, H 4.26%; found: C 56.72, H 4.04%.
[5] a) H. Spies, B. Noll, S. Noll, M. Findeisen, P. Brust, R.
Syhre, R. Berger, Bioorg. Med. Chem. 2002, 10, 3523–
3528; b) B. ter Horst, B. L. Feringa, A. J. Minnaard,
Chem. Commun. 2007, 489–491; c) M. Smietana, P.
Clayette, P. Mialocq, J.-J. Vasseur, J. Oiry, Bioorg.
Chem. 2008, 36, 133–140; d) J. Oiry, P. Mialocq, J.-Y.
Puy, P. Fretier, N. Dereuddre-Bosquet, D. Dormont, J.-
L. Imbach, P. Clayette, J. Med. Chem. 2004, 47, 1789–
1795; e) P. Blakskjær, B. Høj, D. Riber, T. Skrydstrup,
J. Am. Chem. Soc. 2003, 125, 4030–4031.
[6] a) G. S. Hamilton, Y.-Q. Wu, D. C. Limburg, D. E. Wil-
kinson, M. J. Vaal, J.-H. Li, C. Thomas, W. Huang, H.
Sauer, D. T. Ross, R. Soni, Y. Chen, H. Guo, P. Ho-
worth, H. Valentine, S. Liang, D. Spicer, M. Fuller, J. P.
Steiner, J. Med. Chem. 2002, 45, 3549–3557; b) P. Metz-
ner, A. Thuillier, in: Sulfur Reagents in Organic Synthe-
sis, Academic Press, New York, 1994; c) A. Nudelman,
in: The Chemistry of Optically Active Sulfur Com-
pounds, Gordon and Breach, New York, 1984; d) C.
Chatgilialoglu, K. D. Asmus, in: Sulfur-Centered Reac-
tive Intermediates in Chemistry and Biology, Springer,
New York, 1991.
S-2,2-Diethoxyethyl
benzothioate
(1o):
1H NMR
(500 MHz, CDCl3): d=1.25–1.27 (t, J=7.0 Hz, 6H), 3.33 (d,
J=5.5 Hz, 2H), 3.61–3.65 (m, 2H), 3.72–3.78 (m, 2H), 4.62
(t, J=5.5 Hz, 1H), 7.48–7.49 (t, J=7.5 Hz, 2H), 7.58–7.61 (t,
J=7.5 Hz, 1H), 8.01 (d, J=7.5 Hz, 2H); 13C NMR
(125 MHz, CDCl3): d=14.2, 31.3, 81.6, 100.5, 126.3, 127.6,
128.0, 132.5, 135.9, 190.6; MS (ESI): m/z=254; anal. calcd.
for C13H18FO3S: C 61.39, H 7.13%; found: C 61.07, H
7.39%.
S-(1-{4-[(2-{cyclohexylamino}-2-oxo-1-phenylethyl)-
A
methyl
1
benzothioate (3): H NMR (500 MHz, CDCl3): d=1.06–1.17
(m, 3H), 1.32–1.41 (m, 2H), 1.58–1.71 (m, 3H), 1.91–1.99
(m, 2H), 3.86–3.93 (m, 1H), 4.41 (s, 2H), 5.72 (br, 1H), 6.20
(s, 1H), 7.02 (br, 5H), 7.26 (br, 5H), 7.44–7.52 (m, 6H),
7.57–7.60 (t, J=7.0 Hz, 1H), 7.93–7.95 (m, 3H); 13C NMR
(125 MHz, CDCl3): d=22.7, 23.7, 23.8, 24.5, 31.8, 47.9, 65.7,
118.3, 119.6, 126.3, 126.5, 127.6, 127.7, 129.1, 129.3, 129.4,
132.7, 133.6, 135.5, 136.1, 139.9, 144.4, 167.4, 168.8, 170.1,
190.4; MS (ESI): m/z=628 (MÀH)À; anal. calcd. for
[7] a) B. C. Ranu, R. Jana, Adv. Synth. Catal. 2005, 347,
1811–1818; b) S. Iimura, K. Manabe, S. Kobayashi,
Chem. Commun. 2002, 94–95; c) T. Uno, T. Inokuma,
Y. Takemoto, Chem. Commun. 2012, 48, 1901–1903;
d) S. Magens, B. Plietker, Chem. Eur. J. 2011, 17, 8807–
Adv. Synth. Catal. 0000, 000, 0 – 0
ꢁ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
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Guo-ping Lu and Chun Cai
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8809; e) N. Iranpoor, H. Firouzabadi, D. Khalili, S. Mo-
tevalli, J. Org. Chem. 2008, 73, 4882–4887; f) Y. Ka-
geyama, S. Murata, J. Org. Chem. 2005, 70, 3140–3147;
g) H. Cao, L. McNamee, H. Alper, J. Org. Chem. 2008,
73, 3530–3534; h) E. A. Castro, Chem. Rev. 1999, 99,
3505–3524.
Catal. 2012, 354, 839–845; e) G.-P. Lu, C. Cai, Green
Chem. Lett. Rev. 2012, 5, 481–485.
[12] a) P. T. Anastas, J. C. Warner, in: Green Chemistry:
Theory and Practice, Oxford University Press, Oxford,
UK, 1998; b) P. T. Anastas, T. Williamson, in: Green
Chemistry, Frontiers in Benign Chemical Synthesis and
Process, Oxford University of Press, Oxford, UK, 1998;
c) C. Capello, U. Fischer, K. Hungerbuhler, Green
Chem. 2007, 9, 927–934; d) P. G. Jessop, Green Chem.
2011, 13, 1391–1398.
[13] a) A. M. Kuliev, Y. M. Sultanov, I. A. Aliev, N. A.
Mekhraliev, Katalit. Prevrashcheniya Organ. Soedin.
Baku 1981, 51–55; Chem. Abstr. 1983, 98, 178845;
b) G. G. Verba, A. A. Abduvakhabov, A. G. Dobren’
kov, Uzb. Khim. Zh. 1986, 18–21; Chem. Abstr. 1987,
107, 77724; c) S. Voltrova, J. Srogl, Eur. J. Org. Chem.
2008, 1677–1679; d) M. Ojika, Y. Inukai, Y. Kito, M.
Hirata, T. Iizuka, R. Fudou, Chem. Asian J. 2008, 3,
126–133.
[14] a) H.-Y. Tian, Y.-J. Chen, D. Wang, C.-C. Zeng, C.-J.
Li, Tetrahedron Lett. 2000, 41, 2529–2532; b) L. Chen,
C.-J. Li, Org. Lett. 2004, 6, 3151–3153.
[15] a) T.-F. Niu, C. Cai, L. Yi, Helv. Chim. Acta 2012, 95,
87–99; b) T.-F. Niu, L. Gu, L. Wang, W.-B. Yi, C. Cai,
Eur. J. Org. Chem. 2012, 6767–6776.
[16] N-Carbamothioylbenzamide (not S-benzoylisothiouro-
nium salt) is normally formed by the reaction of benzo-
yl chloride and thiourea, see: S. Andreae, E. Schmitz, J.
Prakt. Chem. 1987, 329, 1008–1014.
[8] a) E. Block, E. V. Dikarev, R. S. Glass, L. B. Jin, X. Li,
S.-Z. Zhang, J. Am. Chem. Soc. 2006, 128, 14949–
14961; b) M. A. Karimi Zarchi, M. Nejabat, J. Appl.
Polym. Sci. 2012, 125, 1041–1048; c) G. Petrillo, M.
Novi, G. Garbarino, M. Filiberti, Tetrahedron 1989, 45,
7411–7420.
[9] a) H. Nambu, K. Hata, M. Matsugi, Y. Kita, Chem.
Eur. J. 2005, 11, 719–727; b) H. Nambu, K. Hata, M.
Matsugi, Y. Kita, Chem. Commun. 2002, 1082–1083;
c) S. Singh, L. D. S. Yadav, Tetrahedron Lett. 2012, 53,
5136–5140.
[10] a) P. Gopinath, R. S. Vidyarini, S. Chandrasekaran, J.
Org. Chem. 2009, 74, 6291–6294; b) P. Gopinath, R. S.
Vidyarini, S. Chandrasekaran, Eur. J. Org. Chem. 2009,
6043–6047; c) P. Gopinath, C. Debasree, R. S. Vidyari-
ni, S. Chandrasekaran, Tetrahedron 2010, 66, 7001–
7011.
[11] a) H. Firouzabadi, N. Iranpoor, M. Abbasi, Adv. Synth.
Catal. 2009, 351, 755–766; b) H. Firouzabadi, N. Iran-
poor, M. Abbasi, Tetrahedron 2009, 65, 5293–5301;
c) H. Firouzabadi, N. Iranpoor, M. Gholinejad, Adv.
Synth. Catal. 2010, 352, 119–124; d) L. Wang, W.-Y.
Zhou, S.-C. Chen, M.-Y. He, Q. Chen, Adv. Synth.
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An Odorless, One-Pot Synthesis of Thioesters from Organic
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