AlCl3-promoted thiolation of acyl C-H bonds with arylsulfonyl hydrazides

Article abstract of DOI:10.1016/j.tet.2015.10.030

AlCl₃-promoted thiolation of acyl C-H bonds with arylsulfonyl hydrazides was developed, which represents an effective synthesis of S-aryl thiocarbamates via C-S bond formation reaction.

Full text of DOI:10.1016/j.tet.2015.10.030

Tetrahedron 71 (2015) 9496e9500
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Tetrahedron
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AlCl3-promoted thiolation of acyl CeH bonds with arylsulfonyl
hydrazides
,
b
,
a
a
,
d
c,
*
Jie Chen a, Jincheng Mao a , Yue He , Daqing Shi , Binyang Zou , Guoqi Zhang
*
*
a Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University,
Suzhou 215123, PR China
b State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu 610500, PR China
c Department of Sciences, John Jay College and The Graduate Center, The City University of New York, New York, NY 10019, USA
d College of Petroleum Engineering, China University of Petroleum, Beijing 102249, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
AlCl3-promoted thiolation of acyl CeH bonds with arylsulfonyl hydrazides was developed, which rep-
resents an effective synthesis of S-aryl thiocarbamates via CeS bond formation reaction.
Ó 2015 Elsevier Ltd. All rights reserved.
Received 2 September 2015
Received in revised form 10 October 2015
Accepted 12 October 2015
Available online 2 November 2015
Keywords:
AlCl3
Thiolation
Arylsulfonyl hydrazides
S-aryl thiocarbamates
CeS bond formation
1. Introduction
drawbacks such as low efficacy caused by two-step synthetic
routes, tedious operations, issues of unavoidable side-reaction or
S-aryl thiocarbamate is a key structural unit that is widely
found in some biologically active molecules such as herbicides
thiobencarb and orbencarb (Fig. 1).1 A considerably large number
of methodologies have been developed to construct the S-aryl
thiocarbamate core structure and the emphasis of research has
been on the reactions of amines with thiols and phosgene or with
carbonyl sulfide,2,3 the reactions of dialkylamines with carbon
monoxide and sulfur,1,4 two-step synthesis of S-alkyl thio-
carbamates,5 and metal-catalyzed thiolation of acyl compounds.6
However, the reported protocols usually suffer from some
environmental unfriendliness.1e5
Owing to the increasing importance of the CeS bond forming
process in organosulfur-containing medicinal synthesis,7 in-
tensive research efforts have been focused on metal-promoted
cross coupling for CeS bond formation in recent years. The
metal catalyst systems developed thus far mainly involve Pd, Cu,
Ni, Fe, Mn, Rh and so on.8e12 More recently, CeH bond activation
as a powerful tool in organic synthesis has been exploited for the
cross coupling CeS bond formation. Both sp2 and sp3 CeH bond
sulfenylations have been achieved towards the construction of
diverse sulfide derivatives.13 In addition, the formamide acyl CeH
bond activation was carried out to produce a class of S-aryl thio-
carbamates by copper catalyzed reactions with thiols as a sulfur
source.6 However, the use of the volatile, foul-smelling and ex-
pensive arenethiols in this work largely limited the practical ap-
plications of this method. The development of new synthetic
methods utilizing alternative sulfur sources such as sulfonyl hy-
drazides that are safe, reliable and less expensive is desirable. To
continue our recent efforts on the cross coupling CeS bond for-
mation processes in our group,14 we, herein, report a novel
aluminum-promoted thiolation of formamide CeH bonds with
arylsulfonyl hydrazides.
Fig. 1. The representative known compounds containing thiocarbamate moiety.
* Corresponding authors. Fax: þ86 28 83033546; e-mail addresses: jcmao@suda.
edu.cn (J. Mao), dqshi@suda.edu.cn (D. Shi), guzhang@jjay.cuny.edu (G. Zhang).
http://dx.doi.org/10.1016/j.tet.2015.10.030
0040-4020/Ó 2015 Elsevier Ltd. All rights reserved.

J. Chen et al. / Tetrahedron 71 (2015) 9496e9500
9497
Table 2
2. Results and discussion
Substrate scope for the synthesis of S-aryl thiocarbamate compoundsa
Initially, phenylsulfonyl hydrazide was reacted with N,N-dime-
thylformamide (DMF) at 150 ꢀC in the air, in the presence of cata-
lytic amount of PdCl2 and an oxidant DTBP (2.0 equiv), and to our
delight the desired product 3a was isolated in 25% yield (Table 1,
entry 1). In order to optimize the reaction conditions, various oxi-
dants were tested for this transformation (Table 1, entries 2e5),
however, none of them was effective. It was further observed that
the reaction also proceeded in the absence of a palladium catalyst,
whilst the yield was slightly lower (Table 1, entry 6). We next
screened some other catalysts such as Pd(OAc)2, (Ph3P)2PdCl2, I2,15
Cu(OAc)2, CuI and FeCl3, yet either inferior results or no reaction
were revealed (Table 1, entries 7e12). Interestingly, changing the
reaction conditions by the addition of an extra Lewis acid alumi-
num trichloride (0.2 equiv) into the catalyst system resulted in
a small improvement of the yield (Table 1, entry 13), and the yield
was slightly higher while using AlCl3 alone as a catalyst (Table 1,
entry 14). Consequently, several other Lewis acids were examined
and it turned out that AlCl3 was the best additive for the reaction
(Table 1, entries 14e18). In addition, the loading amounts of both
the additive and oxidant were evaluated, it was found that 53%
yield of 3a was gained when 3.0 equivalents of DTBP and 1.0
equivalent of AlCl3 were utilized (Table 1, entries 19e23). At this
end, the yield was further improved to 65% when conducted under
Ar atmosphere (Table 1, entries 24e25).
Table 1
Optimization of the reaction conditionsa
Entry
Oxidant (equiv)
Catalyst (mol %)
Additive (equiv)
Yieldb (%)
1
2
3
4
5
6
7
8
DTBP(2.0)
TBHP(2.0)c
DCP(2.0)
PdCl2(10)
PdCl2(10)
PdCl2(10)
PdCl2(10)
PdCl2(10)
d
d
25
d
ND
Trace
ND
ND
17
22
20
22
ND
Trace
ND
26
34
27
Trace
22
Trace
38
42
40
d
Na2S2O8(2.0)
PhI(OAc)2(2.0)
DTBP(2.0)
DTBP(2.0)
DTBP(2.0)
DTBP(2.0)
DTBP(2.0)
DTBP(2.0)
DTBP(2.0)
DTBP(2.0)
DTBP(2.0)
DTBP(2.0)
DTBP(2.0)
DTBP(2.0)
DTBP(2.0)
DTBP(2.0)
DTBP(2.0)
DTBP(2.0)
DTBP(3.0)
DTBP(4.0)
DTBP(3.0)
DTBP(3.0)
d
d
d
Pd(OAc)2(10)
(Ph3P)2PdCl2(10)
I2(10)
Cu(OAc)2(10)
CuI(10)
FeCl3(10)
PdCl2(10)
d
d
d
d
d
d
d
d
d
d
d
d
d
d
9
d
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24d
25e
d
d
d
AlCl3(0.2)
AlCl3(0.2)
BF3$Et2O(0.2)
ZnCl2(0.2)
HOAc(0.2)
H2SO4(0.2)
AlCl3(0.5)
AlCl3(1.0)
AlCl3(2.0)
AlCl3(1.0)
AlCl3(1.0)
AlCl3(1.0)
AlCl3(1.0)
with DMF under the optimized conditions, modest to good yields
have been obtained (3a, 3b, 3j, 3ge3i). In addition, halo substituents,
F, Cl, or Br at the para-positions of phenylsulfonyl hydrazide were also
compatible with the optimal conditions, affording the desired prod-
ucts in good yields (3ce3e), although the reaction with meta-bro-
mophenylsulfonyl hydrazide was less efficient (3f). It is worth noting
that this protocol is also applicable to heterocyclic aromatics such as
naphthalene, give 52% yield of the corresponding product (3l). Next,
a variety of formamides were also investigated. Under the optimized
conditions, new formamides including N,N-diethylformamide, N,N-
dibutylformamide, and N,N-diisopropylformamide were found to
react smoothly with toluenesulfonyl hydrazide to generate the cou-
pling products with 36e61% yields (3me3o). Encouraged by the
relatively high yield of 3o, the scope and versatility of this method
was extended to the reactions of N,N-diisopropylformamide with
53
51
65
48
a
Reaction conditions: 1a (0.3 mmol), 2a (1 mL), oxidant (2e4 equiv), additive
(0.2e2 equiv), heated at 150 ꢀC for 12 h.
b
Isolated yield.
70% in water solution.
Under Ar atmosphere.
Under O2 atmosphere. DTBP: di-tert-butyl peroxide; TBHP: tert-butyl hydro-
c
d
e
peroxide; DCP: dicumyl peroxide.
With the optimized conditions in hand, we then explored the
substrate scope of the present protocol (Table 2). When electron-
neutral and -rich phenylsulfonyl hydrazides were used to react

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J. Chen et al. / Tetrahedron 71 (2015) 9496e9500
various substituted phenylsulfonyl hydrazides and accordingly, a di-
verse range of S-aryl thiocarbamate compounds were generated in
reasonable yields (3pe3y). The single-crystal X-ray structure of the
thiocarbamate product 3l was obtained and the ORTEP presentation
of the molecule is illustrated in Fig. 2. The result matches with the
proposed molecular structure, being in full agreement with the
spectroscopic data.
Scheme 2. The Plausible mechanism.
Fig. 2. An ORTEP diagram of product 3l.
thiolation of acyl CeH bonds using arylsulfonyl hydrazides as thiol
surrogates. This work represents a new example for the CeS bond
formation. Further investigations are in progress to expand the
scope of the reaction.
To gain insights on the reaction mechanisms, control experi-
ments were carried out as shown in Scheme 1.16 When the reaction
between phenylsulfonyl hydrazide and DMF was performed under
the standard reaction conditions without the addition of DTBP,
a disulfide product was obtained in 74% yield. Subsequently, the
4. Experiment
4.1. General information
All reactions were carried out under Ar atmosphere. Solvents
were dried and degassed by standard methods. Flash column
chromatography was performed using silica gel (300e400 mesh).
Analytical thin-layer chromatography was performed using glass
plates pre-coated with 200e400 mesh silica gel impregnated with
a fluorescent indicator (254 nm). Melting points were measured
using a XT-4 micro melting point apparatus and were uncorrected.
The 1H and 13C NMR spectra of the new compounds were measured
at 400 MHz and 100 MHz in CDCl3 with TMS as the internal stan-
dard. HRMS analyses were carried out using a Bruker micrOTOF-Q
instrument.
Scheme 1. Control experiments.
4.2. General procedure for the synthesis of 3
disulfide was used to further react with DMF in the presence of
DTBP, and the same thiocarbamate product 3a was harvested in 60%
yield, comparable to the result above when the reaction was carried
out in one pot. This result indicates that the reduced disulfide has
participated in the reaction as an intermediate.
A 25 mL tube was charged with phenylsulfonyl hydrazide
(0.3 mmol), AlCl3 (1 equiv), DTBP (3 equiv) and DMF (1 mL) under
Ar atmosphere. The resulting reaction mixture was kept stirring at
150 ꢀC for 12 h. Upon completion of the reaction, the reaction
mixture was cooled to room temperature. After removal of the
solvent, the residue was subjected to column chromatography on
silica gel using ethyl acetate and petroleum ether mixtures to afford
the desired product in high purity.
A proposed reaction mechanism is outlined in Scheme 2 based
upon both the results obtained here and the literature reports.17 The
aluminum trichloride is responsible for the sequential removal of
hydrogen and oxygen atoms from phenylsulfonyl hydrazide to
genete intermediate B, which reacted further with the metal to form
aryl disulfide as confirmed previously through the elimination of N2
molecules. On the other side, DTBP would experience hemolytic
cleavage to give tert-butoxyl radicals upon heating, which abstracts
hydrogen from formamide to generate the crucial radical A. Conse-
quently, radical A reacts with either the intermediate B or aryl
disulfide, resulting in the formation of 3a and ArSꢁ free radical. The
ArSꢁ free radical also readily combines with another radical A to form
the product 3a and the reaction is terminated.
4.3. S-p-Tolyl dimethylcarbamothioate (3a)
Pale yellow liquid. 1H NMR (400 MHz, CDCl3)
J¼8.0 Hz, 2H), 7.24 (d, J¼8.0 Hz, 2H), 3.13 (s, 3H), 3.08 (s, 3H), 2.42
d 7.42 (d,
(s, 3H); 13C NMR (100 MHz, CDCl3)
d 166.9, 138.9, 135.2, 129.3,
124.7, 36.4, 20.8; HRMS calcd for C10H13NOS [MþH]þ: 196.0791,
found: 196.0788.
4.4. S-o-Tolyl dimethylcarbamothioate (3b)
3. Conclusions
Pale yellow liquid. 1H NMR (400 MHz, CDCl3)
1H), 7.40e7.34 (m, 2H), 7.27e7.23 (m, 1H), 3.18 (s, 3H), 3.08 (s, 3H),
2.47 (s, 3H); 13C NMR (100 MHz, CDCl3)
166.0, 142.6, 136.6, 130.1,
d
7.53 (d, J¼7.6 Hz,
In conclusion, we have disclosed a direct approach for synthe-
sizing S-aryl thiocarbamate compounds from AlCl3-promoted
d

J. Chen et al. / Tetrahedron 71 (2015) 9496e9500
9499
129.4, 127.7, 125.9, 36.5, 20.6; HRMS calcd for C10H13NOS [MþH]þ:
4.13. S-(4-(Trifluoromethyl)phenyl) dimethylcarbamothioate
(3k)
196.0791, found: 196.0790.
Pale yellow liquid. 1H NMR (400 MHz, CDCl3)
d
7.70e7.65 (m,
4.5. S-(4-Fluorophenyl) dimethylcarbamothioate (3c)
4H), 3.15 (s, 3H), 3.09 (s, 3H); 13C NMR (100 MHz, CDCl3)
d 165.1,
135.2, 133.1 (d, J¼1.3 Hz), 130.5 (q, J¼32.4 Hz), 125.1 (q, J¼3.7 Hz),
123.4 (q, J¼270.6 Hz), 36.5; HRMS calcd for C10H10F3NOS [MþH]þ:
250.0508, found: 250.0524.
Pale yellow liquid. 1H NMR (400 MHz, CDCl3)
2H), 7.15e7.10 (m, 2H), 3.13 (s, 2H), 3.08 (s, 2H); 13C NMR (100 MHz,
CDCl3)
d 7.53e7.49 (m,
d
166.3, 163.0 (d, J¼247.9 Hz), 137.3 (d, J¼8.5 Hz), 123.6 (d,
J¼3.4 Hz), 115.6 (d, J¼21.9 Hz), 36.4; HRMS calcd for C9H10FNOS
4.14. S-Naphthalen-2-yl dimethylcarbamothioate (3l)
[MþH]þ: 200.0540, found: 200.0555.
White solid, mp¼106e108 ꢀC. 1H NMR (400 MHz, CDCl3)
d
8.09 (s, 1H), 7.92e7.87 (m, 3H), 7.63e7.53 (m, 3H), 3.17 (s, 3H),
4.6. S-(4-Chlorophenyl) dimethylcarbamothioate (3d)
3.10 (s, 3H); 13C NMR (100 MHz, CDCl3)
d 166.5, 134.8, 133.0,
White solid, mp¼76e78 ꢀC. 1H NMR (400 MHz, CDCl3)
132.8, 131.8, 128.0, 127.5, 127.3, 126.5, 125.9, 125.6, 36.5; HRMS
calcd for C13H13NOS [MþH]þ: 232.0791, found: 232.0803.
d
7.48e7.45 (m, 2H), 7.42e7.38 (m, 2H), 3.13 (s, 2H), 3.08 (s, 1H);
13C NMR (100 MHz, CDCl3)
d 165.8, 136.4, 135.1, 128.6, 126.8, 36.5;
HRMS calcd for C9H10ClNOS [MþH]þ: 216.0244, found: 216.0252.
4.15. S-p-Tolyl diethylcarbamothioate (3m)
Pale yellow liquid. 1H NMR (400 MHz, CDCl3)
2H), 7.25 (d, J¼7.6 Hz, 2H), 3.51e3.46 (m, 4H), 2.42 (s, 3H), 1.32 (s,
3H), 1.23 (s, 3H); 13C NMR (100 MHz, CDCl3)
165.6, 138.8, 135.3,
d
7.44 (d, J¼8.0 Hz,
4.7. S-(4-Bromophenyl) dimethylcarbamothioate (3e)
d
White solid, mp¼84e86 ꢀC. 1H NMR (400 MHz, CDCl3)
d 7.55 (d,
129.2, 124.8, 41.8, 20.8, 13.4, 12.7; HRMS calcd for C12H17NOS
J¼8.4 Hz, 2H), 7.40 (d, J¼8.8 Hz, 2H), 3.12 (s, 2H), 3.08 (s, 2H); 13C
[MþH]þ: 224.1104, found: 224.1121.
NMR (100 MHz, CDCl3) d 165.7,136.7,131.6, 127.5, 123.4, 36.5; HRMS
calcd for C9H10BrNOS [MþH]þ: 259.9739, found: 259.9752.
4.16. S-p-Tolyl dibutylcarbamothioate (3n)
Pale yellow liquid. 1H NMR (400 MHz, CDCl3)
d
7.43 (d, J¼8.0 Hz,
4.8. S-(3-Bromophenyl) dimethylcarbamothioate (3f)
2H), 7.24 (d, J¼7.6 Hz, 2H), 3.40 (t, J¼7.6 Hz, 4H), 2.41 (s, 3H), 1.72 (s,
Pale yellow liquid. 1H NMR (400 MHz, CDCl3)
1H), 7.58e7.55 (m, 1H), 7.49e7.41 (m, 1H), 7.34e7.29 (m, 1H), 3.12
d
7.71 (t, J¼1.6 Hz,
2H), 1.61 (s, 2H), 1.44 (s, 2H), 1.34 (s, 2H), 1.05 (s, 3H), 0.98 (s, 3H);
13C NMR (100 MHz, CDCl3)
d 166.0, 138.7, 135.3, 129.2, 124.9, 47.6,
47.4, 30.2, 29.4, 20.8, 19.7, 13.3; HRMS calcd for C16H25NOS [MþH]þ:
(s, 3H), 3.09 (s, 3H); 13C NMR (100 MHz, CDCl3)
d 165.5, 137.6, 133.8,
131.7,130.3,129.7,121.8, 36.5; HRMS calcd for C9H10BrNOS [MþH]þ:
280.1730, found: 280.1738.
259.9739, found: 259.9752.
4.17. S-p-Tolyl diisopropylcarbamothioate (3o)
4.9. S-Phenyl dimethylcarbamothioate (3g)
White solid, mp¼95e97 ꢀC. 1H NMR (400 MHz, CDCl3)
d 7.44 (d,
J¼8.0 Hz, 2H), 7.25 (d, J¼8.0 Hz, 2H), 4.25 (s,1H), 3.55 (s, 1H), 2.41 (s,
Pale yellow liquid. 1H NMR (400 MHz, CDCl3)
2H), 7.43e7.39 (m, 3H), 3.11 (s, 3H), 3.06 (s, 3H); 13C NMR (100 MHz,
d 7.54e7.50 (m,
3H), 1.39 (s, 12H); 13C NMR (100 MHz, CDCl3)
d 163.7, 138.6, 135.5,
129.2, 125.3, 49.0, 47.1, 20.9, 20.2; HRMS calcd for C14H21NOS
CDCl3)
d 166.5, 135.3, 128.7, 128.4, 128.3, 36.4; HRMS calcd for
[MþH]þ: 252.1417, found: 252.1429.
C9H11NOS [MþH]þ: 182.0634, found: 182.0646.
4.18. S-Phenyl diisopropylcarbamothioate (3p)
4.10. S-(4-(tert-Butyl)phenyl) dimethylcarbamothioate (3h)
White solid, mp¼68e70 ꢀC. 1H NMR (400 MHz, CDCl3)
Pale yellow liquid. 1H NMR (400 MHz, CDCl3)
2H), 7.47e7.42 (m, 3H), 4.25 (s, 1H), 3.57 (s, 1H), 1.39 (s, 12H); 13C
d 7.57e7.54 (m,
d
7.49e7.44 (m, 4H), 3.13 (s, 3H), 3.09 (s, 3H), 1.37 (s, 9H); 13C NMR
NMR (100 MHz, CDCl3) d 163.4, 135.4, 128.8, 128.4, 128.4, 49.2, 47.1,
20.2; HRMS calcd for
238.1275.
C
13H19NOS [MþH]þ: 238.1260, found:
(100 MHz, CDCl3) d 166.8, 151.8, 134.9, 125.6, 124.8, 36.4, 34.2, 30.8;
HRMS calcd for C13H19NOS [MþH]þ: 238.1260, found: 238.1257.
4.19. S-(4-Fluorophenyl) diisopropylcarbamothioate (3q)
4.11. S-Mesityl dimethylcarbamothioate (3i)
Pale yellow liquid. 1H NMR (400 MHz, CDCl3)
d 7.51e7.46 (m,
Pale yellow liquid. 1H NMR (400 MHz, CDCl3)
(s, 3H), 3.07 (s, 3H), 2.44 (s, 6H), 2.34 (s, 3H); 13C NMR (100 MHz,
d 7.03 (s, 2H), 3.21
2H), 7.12e7.06 (m, 2H), 4.18 (s, 1H), 3.53 (s, 1H), 1.35 (s, 12H); 13C
NMR (100 MHz, CDCl3)
d
163.2, 162.9 (d, J¼247.5 Hz), 137.4 (d,
CDCl3)
d 165.9, 142.9, 139.0, 128.6, 124.2, 36.5, 21.4, 20.7; HRMS
J¼8.5 Hz), 124.1 (d, J¼3.4 Hz), 115.5 (d, J¼21.9 Hz), 49.3, 47.0, 20.2;
calcd for C12H17NOS [MþH]þ: 224.1104, found: 224.1122.
HRMS calcd for C13H18FNOS [MþH]þ: 256.1166, found: 256.1163.
4.12. S-(4-Methoxyphenyl) dimethylcarbamothioate (3j)
4.20. S-(4-Chlorophenyl) diisopropylcarbamothioate (3r)
White solid, mp¼110e112 ꢀC. 1H NMR (400 MHz, CDCl3)
White solid, mp¼88e90 ꢀC. 1H NMR (400 MHz, CDCl3)
d 7.45 (d,
J¼9.2 Hz, 2H), 6.96 (d, J¼9.2 Hz, 2H), 3.86 (s, 3H), 3.12 (s, 3H), 3.08
d 7.49e7.46 (m, 2H), 7.41e7.58 (m, 2H), 4.20 (s, 1H), 3.56 (s, 1H), 1.38
(s, 3H); 13C NMR (100 MHz, CDCl3)
d
167.2, 160.1, 136.9, 118.9, 114.1,
(s, 12H); 13C NMR (100 MHz, CDCl3)
d 162.7, 136.6, 134.9, 128.6,
54.9, 36.4; HRMS calcd for C10H13NO2S [MþH]þ: 212.0740, found:
127.4, 49.4, 47.2, 20.2; HRMS calcd for C13H18ClNOS [MþH]þ:
212.0751.
272.0870, found: 272.0865.

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J. Chen et al. / Tetrahedron 71 (2015) 9496e9500
4.21. S-(4-Bromophenyl) diisopropylcarbamothioate (3s)
White solid, mp¼131e133 ꢀC. 1H NMR (400 MHz, CDCl3)
126.2, 125.7, 49.4, 47.1, 20.2; HRMS calcd for C17H21NOS [MþH]þ:
288.1417, found: 288.1434.
d
7.57e7.54 (m, 2H), 7.42e7.39 (m, 2H), 4.20 (s, 1H), 3.55 (s, 1H),1.38
Acknowledgements
(s, 12H); 13C NMR (100 MHz, CDCl3)
d 162.6, 136.9, 131.5, 128.0,
123.2, 49.5, 47.2, 20.2; HRMS calcd for C13H18BrNOS [MþH]þ:
We are grateful to the grants from the Scientific Research
Foundation for the Returned Overseas Chinese Scholars, State
Education Ministry, the Priority Academic Program Development
of Jiangsu Higher Education Institutions, and the Key Laboratory
of Organic Synthesis of Jiangsu Province. GZ acknowledges a PSC-
CUNY award (#67312-0045) from the City University of New
York.
316.0365, found: 316.0364.
4.22. S-(4-(tert-Butyl)phenyl) diisopropylcarbamothioate (3t)
Pale yellow liquid. 1H NMR (400 MHz, CDCl3)
4H), 4.27 (s, 1H), 3.56 (s, 1H), 1.38 (s, 21H); 13C NMR (100 MHz,
d 7.50e7.45 (m,
CDCl3)
d 163.8, 151.4, 135.1, 125.6, 125.3, 49.2, 47.1, 34.2, 30.8, 20.2;
Supplementary data
HRMS calcd for C17H27NOS [MþH]þ: 294.1886, found: 294.1901.
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.tet.2015.10.030.
4.23. S-Mesityl diisopropylcarbamothioate (3u)
Pale yellow liquid. 1H NMR (400 MHz, CDCl3)
(s,1H), 3.55 (s,1H), 2.45 (s, 6H), 2.34 (s, 3H),1.40 (s, 6H),1.39 (s, 6H);
d 7.03 (s, 2H), 4.41
References and notes
13C NMR (100 MHz, CDCl3)
d 162.8, 142.9, 138.7, 128.5, 125.0, 49.4,
1. Mizuno, T.; Iwai, T.; Ito, T. Tetrahedron 2004, 60, 2869.
2. Tilles, H. J. Am. Chem. Soc. 1959, 81, 714.
3. Chin-Hsien, W. Synthesis 1981, 8, 622.
47.1, 21.4, 20.7, 20.3; HRMS calcd for C16H25NOS [MþH]þ: 280.1730,
found: 280.1728.
4. Grisley, D. W., Jr.; Stephens, J. A. J. Org. Chem. 1961, 26, 3568.
5. Wynne, J. H.; Jensen, S. D.; Snow, A. W. J. Org. Chem. 2003, 68, 3733.
6. Yuan, Y.-Q.; Guo, S.-R.; Xiang, J.-N. Synlett 2013, 443.
7. (a) Musah, R. A.; He, Q.; Kubec, R. Plant Physiol. 2009, 151, 1294; (b) El-Bayoumy,
K.; Sinha, R.; Pinto, J. T.; Rivlin, R. S. J. Nutr. 2006, 136, 864.
8. Pd-catalyzed CeS bond formation: (a) Qiao, Z.; Liu, H.; Xiao, X.; Fu, Y.; Wei, J.; Li,
Y.; Jiang, X. Org. Lett. 2013, 15, 2594; (b) Cheng, Y.; Peng, Q.; Fan, W.; Li, P. J. Org.
Chem. 2014, 79, 5812.
9. Cu-catalyzed CeS bond formation: (a) Zhang, X.; Zeng, W.; Yang, Y.; Huang, H.;
Liang, Y. Org. Lett. 2014, 16, 876; (b) Li, Y.; Pu, J.; Jiang, X. Org. Lett. 2014, 16, 2692.
10. Ni-catalyzed CeS bond formation: (a) Venkanna, G. T.; Arman, H. D.;
Tonzetich, Z. J. ACS Catal. 2014, 4, 2941; (b) Brachet, E.; Brion, J.-D.; Alami,
M.; Messaoudi, S. Chem.dEur. J. 2013, 19, 15276; (c) Singh, R.; Allam, B. K.;
Singh, N.; Kumari, K.; Singh, S. K.; Singh, K. N. Adv. Synth. Catal. 2015, 357,
1181.
4.24. S-(4-Methoxyphenyl) diisopropylcarbamothioate (3v)
Pale yellow liquid. 1H NMR (400 MHz, CDCl3)
2H), 6.99e6.95 (m, 2H), 4.24 (s, 1H), 3.86 (s, 3H), 3.54 (s, 1H), 1.38 (s,
d 7.47e7.44 (m,
12H); 13C NMR (100 MHz, CDCl3)
d 164.1, 159.9, 137.0, 119.5, 114.1,
54.8, 49.1, 46.9, 20.2; HRMS calcd for C14H21NO2S [MþH]þ:
268.1366, found: 268.1365.
4.25. S-(3-Bromophenyl) diisopropylcarbamothioate (3w)
11. Fe-catalyzed CeS bond formation: (a) Shen, T.; Yuan, Y.; Song, S.; Jiao, N. Chem.
Commun. 2014, 4115; (b) Wang, H.; Wang, L.; Shang, J.; Li, X.; Wang, H.; Gui, J.;
Lei, A. Chem. Commun. 2012, 76.
Pale yellow liquid. 1H NMR (400 MHz, CDCl3)
1H), 7.56e7.53 (m,1H), 7.50e7.48 (m,1H), 7.30 (t, J¼8.0 Hz,1H), 4.18
(s, 1H), 3.56 (s, 1H), 1.38 (s, 12H); 13C NMR (100 MHz, CDCl3)
162.4,
d
7.71 (t, J¼1.6 Hz,
12. (a) Wong, Y.-C.; Jayanth, T. T.; Cheng, C.-H. Org. Lett. 2006, 8, 5613; (b) Liu, K.;
d
Jia, F.; Xi, H.; Li, Y.; Zheng, X.; Guo, Q.; Shen, B.; Li, Z. Org. Lett. 2013, 15, 2026; (c)
137.7,134.1, 131.5, 131.0, 129.6,121.8, 49.4, 47.2, 20.2; HRMS calcd for
ꢀ
Hooper, J. F.; Chaplin, A. B.; Gonzalez-Rodríguez, C.; Thompson, A. L.; Weller, A.
C
13H18BrNOS [MþH]þ: 316.0365, found: 316.0360.
S.; Willis, M. C. J. Am. Chem. Soc. 2012, 134, 2906.
13. (a) Yuan, J.; Ma, X.; Yi, H.; Liu, C.; Lei, A. Chem. Commun. 2014, 14386; (b)
Guntreddi, T.; Vanjari, R.; Singh, K. N. Tetrahedron 2014, 70, 3887; (c) Feng, J.;
Lu, G.-P.; Cai, C. RSC Adv. 2014, 4, 54409; (d) Chen, C.; Xu, X.-H.; Yang, B.;
Qing, F.-L. Org. Lett. 2014, 16, 3372; (e) Yu, M.; Xie, Y.; Xie, C.; Zhang, Y. Org.
Lett. 2012, 14, 2164; (f) Zeng, J.-W.; Liu, Y.-C.; Hsieh, P.-A.; Huang, Y.-T.; Yi, C.-
L.; Badsara, S. S.; Lee, C.-F. Green Chem. 2014, 16, 2644; (g) Bhat, V. T.;
Duspara, P. A.; Seo, S.; Abu Bakar, N. S. B.; Greaney, M. F. Chem. Commun.
2015, 4383; (h) Foster, J. C.; Powell, C. R.; Radzinski, S. C.; Matson, J. B. Org.
Lett. 2014, 16, 1558; (i) Zhu, X.; Shi, Y.; Mao, H.; Cheng, Y.; Zhu, C. Adv. Synth.
Cat. 2013, 355, 3558; (j) He, C.; Qian, X.; Sun, P. Org. Biomol. Chem. 2014, 12,
6072.
4.26. S-(4-(Trifluoromethyl)phenyl) diisopropylcarbamo-
thioate (3x)
Pale yellow liquid. 1H NMR (400 MHz, CDCl3)
(s, 1H), 3.57 (s, 1H), 1.39 (s, 12H); 13C NMR (100 MHz, CDCl3)
d
7.68 (s, 4H), 4.22
162.0,
d
135.4, 133.7, 130.2 (q, J¼32.4 Hz), 125.0 (q, J¼3.8 Hz), 123.5 (q,
J¼270.6 Hz), 49.6, 47.3, 20.1; HRMS calcd for C14H18F3NOS [MþH]þ:
306.1134, found: 306.1151.
14. (a) Rong, G.; Mao, J.; Liu, D.; Yan, H.; Zheng, Y.; Chen, J. RSC Adv. 2015, 5, 26461;
(b) Rong, G.; Mao, J.; Yan, H.; Zheng, Y.; Zhang, G. J. Org. Chem. 2015, 80, 4697;
(c) Chen, J.; Mao, J.; Zheng, Y.; Liu, D.; Rong, G.; Yan, H.; Zhang, C.; Shi, D. Tet-
rahedron 2015, 71, 5059.
4.27. S-Naphthalen-2-yl diisopropylcarbamothioate (3y)
15. Yang, F. L.; Tian, S. K. Angew. Chem., Int. Ed. 2013, 52, 4929.
16. (a) Guo, S.; Yuan, Y.; Xiang, J. Org. Lett. 2013, 15, 4654; (b) Tang, R.; Xie, Y.-X.;
Pale yellow liquid. 1H NMR (400 MHz, CDCl3)
d 8.10 (s, 1H),
Xie, Y.-L.; Xiang, J.-N.; Li, J.-H. Chem. Commun. 2011, 12867.
17. (a) Sun, J.; Wang, Y.; Pan, Y. Org. Biomol. Chem. 2015, 13, 3878; (b) Kumar-
aswamy, G.; Raju, R. Adv. Synth. Catal. 2014, 356, 2591; (c) Singh, R.; Raghu-
vanshi, D. S.; Singh, K. N. Org. Lett. 2013, 15, 16; (d) Guo, S.-R.; He, W.-M.; Xiang,
J.-N.; Yuan, Y.-Q. Chem. Commun. 2014, 8578.
7.93e7.88 (m, 3H), 7.66e7.63 (dd, J¼8.8, 2.0 Hz, 1H), 7.58e7.52 (m,
2H), 4.31 (s, 1H), 3.58 (s, 1H), 1.42 (s, 12H); 13C NMR (100 MHz,
CDCl3)
d 163.5, 134.9, 133.1, 132.8, 132.2, 127.9, 127.5, 127.2, 126.4,