Iodine-mediated thiolation of substituted naphthols/naphthylamines and arylsulfonyl hydrazides via C(sp2)-H bond functionalization

Article abstract of DOI:10.1021/jo501778h

A direct method has been developed for iodine-mediated thiolation of naphthols/naphthylamines and arylsulfonyl hydrazides through the formation of C-S bond and cleavage of S-N/S-O bonds. In this transformation, a range of valuable thioethers are easily achieved in moderate to good yields.

Full text of DOI:10.1021/jo501778h

Note
pubs.acs.org/joc
Iodine-Mediated Thiolation of Substituted Naphthols/2
Naphthylamines and Arylsulfonyl Hydrazides via C(sp )−H Bond
Functionalization
Xing Kang, Rulong Yan,* Guiqin Yu, Xiaobo Pang, Xingxing Liu, Xiaoni Li, Likui Xiang,
and Guosheng Huang*
State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of
Gansu Province, Department of Chemistry, Lanzhou University, Lanzhou 730000, China
*
S Supporting Information
ABSTRACT: A direct method has been developed for iodine-mediated thiolation of naphthols/naphthylamines and arylsulfonyl
hydrazides through the formation of C−S bond and cleavage of S−N/S−O bonds. In this transformation, a range of valuable
thioethers are easily achieved in moderate to good yields.
he development of C−S bond formation has emerged as a
significant field of research in organic chemistry because
Sulfonyl hydrazides as ideal thiolating agents have been
widely used to construct the C−S bond because they are readily
accessibile and stable. Inspired by Tian’s thiolation reaction of
T
organosulfur compounds are widely present in natural products
and are applied in total organic synthesis, medical chemistry,
10
sulfonyl hydrazides and indoles catalyzed by iodine and our
1
1
1
experiences in the transformation of C−H bond activation,
and functional materials science. Among them, diaryl sulfides,
we envisaged a new method for forming C−S bonds with
naphthols/naphthylamines and sulfonyl hydrazides via C(sp )−
as valuable building blocks, are found in many pharmacological
2
compounds for HIV and cancer as well as Alzheimer’s and
2
H functionalization. Thus, naphthalen-2-ol (1a) and sulfonyl
hydrazide (2b) were subjected to the reaction conditions
reported by Tian to test this approach. As expected, 1-(p-
tolylthio)naphthalen-2-ol (3ab) was successfully obtained in
Parkinson’s diseases. Given the tremendous importance of
functionalized diaryl sulfides, numerous catalytic reactions have
been improved for C−S bond formation. With the develop-
ment of green chemistry and increased concern over environ-
mental issues, direct oxidative coupling by selective function-
alization of the C−H bond has developed as an efficient
methodology for C−S bond formation. Among recent reports,
the groups of Yu, Yuan, Fu, Tian, and Jiang et al. have described
different approaches for C−S bond formation via C−H bond
4
2% yield in this reaction (Scheme 1, entry 1). Herein, we
disclose a practical and convenient procedure to synthesize
various thioethers with sulfonyl hydrazides and naphthols/
naphthylamines.
Encouraged by this result, we initiated our investigation with
the reaction of 1a and 2b as a model reaction to identify the
optimal reaction conditions. On the basis of the result in Table
1, entry 1, reactions were carried out in the presence of iodine.
After screening the temperature of the reaction, we found that
the substrate showed the highest activity for this reaction at 100
°C. Moreover, further improvement of the process was
3
4
activation catalyzed by transition metals, such as Pd, Cu, and
5
Fe. In those transformations, different thiolating/sulfenylating
reagents, for example, sulfonyl hydrazides, sodium sulfinates,
diaryldisulfides, and arylthiols, were employed. Nonetheless,
these methods suffer from the use of expensive or toxic metal
salts, harsh reaction conditions, and narrow substrate scopes.
Certainly, many environmentally friendly methods have also
made great progress, which have been reported by the groups
achieved when I
Among the different solvents tested, THF gave the best result
Table 1, entry 4). Nevertheless, the yield decreased when
(0.5 equiv) was used (Table 1, entry 3).
2
(
6
7
8
9
of Jiang, Tian, Xiang, and others. However, the develop-
ment of green, efficient, and practical access to C−S bond
formation is still highly desired.
Received: August 2, 2014
©
XXXX American Chemical Society
A
dx.doi.org/10.1021/jo501778h | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
2
Scheme 1. I -Mediated C(sp )−S Bond Formation
Table 2. Thiolation of Substituted Naphthols and Sulfonyl
Hydrazides
2
a
a
Table 1. Optimization of Reaction Conditions
b
entry
catalyst/equiv
solvent
EtOH
temp. (°C)
yield (%)
1
2
3
4
5
6
7
8
9
I2 (0.2)
I2 (0.2)
I2 (0.5)
I2 (0.5)
I2 (1.0)
I2 (0.5)
I2 (0.5)
I2 (0.5)
I2 (0.5)
I2 (0.5)
I2 (0.5)
NIS (1.2)
70
42
61
70
95
93
EtOH
EtOH
THF
THF
THF
100
100
100
100
25
CH CN
100
100
100
100
100
100
100
73
72
63
3
PhMe
ClCH CH Cl
2
2
10
11
12
13
DMF
DMSO
THF
78
THF
a
Reaction conditions: 1a (0.3 mmol), 2b (0.36 mmol), and additive in
mL of solvent. Isolated yield.
b
a
2
Reaction conditions: 1 (0.3 mmol), 2 (0.36 mmol), and I
(0.15
2
mmol) in 2 mL of THF at 100 °C for 10 h.
In order to enlarge the scope of this transformation, further
experiments were conducted for the reaction of naphthalen-2-
amine 4a with 2b under the optimized conditions, and 1-(p-
tolylthio)naphthalen-2-amine 5ab was obtained in 62% yield.
After screening the paramaters of temperature, acids, and
solvents, a higher yield was achieved when the reaction was
replacing iodine with N-iodosuccinimide (NIS) (Table 1, entry
2). In the absence of iodine, no desired product was detected,
which indicated that iodine was essential to this reaction (Table
1
1
, entry 13).
With the optimized conditions in hand, the scope of the
substrates using naphthols and sulfonyl hydrazides was
examined, and the results are illustrated in Table 2. It was
gratifying to find that a variety of substituted sulfonyl
hydrazides could couple with naphthols in moderate to high
yields.
Generally, sulfonyl hydrazides with electron-donating groups
gave higher yields than that of substrates with electron-
withdrawing groups. Obviously, when 4-nitrobenzenesulfono-
hydrazide 2l was employed under the optimized conditions,
only a trace amount of 3al was detected by TLC. Thiophene-2-
sulfonohydrazide 2m was also tolerated in this transformation,
generating the target compound 3am in 85% yield. Further
investigation showed that even 2-methoxynaphthalene 1e and
carried out with I (0.5 equiv) and HOAc (0.5 equiv) in THF
2
at 100 °C. The scope of the substrates using naphthylamines
and sulfonyl hydrazides was also examined, and the results are
illustrated in Table 3. Generally, the reaction between
substituted sulfonyl hydrazides and naphthylamines proceeded
smoothly and afforded the corresponding products with high
efficiency. It was observed that the nature of the substituent on
the aromatic rings of the sulfonyl hydrazides did not
significantly affect the yields of this reaction. Sulfonyl
hydrazides with electron-withdrawing groups gave slightly
higher yields than those with electron-donating groups. When
N-phenylnaphthalen-2-amine 4b was subjected to the reaction,
only a trace amount of 5bb was detected.
2
-ethoxynaphthalene 1f can also proceed smoothly in this
Remarkably, when naphthalen-1-ol 1h and naphthalen-1-
amine 4c were subjected to the transformation under standard
conditions, the expected products 3hb and 5cb were isolated in
72 and 64% yields, respectively (Scheme 2).
reaction, and the desired products were isolated in 61 and 73%
yields, respectively. Of note, when 5,6,7,8-tetrahydronaphtha-
len-2-ol 1g and 2b were reacted out under standard conditions,
1
-(p-tolylthio)-5,6,7,8-tetrahydronaphthalen-2-ol 3gb was ob-
In order to gain further insight into the mechanism, some
control experiments were investigated. First, when coupling 1a
tained in 36% yield.
B
dx.doi.org/10.1021/jo501778h | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
Table 3. Thiolation of Substituted Naphthylamines and
Sulfonyl Hydrazides
6/7 was approximately 8:8:15. Then, when compound 6 was
subjected to the reaction with 1a under the optimized
conditions, desired product 2b was also isolated in 82% yield
a
(
Scheme 3). Thus, we speculate that compound 6 is the
intermediate of this reaction. On the basis of these results, a
proposed mechnism for C(sp )−S bond formation is illustrated
in Scheme 4. Initially, substrate 2 is converted to intermediate 7
2
Scheme 4. Proposed Mechanism
with the aid of iodine. Meanwhile, N , HOI, and HI are
2
a
released in this transformation. Subsequently, intermediate 6 is
Reaction conditions: 1 (0.3 mmol), 2 (0.36 mmol), I (0.15 mmol),
2
10
and HOAc (0.15 mmol) in 2 mL of THF at 100 °C for 5 h.
produced by reduction of 7. Then, 6 reacts with HI to give
sulfenyl iodide 8, which attacks sustrates 1 or 4 to produce
desired compounds 3 or 5 via an electrophilic reaction (Scheme
Scheme 2. Reaction of 1h and 4c with Sulfonyl Hydrazide
4
).
In conclusion, we have developed a significant method to
afford synthetically valuable thioethers easily with readily
accessible substrates: substituted naphthols/naphthylamines
and sulfonyl hydrazides. The thiolation of naphthols/naphthyl-
amines and sulfonyl hydrazides undergoes C−H bond
functionalization, C−S bond formation, and S−N/S−O
bonds cleavage. In this procedure, various substituents, such
as alkyl, methoxyl, chloro, bromo, and fluoro groups, are
achieved smoothly by the thiolation in moderate to good yields.
EXPERIMENTAL SECTION
■
General Remarks. H and 13C NMR spectra were recorded at 400
1
and 100 MHz in CDCl . All chemical shifts are given as δ values
3
(
ppm) with reference to tetramethylsilane (TMS) as an internal
standard. HRMS was performed on an FT-ICRMS mass instrument
1
and 2b were carried out at 70 °C with 0.5 equiv of I in THF
and measured with electrospray ionization (ESI). Copies of the H and
2
13
after 5 h, byproducts 6 and 7 were observed in the reaction
mixture. In this transformation, the molar ratio of isolated 3ab/
C NMR spectra are provided in the Supporting Information.
Products were purified by flash chromatography on 200−300 mesh
Scheme 3. Control Experiments
C
dx.doi.org/10.1021/jo501778h | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
silica gel. All melting points were determined without correction.
Commercially available reagents and solvents were used without
further purification except where noted.
General Procedure for the Synthesis of the Desired
Thioethers 3. An oven-dried pressure tube was charged with 0.3
1-((3-Fluorophenyl)thio)naphthalen-2-ol (3ag). Yellow solid
1
(41.3 mg, 51% yield); mp 79−81 °C. H NMR (400 MHz, CDCl ) δ
3
8.10−8.08 (d, J = 8.0 Hz, 1H), 7.85−7.83 (d, J = 8.0 Hz, 1H), 7.75−
7.73 (d, J = 8.0 Hz, 1H), 7.44−7.42 (m, 1H), 7.40−7.25 (m, 2H),
7.08−7.02 (m, 1H), 6.99 (s, 1H), 6.76−6.68 (m, 2H), 6.60−6.57 (m,
1H). 13C NMR (100 MHz, CDCl ) δ 164.4−161.9 (d, J = 247.2 Hz),
mmol of naphthols 1, 0.36 mmol of arylsulfonyl hydrazides 2, I (0.15
2
3
mmol), and 2 mL of THF. Then, the reaction was stirred at 100 °C for
157.1, 137.9−137.8 (d, J = 7.6 Hz), 135.3, 133.2, 130.5−130.4 (d, J =
8.3 Hz), 129.5, 128.7, 128.1, 124.4, 124.0, 121.9−121.8 (d, J = 2.9 Hz),
1
0 h. After cooling to room temperature, the solvent was evaporated in
vacuo, and the residues were purified by column chromatography,
eluting with petroleum ether/EtOAc to afford the disired thioethers 3.
General Procedure for the Synthesis of the Desired
Thioethers 5. An oven-dried pressure tube was charged with 0.3
mmol of naphthylamine 4, 0.36 mmol of arylsulfonyl hydrazides 2, I2
116.9, 113.4−113.1 (d, J = 24.1 Hz), 113.0−112.8 (d, J = 21.5 Hz),
+
107.2. HRMS (ESI): m/z calcd for C16
H
12FOS [M + H] , 271.0588;
found, 271.0591.
1-((4-Chlorophenyl)thio)naphthalen-2-ol (3ah). Yellow solid
1
(69.5 mg, 81% yield); mp 85−87 °C. H NMR (400 MHz, CDCl ) δ
3
(
0.15 mmol), HOAc (0.15 mmol), and 2 mL of THF. Then, the
8.16−8.14 (d, J = 8.0 Hz, 1H), 7.91−7.89 (d, J = 8.0 Hz, 1H), 7.81−
7.79 (d, J = 8.0 Hz, 1H), 7.51−7.47 (m, 1H), 7.39−7.31 (m, 2H),
reaction was stirred at 100 °C for 5 h. After cooling to room
temperature, the solvent was evaporated in vacuo, and the residues
were purified by column chromatography, eluting with petroleum
ether/EtOAc to afford the disired thioethers 5.
13
7.13−7.10 (m, 3H), 7.94−6.92 (m, 2H). C NMR (100 MHz,
CDCl
127.6, 124.4, 124.0, 116.9, 107.6. HRMS (ESI): m/z calcd for
) δ 157.0, 135.2, 133.9, 133.1, 131.9, 129.5, 129.3, 128.6, 128.1,
3
+
1
-(Phenylthio)naphthalen-2-ol (3aa). Yellow solid (62.0 mg,
C
16
H
12ClOS [M + H] 287.0292, found 287.0294.
1
8
(
8
7
2% yield); mp 65−67 °C. H NMR (400 MHz, CDCl ) δ 8.22−8.20
1-((2-Chlorophenyl)thio)naphthalen-2-ol (3ai). Yellow solid
3
1
d, J = 8.0 Hz, 1H), 7.90−7.88 (d, J = 8.0 Hz, 1H), 7.81−7.79 (d, J =
(63.5 mg, 74% yield); mp 59−61 °C. H NMR (400 MHz, CDCl ) δ
3
8
7
6
1
.08−8.06 (d, J = 8.0 Hz, 1H), 7.87−7.85 (d, J = 8.0 Hz, 1H), 7.76−
.0 Hz, 1H), 7.50−7.46 (m, 1H), 7.38−7.32 (m, 2H), 7.23 (s, 3H),
13
.74 (d, J = 8.0 Hz, 1H), 7.44−7.40 (m, 1H), 7.33−7.26 (m, 3H),
.17−7.14 (m, 1H), 7.10−7.01 (m, 2H). C NMR (100 MHz,
.97−6.94 (m, 2H), 6.84−6.80 (m, 1H), 6.30−6.28 (d, J = 8.0 Hz,
CDCl ) δ 157.0, 135.4, 135.3, 132.8, 129.5, 129.2, 128.6, 127.9, 126.4,
3
H). 13C NMR (100 MHz, CDCl ) δ 157.3, 135.4, 134.5, 133.3, 131.6,
1
25.9, 124. 7, 123.8, 116.9, 108.1. HRMS (ESI): m/z calcd for
3
+
129.7, 129.6, 128.6, 128.2, 127.4, 126.6, 126.4, 124.5, 124.1, 117.0,
C H OS [M + H] , 253.0682; found, 253.0685.
1
6
13
+
1
06.6. HRMS (ESI)m/z calcd for C H ClOS [M + H] , 287.0292,
1
-(p-Tolylthio)naphthalen-2-ol (3ab). Yellow solid (75.8 mg,
16 12
1
found 287.0295.
-((4-Bromophenyl)thio)naphthalen-2-ol (3aj). Yellow solid
9
(
8
6
1
1
5% yield); mp 77−79 °C. H NMR (400 MHz, CDCl ) δ 8.23−8.21
3
1
d, J = 8.0 Hz, 1H), 7.83−7.81 (d, J = 8.0 Hz, 1H), 7.75−7.73 (d, J =
1
(
83.9 mg, 85% yield); mp 103−105 °C. H NMR (400 MHz, CDCl )
.0 Hz, 1H), 7.46−7.23 (m, 1H), 7.32−7.28 (m, 2H), 7.22 (s, 1H),
3
.92 (s, 4H), 2.18 (s, 3H). 13C NMR (100 MHz, CDCl ) δ 156.8,
δ 8.15−8.13 (d, J = 8.0 Hz, 1H), 7.89−7.87 (d, J = 8.0 Hz, 1H), 7.80−
3
7
7
.78 (d, J = 8.0 Hz, 1H), 7.49−7.45 (m, 1H), 7.37−7.30 (m, 2H),
35.8, 135.4, 132.6, 131.7, 129.9, 129.4, 128.5, 127.8, 126.6, 124.7,
13
.25−7.23 (m, 2H), 7.08 (s, 1H), 6.86−6.84 (d, J = 8.0 Hz, 2H).
C
23.7, 116.8, 108.7, 20.8. HRMS (ESI): m/z calcd for C H OS [M +
17
15
+
NMR (100 MHz, CDCl ) δ 157.0, 135.1, 134.6, 133.1, 132.1, 129.5,
3
H] , 267.0838; found, 267.0839.
-(o-Tolylthio)naphthalen-2-ol (3ac). Yellow solid (67.0 mg,
1
28.6, 128.1, 127.9, 124.4, 124.0, 119.6, 116.9, 107.4. HRMS (ESI):
1
+
1
m/z calcd for C16
H12BrOS [M + H] , 330.9787; found, 330.9788.
8
(
8
=
4% yield); mp 65−67 °C. H NMR (400 MHz, CDCl ) δ 8.13−8.11
3
1
-((4-(Trifluoromethyl)phenyl)thio)naphthalen-2-ol (3ak).
d, J = 8.0 Hz, 1H), 7.90−7.87 (d, J = 12.0 Hz, 1H), 7.80−7.78 (d, J =
.0 Hz, 1H), 7.47−7.43 (m, 1H), 7.36−7.32 (m, 2H), 7.16−7.14 (d, J
8.0 Hz, 1H), 7.07 (s, 1H), 7.00−6.94 (m, 1H), 6.84−6.80 (m, 1H),
1
Yellow solid (58.6 mg, 61% yield); mp 82−84 °C. H NMR (400
MHz, CDCl ) δ 8.18−8.16 (d, J = 8.0 Hz, 1H), 7.98−7.95 (d, J = 12.0
3
13
Hz, 1H), 7.87−7.85 (d, J = 8.0 Hz, 1H), 7.55−7.51 (m, 1H), 7.44−
6
.38−6.36 (d, J = 8.0 Hz, 1H), 2.56 (s, 3H). C NMR (100 MHz,
CDCl ) δ 157.1, 135.5, 135.1, 134.3, 132.7, 130.3, 129.5, 128.6, 127.9,
13
7
1
3
=
[
.37 (m, 4H), 7.11−7.05 (m, 3H). C NMR (100 MHz, CDCl ) δ
3
3
57.2, 140.5, 135.2, 133.4, 129.6, 128.3, 128.2, 128.5−127.5 (q, J =
2.5 Hz), 126.03−125.93 (m), 126.0, 124.3, 124.1, 128.0−120.0 (q, J
1
26.7, 125.4, 124.7, 124.6, 123.8, 116.9, 107.3, 20.0. HRMS (ESI): m/z
+
calcd for C H OS [M + H] , 267.0838; found, 267.0839.
17
15
270.1 Hz), 117.0, 106.5. HRMS (ESI): m/z calcd for C H F OS
17 12 3
1
-((2,5-Dimethylphenyl)thio)naphthalen-2-ol (3ad). Yellow
+
M + H] , 321.0556; found, 321.0559.
-(Thiophen-2-ylthio)naphthalen-2-ol (3am). Yellow solid
1
solid (75.6 mg, 90% yield); mp 58−60 °C. H NMR (400 MHz,
1
CDCl ) δ 8.15−8.12 (d, J = 12.0 Hz, 1H), 7.91−7.89 (d, J = 8.0 Hz,
1
3
(
65.8 mg, 85% yield); mp 54−56 °C. H NMR (400 MHz, CDCl )
3
1
(
1
1
1
H), 7.81−7.79 (d, J = 8.0 Hz, 1H), 7.48−7.44 (m, 1H), 7.37−7.33
δ 8.46−8.44 (d, J = 8.0 Hz, 1H), 7.83−7.80 (d, J = 1.20 Hz, 1H),
m, 2H), 7.08−7.04 (m, 2H), 6.81−6.79 (d, J = 8 Hz, 1H), 6.21(s,
7
1
6
1
.77−7.75 (d, J = 8.0 Hz, 1H), 7.58−7.54 (m, 1H), 7.38−7.34 (m,
H), 2.53 (s, 3H), 1.97 (s, 3H). 13C NMR (100 MHz, CDCl ) δ
3
H), 7.28−7.23 (m, 2H), 7.15−7.13 (m, 1H), 7.10−7.09 (m, 1H),
57.1, 136.4, 135.6, 133.9, 132.7, 132.2, 130.2, 129.5, 128.5, 127.8,
26.4, 125.3, 124.7, 123.8, 116.9, 107.6, 21.0, 19.6. HRMS (ESI): m/z
calcd for C H OS [M + H] , 281.0995; found,281.0998.
13
.86−6.83 (m, 1H). C NMR (100 MHz, CDCl ) δ 156.0, 134.8,
3
33.8, 132.7, 130.6, 129.5, 128.6, 127.8, 127.7, 127.4, 124.5, 123.8,
+
+
18
17
116.9, 111.6. HRMS (ESI): m/z calcd for C H OS [M + H] ,
14
11
2
1
-((4-(tert-Butyl)phenyl)thio)naphthalen-2-ol (3ae). Yellow
2
59.0246; found, 259.0249.
-(p-Tolylthio)naphthalene-2,7-diol (3bb). Yellow solid (66.0
1
solid (73.9 mg, 80% yield); mp 71−72 °C. H NMR (400 MHz,
1
CDCl ) δ 8.16 (s, 1H), 7.81−7.79 (d, J = 8.0 Hz, 1H), 7.72−7.70 (d, J
1
3
mg, 78% yield); mp 71−73 °C. H NMR (400 MHz, CDCl ) δ 7.79−
3
=
3
8.0 Hz, 1H), 7.43−7.38 (m, 1H), 7.29−7.23 (m, 2H), 7.15−7.09 (m,
7
.77 (d, J = 8.0 Hz, 1H), 7.69−7.67 (d, J = 8.0 Hz, 1H), 7.52−7.51 (d,
13
H), 6.91−6.87 (m, 2H), 1.14 (s, 9H). C NMR (100 MHz, CDCl )
3
J = 4.0 Hz, 1H), 7.19−7.14 (m, 2H), 6.98−6.90 (m, 5H), 5.37 (s, 1H),
δ 156.9, 149.1, 135.6, 132.6, 131.8, 129.5, 128.5, 127.9, 126.3, 126.2,
24.8, 123.8, 116.8, 108.6, 34.4, 31.2. HRMS(ESI) m/z calcd for
2
1
.23 (s, 3H). 13C NMR (100 MHz, CDCl ) δ 157.5, 155.5, 137.3,
3
1
35.8, 132.5, 131. 6, 130.7, 123.0, 126.4, 124.7, 115.2, 114.2, 107.3,
+
+
C H OS [M + H] , 309.1308; found, 309.1310.
0
2
21
107.0, 20.8. HRMS (ESI): m/z calcd for C H O S [M + H] ,
17
15
2
1
-((4-Methoxyphenyl)thio)naphthalen-2-ol (3af). Yellow solid
2
83.0788; found, 287.0790.
4-(p-Tolylthio)naphthalene-1,3-diol (3cb). Yellow solid (36.4
1
(
66.0 mg, 78% yield); mp 68−70 °C. H NMR (400 MHz, CDCl ) δ
3
1
8
7
7
3
1
.27−8.25 (d, J = 8.0 Hz, 1H), 7.86−7.84 (d, J = 8.0 Hz, 1H), 7.79−
.77 (d, J = 8.0 Hz, 1H), 7.51−7.46 (m, 1H), 7.36−7.29 (m, 3H),
.04−7.02 (d, J = 8 Hz, 2H), 6.72−6.70 (d, J = 8 Hz, 2H), 3.69 (s,
mg, 43% yield); mp 75−77 °C. H NMR (400 MHz, CDCl ) δ 8.11−
3
8.06 (m, 2H), 7.43−7.39 (m, 1H), 7.29−7.25 (m, 1H), 7.17−7.15 (d, J
= 8.0 Hz, 1H), 6.91−6.83 (m, 4H), 6.62 (s, 1H), 5.90 (s, 1H), 2.15 (s,
H). 13C NMR (100 MHz, CDCl ) δ 158.4, 156.7, 135.3, 132.5, 129.5,
13
3
3H). C NMR (100 MHz, CDCl ) δ 157.5, 155.3, 136.4, 135.6, 132.5,
3
28.7, 128.5, 127.8, 125.9, 124.7, 123.7, 116.8, 114.9, 109.7, 55.3.
129.9, 128.6, 126.2, 124.6, 123.2, 122.3, 121.2, 100.3, 99.7, 20.8.
+
+
HRMS (ESI): m/z calcd for C H O S [M + H] , 283.0788; found,
HRMS (ESI): m/z calcd for C H O S [M + H] , 283.0788; found,
17
15
2
17 15
2
2
83.0789.
283.0791.
D
dx.doi.org/10.1021/jo501778h | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
6
-Bromo-1-(p-tolylthio)naphthalen-2-ol (3db). Yellow solid
2H), 4.65 (s, 2H), 3.62 (s, 3H). 13C NMR (100 MHz, CDCl ) δ
157.8, 148.2, 136.6, 131.5, 128.4, 128.3, 127.9, 127.7, 127.5, 124.3,
3
1
(
53.7 mg, 52% yield); mp 112−114 °C. H NMR (400 MHz, CDCl )
3
δ 8.01−7.99 (d, J = 8 Hz, 1H), 7.85−7.84 (d, J = 4.0 Hz, 1H), 7.69−
.67 (d, J = 8.0 Hz, 1H), 7.45−7.42 (m, 1H), 7.26−7.23 (d, J = 12.0
Hz, 1H), 7.12 (s, 1H), 6.90−6.88 (d, J = 8.0 Hz, 2H), 6.84−6.82 (d, J
8.0 Hz, 2H), 2.15(s, 3H). 13C NMR (100 MHz, CDCl ) δ 157.1,
122.5, 117.6, 114.8, 106.2, 55.3. HRMS (ESI): m/z calcd for
+
7
C H NOS [M + H] , 282.0947; found, 282.0950.
17
16
1-((3-Fluorophenyl)thio)naphthalen-2-amine (5ae). Red solid
1
=
(64.6 mg, 80% yield); mp 113−115 °C. H NMR (400 MHz, CDCl )
3
3
1
1
+
36.2, 134.0, 131.5, 131.3, 131.0, 130.5, 130.4, 130.0, 126.8, 126.7,
18.0, 117.6, 109.2, 20.9. HRMS (ESI): m/z calcd for C H BrOS [M
δ 8.13−8.11 (d, J = 8.0 Hz, 1H), 7.67−7.61 (m, 2H), 7.36−7.32 (m,
1H), 7.19−7.12 (m, 1H), 7.03−6.98 (m, 1H), 6.93−6.91 (d, J = 8.0
Hz, 1H), 6.74−6.72 (m, 1H), 6.66−6.64 (m, 1H), 6.62−6.55 (m, 1H),
17
14
+
H] , 344.9943; found, 344.9945.
2-Methoxynaphthalen-1-yl)(p-tolyl)sulfane (3eb). Yellow
4.60 (s, 2H). 13C NMR (100 MHz, CDCl ) δ 164.4−162.0 (d, J =
(
3
1
solid (51.2 mg, 61% yield); mp 57−59 °C. H NMR (400 MHz,
246.1 Hz), 148.6, 139.5−139.4 (d, J = 7.5 Hz), 136.4, 132.2, 130.2−
130.1 (d, J = 8.5 Hz), 128.4, 128.3, 127.9, 123.9, 122.7, 121.4−121.4
(d, J = 2.8 Hz), 117.6, 112.8−112.5 (d, J = 24.0 Hz), 112.1−111.9 (d, J
CDCl ) δ 8.41−8.38 (d, J = 8.0 Hz, 1H), 7.84−7.82 (d, J = 8.0 Hz,
3
1
(
(
H), 7.71−7.69 (d, J = 8.0 Hz, 1H), 7.40−7.37 (m, 1H), 7.28−7.22
13
+
m, 2H), 6.87−6.82(m, 4H), 3.84 (s, 3H), 2.12 (s, 3H). C NMR
= 21.3 Hz), 103.6. HRMS (ESI): m/z calcd for C H FNS [M + H] ,
16
13
100 MHz, CDCl ) δ 159.2, 136.3, 134.5, 131.8, 129.5, 129.4, 128.2,
270.0747; found, 270.0751.
3
1
27.6, 126.7, 125.5, 124.0, 113.7, 113.5, 56.9, 20.8. HRMS (ESI): m/z
1-((4-Chlorophenyl)thio)naphthalen-2-amine (5af). Red solid
+
1
calcd for C H OS [M + H] , 281.0995; found, 281.0998.
(71.8 mg, 84% yield); mp 123−125 °C. H NMR (400 MHz, CDCl )
18
17
3
(
2-Ethoxynaphthalen-1-yl)(p-tolyl)sulfane (3fb). Yellow solid
δ 8.13−8.10 (d, J = 8.0 Hz, 1H), 7.65−7.60 (m, 2H), 7.35−7.31 (m,
1H), 7.18−7.12 (m, 1H), 7.01−6.99 (m, 2H), 6.92−6.90 (d, J = 8.0
1
(
64.4 mg, 73% yield); mp 63−65 °C. H NMR (400 MHz, CDCl ) δ
3
13
8
7
7
3
1
1
.45−8.43 (d, J = 8.0 Hz, 1H), 7.83−7.81 (d, J = 8.0 Hz, 1H), 7.73−
.71(d, J = 8.0 Hz, 1H), 7.43−7.39 (m, 1H), 7.31−7.27 (m, 1H),
.24−7.17 (m, 1H), 6.92−6.85 (m,4H), 4.12−4.07 (m, 2H), 2.15 (s,
Hz, 1H), 6.84−6.81 (m, 2H), 4.58 (s, 2H). C NMR (100 MHz,
CDCl ) δ 148.5, 136.4, 135.4, 132.0, 130.8, 129.0, 128.4, 128.3, 127.9,
3
127.1, 123.9, 122.7, 117.6, 104.0. HRMS (ESI): m/z calcd for
13
+
H), 1.25−1.22 (m, 3H). C NMR (100 MHz, CDCl ) δ 158.5,
36.3, 134.8, 134.6, 131.4, 129.6, 129.4, 128.2, 127.4, 127.2, 125.6,
24.0, 115.1, 65.5, 20.9, 14.9. HRMS (ESI): m/z calcd for C H OS
C H ClNS [M + H] , 286.0452; found, 286.0454.
3
16 13
1-((2-Chlorophenyl)thio)naphthalen-2-amine (5ag). Red solid
1
19
19
(62.4 mg, 73% yield); mp 115−117 °C. H NMR (400 MHz, CDCl )
3
+
[
M + H] , 295.1151; found, 295.1154.
-(p-Tolylthio)-5,6,7,8-tetrahydronaphthalen-2-ol (3gb).
δ 8.11−8.09 (d, J = 8.0 Hz, 1H), 7.69−7.62 (m, 2H), 7.36−7.27 (m,
1
1H), 7.26−7.25 (d, J = 4.0 Hz, 1H), 7.19−7.14(m, 1H), 6.96−6.87
1
13
White solid (29.4 mg, 36% yield); mp 53−55 °C. H NMR (400
(m, 2H), 6.81−6.77 (m, 1H), 6.34−6.32 (m, 1H), 4.60 (s, 2H).
C
MHz, CDCl ) δ 7.18−7.14 (d, J = 16.0 Hz, 1H), 6.98−6.92 (m, 4H),
NMR (100 MHz, CDCl ) δ 148.8, 136.5, 135.6, 132.2, 131.3, 129.5,
3
3
6
1
.68 (s, 1H), 6.18 (s, 1H), 2.68−2.60 (m, 4H), 2.20 (s, 3H), 1.71−
128.4, 128.0, 127.1, 125.9, 125.7, 124.0, 122.7, 117.6, 102.9. HRMS
.68 (m, 4H). 13C NMR (100 MHz, CDCl ) δ 154.6, 141.8, 136.8,
+
3
(ESI): m/z calcd for C H ClNS [M + H] , 286.0452; found,
16 13
1
2
35.9, 132.8, 130.1, 129.9, 127.2, 115.1, 113.8, 29.5, 28.4, 23.2, 22.9,
286.0453.
+
0.9. HRMS (ESI): m/z calcd for C H OS [M + H] , 271.1151;
1-((4-Bromophenyl)thio)naphthalen-2-amine (5ah). Red solid
17
19
1
found, 271.1154.
(84.9 mg, 86% yield); mp 119−121 °C. H NMR (400 MHz, CDCl )
3
4
-(p-Tolylthio)naphthalen-1-ol (3hb). Yellow solid (57.5 mg,
δ 8.10−8.08 (d, J = 8.0 Hz, 1H), 7.62−7.57 (m, 2H), 7.33−7.29 (m,
1H), 7.16−7.10 (m, 3H), 6.88−6.85(d, J = 8.0 Hz, 1H), 6.75−6.73 (d,
1
7
2% yield); mp 73−75 °C. H NMR (400 MHz, CDCl ) δ 8.27−8.25
3
J = 8.0 Hz, 2H), 4.54 (s, 2H). 13C NMR (100 MHz, CDCl ) δ 148.4,
(
m, 1H), 8.16−8.13 (m, 1H), 7.57−7.55 (d, J = 8.0 Hz, 1H), 7.45−
.39 (m, 2H), 6.92−6.87 (m, 4H), 6.70−6.68 (d, J = 8.0 Hz, 1H), 5.54
s, 1H), 2.15 (s, 3H). 13C NMR (100 MHz, CDCl ) δ 152.9, 135.4,
3
7
(
136.3, 136.1, 132.0, 131.9, 128.4, 128.3, 127.9, 127.4, 123.9, 122.6,
3
118.5, 117.5, 103.8. HRMS (ESI): m/z calcd for C H BrNS [M +
16 13
+
1
1
2
35.2, 134.9, 134.8, 129.7, 127.6, 127.5, 126.1, 125.7, 125.3, 122.2,
21.6, 108.8, 20.9. HRMS (ESI): m/z calcd for C H OS [M + H] ,
67.0838; found, 267.0839..
-(Phenylthio)naphthalen-2-amine (5aa). Red solid (52.7 mg,
H] , 329.9947; found, 329.9949.
+
17
15
1-((4-(Trifluoromethyl)phenyl)thio)naphthalen-2-amine
1
(5ai). Red solid (85.2 mg, 89% yield); mp 116−118 °C. H NMR
1
(400 MHz, CDCl ) δ 8.09−8.07 (d, J = 8.0 Hz, 1H), 7.69−7.62 (m,
3
1
7
8
7
2
1
0% yield); mp 99−101 °C. H NMR (400 MHz, CDCl ) δ 8.19−
2H), 7.36−7.32 (m, 1H), 7.29−7.27 (d, J = 8.0 Hz, 2H), 7.20−7.12
3
13
.17 (d, J = 8.0 Hz, 1H), 7.65−7.60 (m, 2H), 7.35−7.31 (m, 1H),
.18−7.12 (m, 1H), 7.06−7.03 (m, 2H), 6.97−6.91 (m, 4H), 4.59 (s,
(m, 1H), 6.98−6.92 (m, 3H), 4.59 (s, 2H). C NMR (100 MHz,
CDCl ) δ 148.6, 142.1, 136.4, 132.4, 128.5, 128.4, 128.1, 127.1 (q, J =
3
H). 13C NMR (100 MHz, CDCl ) δ 148.4, 136.8, 136.6, 131.8, 128.9,
3
32.5 Hz), 125.7 (q, J = 3.9 Hz), 125.5, 123.8, 122.8, 117.6, 102.8.
+
28.4, 128.3, 127.7, 125.8, 125.0, 124.2, 122.5, 117.6, 104.6. HRMS
HRMS (ESI): m/z calcd for C H F NS [M + H] , 320.0716; found,
17
13 3
+
(
ESI): m/z calcd for C H NS [M + H] , 252.0842; found, 252.0845.
320.0718.
16
14
1
-(p-Tolylthio)naphthalen-2-amine (5ab). Red solid (66.8 mg,
1-(Thiophen-2-ylthio)naphthalen-2-amine (5ak). Red solid
1
1
8
8
7
4% yield); mp 113−115 °C. H NMR (400 MHz, CDCl ) δ 8.20−
(50.1 mg, 66% yield); mp 109−110 °C. H NMR (400 MHz,
3
.18 (d, J = 8.0 Hz, 1H), 7.62−7.58 (m, 2H), 7.34−7.29 (m, 1H),
.16−7.12 (m, 1H), 6.90−6.81 (m, 5H), 4.56 (s, 2H), 2.12 (s, 3H).
CDCl ) δ 8.42−8.40 (d, J = 8.0 Hz, 1H), 7.62−7.60 (d, J = 8.0 Hz,
3
2H), 7.45−7.41 (m, 1H), 7.21−7.17 (m, 1H), 7.04−7.03 (m, 1H),
6.97−6.96 (m, 1H), 6.92−6.90 (d, J = 8.0 Hz, 1H), 6.79−6.77 (m,
1
3
C NMR (100 MHz, CDCl ) δ 148.3, 136.6, 134.8, 133.2, 131.6,
3
1H), 4.75 (s, 2H). 13C NMR (100 MHz, CDCl
) δ 147.6, 136.0,
1
29.7, 128.3, 128.2, 127.7, 126.0, 124.2, 122.5, 117.6, 105.2, 20.8.
HRMS (ESI): m/z calcd for C H NS [M + H] , 266.0998; found,
3
+
135.9, 131.7, 129.0, 128.4, 128.3, 127.7, 127.2, 126.6, 124.1, 122.5,
17
16
+
2
66.0999.
-((2,5-Dimethylphenyl)thio)naphthalen-2-amine (5ac). Red
117.7, 108.2. HRMS (ESI): m/z calcd for C14H12NS [M + H] ,
2
1
258.0406; found, 258.0410.
1
solid (58.6 mg, 70% yield); mp 60−62 °C. H NMR (400 MHz,
4-(p-Tolylthio)naphthalen-1-amine (5cb). Red solid (50.9 mg,
1
CDCl ) δ 8.15−8.13 (d, J = 8.0 Hz, 1H), 7.70−7.64 (m, 2H), 7.36−
64% yield); mp 75−78 °C. H NMR (400 MHz, CDCl ) δ 7.74−7.70
3
3
7
=
.32(m, 1H), 7.21−7.17 (m, 1H), 7.00−6.96 (m, 2H), 6.72−6.70 (d, J
(m, 2H), 7.44−7.37 (m, 3H), 7.18−7.16 (d, J = 8.0 Hz, 1H), 6.93 (s,
4H), 4.90 (s, 2H), 2.18 (s, 3H). C NMR (100 MHz, CDCl ) δ
8.0 Hz, 1H), 6.19 (s, 1H), 2.43 (s, 3H), 1.92 (s, 3H). 13C NMR (100
MHz, CDCl ) δ 148.5, 136.8, 136.1, 135.1, 131.9, 131.6, 130.0, 128.5,
13
3
145.4, 135.3, 134.9, 133.5, 133.4, 129.8, 128.6, 126.9, 126.8, 125.3,
3
1
28.3, 127.7, 125.6, 124.7, 124.3, 122.5, 117.6, 104.3, 21.1, 19.6.
123.2, 121.5, 118.5, 109.0, 20.9. HRMS (ESI): m/z calcd for
+
+
HRMS (ESI): m/z calcd for C H NS [M + H] , 280.1155; found,
C H NS [M + H] , 266.0998; found, 266.0995.
18
18
17 16
2
80.1158.
-((4-Methoxyphenyl)thio)naphthalen-2-amine (5ad). Red
1,2-Di-p-tolyldisulfane (6). Yellow solid; mp 47−49 °C. 1H
1
NMR (400 MHz, CDCl ) δ 7.41−7.39 (d, J = 8.0 Hz, 4H), 7.13−7.11
3
1
13
solid (48.1 mg, 57% yield); mp 101−105 °C. H NMR (400 MHz,
(d, J = 8.0 Hz, 4H), 2.34 (s, 6H). C NMR (100 MHz, CDCl ) δ
3
CDCl ) δ 8.25−8.23 (d, J = 8.0 Hz, 1H), 7.65−7.61 (m, 2H), 7.38−
137.4, 133.9, 129.8, 128.6, 21.0. HRMS (ESI): m/z calcd for C H S
3
14 15 2
+
7
.34 (m, 1H), 7.19−7.15 (m, 1H), 6.95−6.92 (m, 3H), 6.65−6.62 (m,
[M + H] , 247.0610; found, 247.0611.
E
dx.doi.org/10.1021/jo501778h | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
S-(p-Tolyl)4-methylbenzenesulfonothioate (7). White solid;
(7) (a) Yang, F.-L.; Wang, F.-X.; Wang, T.-T.; Wang, Y.-J.; Tian, S.-K.
Chem. Commun. 2014, 50, 2111. (b) Yang, F.-L.; Ma, X.-T.; Tian, S.-K.
Chem.Eur. J. 2012, 18, 1582. (c) Wang, T.-T.; Wang, F.-X.; Yang, F.-
L.; Tian, S.-K. Chem. Commun. 2014, 50, 3802.
(8) (a) Guo, S.-R.; Yuan, Y.-Q.; Xiang, J.-N. Org. Lett. 2013, 15, 4654.
(b) Tang, R.-Y.; Xie, Y.-X.; Xie, Y.-L.; Xiang, J.-N.; Li, J.-H. Chem.
Commun. 2011, 47, 12867.
1
mp 76−78 °C. H NMR (400 MHz, CDCl ) δ 7.47−7.45 (d, J = 8.0
3
Hz, 2H), 7.26−7.20 (m, 4H), 7.15−7.13 (d, J = 8.0 Hz, 2H), 2.42 (s,
3
1
H), 2.38(s, 3H). 13C NMR (100 MHz, CDCl ) δ 144.6, 142.0, 140.5,
3
36.5, 130.2, 129.3, 127.6, 124.6, 21.6, 21.4. HRMS (ESI): m/z calcd
+
for C H O S [M + H] , 279.0508; found, 279.0511.
14
15
2 2
(
9) Xiao, F.; Xie, H.; Liu, S.; Deng, G. Adv. Synth. Catal. 2014, 356,
ASSOCIATED CONTENT
■
3
64.
*
S
Supporting Information
(10) Yang, F.-L.; Tian, S.-K. Angew. Chem., Int. Ed. 2013, 52, 4929.
1
H and 13C NMR spectra of all compounds. This material is
(11) (a) Yan, R.- L.; Yan, H.; Ma, C.; Ren, Z.- Y.; Gao, X.- A.; Huang,
available free of charge via the Internet at http://pubs.acs.org.
G.- S.; Liang, Y.- M. J. Org. Chem. 2012, 77, 2024. (b) Yan, R.; Liu, X.;
Pan, C.; Zhou, X.; Li, X.; Kang, X.; Huang, G. Org. Lett. 2013, 15,
4
876.
AUTHOR INFORMATION
■
Corresponding Authors
*
(R.Y.) E-mail: yanrl@lzu.edu.cn. Fax: +86 931 8912596. Tel.:
86 931 8912586.
(G.H.) E-mail: hgs@lzu.edu.cn.
+
*
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by the National Natural Science
Foundation of China (21202067) and the Fundamental
Research Funds for the Central Universities (lzujbky-2014-71).
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dx.doi.org/10.1021/jo501778h | J. Org. Chem. XXXX, XXX, XXX−XXX