Palladium-Catalyzed Oxidative Cross-Coupling of Arylhydrazines and Arenethiols with Molecular Oxygen as the Sole Oxidant

Article abstract of DOI:10.1021/acs.joc.7b02926

A highly efficient palladium-catalyzed oxidative cross-coupling of arylhydrazines and arenethiols with molecular oxygen as the sole oxidant to afford unsymmetrical diaryl sulfides has been developed. The only byproducts are nitrogen and water. A broad range of functional groups, even the reactive iodides, are tolerated and thus offer the opportunity for further functionalization.

Full text of DOI:10.1021/acs.joc.7b02926

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Note
Palladium-Catalyzed Oxidative Cross-Coupling of Arylhydrazines
and Arenethiols with Molecular Oxygen as the Sole Oxidant
Changliu Wang, Zhenming Zhang, Yongliang Tu, Ying Li, Jiale Wu, and Junfeng Zhao
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.7b02926 • Publication Date (Web): 16 Jan 2018
Downloaded from http://pubs.acs.org on January 16, 2018
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Page 1 of 6
The Journal of Organic Chemistry
Palladium-Catalyzed Oxidative Cross-Coupling of Arylhydra-
zines and Arenethiols with Molecular Oxygen as the Sole Oxidant
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Changliu Wang, Zhenming Zhang, Yongliang Tu, Ying Li, Jiale Wu, Junfeng Zhao**
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Key Laboratory of Chemical Biology of Jiangxi Province, College of Chemistry and Chemical Engineering, Jiangxi Normal
University, Nanchang, 330022, P. R. China
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Supporting Information
ABSTRACT: A highly efficient palladiumꢀcatalyzed oxidaꢀ
tive crossꢀcoupling of arylhydrazines and arenethiols with
molecular oxygen as the sole oxidant to afford unsymmetrical
diaryl sulfides has been developed. The only byꢀproducts are
nitrogen and water. A broad range of functional groups, even
the reactive iodides are tolerated and thus offering opportuniꢀ
ty for further functionalization.
Transition metalꢀcatalyzed oxidative crossꢀcoupling reacꢀ
tions have emerged as powerful and general tools for carbonꢀ
carbon and carbonꢀheteroatom bonds formation during the
past decade.1 However, among these reactions, the formation
of carbonꢀsulfur bond via oxidative crossꢀcoupling of thiols
has attracted less attention2 due to the homo coupling of thiols
under the oxidative reaction conditions.3 In addition, diaryl
sulfides are of great importance as building block in biologiꢀ
cally active molecules,4 pharmaceutical,5 and natural prodꢀ
ucts.6 As a consequence, their syntheses have attracted considꢀ
erable attention.7 Recently, transition metalꢀcatalyzed tradiꢀ
tional crossꢀcoupling reactions have been developed to conꢀ
struct sp2 CꢀS bond.8 Although significant advances have been
made along these lines, the development of efficient synthetic
methodologies for diaryl sulfides via palladiumꢀcatalyzed oxiꢀ
dative crossꢀcoupling still remains a challenging topic.
The palladiumꢀcatalyzed crossꢀcoupling reaction of aryl thiꢀ
ols with different electrophiles represents one of the most
straightforward tools to afford a variety of unsymmetrical diꢀ
aryl sulfides (Scheme 1, eq 1).9 These classic methods for
carbonꢀsulfur bond formation involve an additionꢀelimination
mechanism by using Pd(0) as catalyst. However, these methꢀ
ods are usually limited in substrate scope and require harsh
reaction conditions.10 Compared with Pd(0) catalyzed reacꢀ
tions carried out under inert atmosphere, Pd(II) catalyzed couꢀ
pling reactions are relatively easy to handle.11 Recently,
Pd(II)ꢀcatalyzed decarboxylative crossꢀcoupling reaction of
benzoic acids with thiols or disulfides using Ag or Cu salts as
oxidant to afford diaryl sulfides derivatives is reported
(Scheme 1, eq 2).12 Herein, we disclosed a novel and efficient
Pd(II)ꢀcatalyzed oxidative crossꢀcoupling reaction of arylhyꢀ
drazines with aryl thiols using O2 as the sole oxidant to give
unsymmetrical diaryl sulfides (Scheme 1, eq 3).
amines.14 Based on these works, we envisioned that aryl thiols
could also react with arylhydrazines to afford the
Scheme 1. Synthetic strategies for diaryl sulfides via palla-
dium-catalyzed cross-coupling of arenethiols
corresponding diaryl sulfides through palladiumꢀcatalyzed
oxidative crossꢀcoupling. With this proposal in mind, we startꢀ
ed from testing different palladium catalysts in the oxidative
coupling of phenylhydrazine 1a and 4ꢀmethoxybenzenethiol
2a with 10 mol % of PPh3, 2 equiv of Na2CO3 in dimethyl
o
sulfoxide (DMSO) at 100 C for 12 h under balloon pressure
of O2 (Table 1). Preliminary screening revealed that Pd(OAc)2
was most effective for this transformation (Table 1, entries 1ꢀ
6). Further exploration of ligands disclosed that the ligand is
crucial and PCy3 gave the best yield (Table 1, entries 7ꢀ12).
Base also played an important role in this reaction and Na2CO3
was identified to be the best one among others (Table 1, enꢀ
tries 13ꢀ17). In addition, toluene demonstrated a beneficial
effect on this reaction (Table 1, entries 18ꢀ20). Decrease of
reaction temperature has a deleterious effect on the reaction
efficiency (Table 1, entry 21). As expected, there is no reacꢀ
tion at all when the experiment was performed under N2 atꢀ
mosphere (Table 1, entry 23).
Arylhydrazines have evolved into environmentally friendly
arylation agents for the palladiumꢀcatalyzed oxidative crossꢀ
coupling reactions because the only side products are water
and nitrogen.13 Our group is interested in CꢀN bond cleavage
of arylhydrazines and reported the palladium catalyzed oxidaꢀ
tive carbonylation of arylhydrazines with alkynes, phenols and
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Table 1. Optimization of the Reaction Conditionsa
Scheme 2. Substrate Scope of Arylhydrazinesa
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yield
(%)b
entry catalyst
ligand
base
solvent
1
PdCl2(PPh3)2 PPh3
PdCl2(dppf) PPh3
Na2CO3 DMSO
Na2CO3 DMSO
Na2CO3 DMSO
Na2CO3 DMSO
Na2CO3 DMSO
Na2CO3 DMSO
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51
58
43
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70
27
77
47
53
64
trace
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75
27
38
30
82
46
67
60
25
trace
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3
Pd(PPh3)4
Pd2(dba)3
Pd(TFA)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
PPh3
PPh3
PPh3
PPh3
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5
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7
P(oꢀTol)3 Na2CO3 DMSO
PCy3 Na2CO3 DMSO
P(2ꢀfuryl)3 Na2CO3 DMSO
Binap Na2CO3 DMSO
1,10ꢀPhen Na2CO3 DMSO
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aReaction conditions: 1 (0.4 mmol), 2a (0.2 mmol), Pd(OAc)2 (5
mol%), PCy3 (10 mol%), Na2CO3 (0.4 mmol), PhMe (2.0 mL) under
O2 balloon at 100 oC for 12 h.
ꢀꢀ
Na2CO3 DMSO
Cs2CO3 DMSO
PCy3
PCy3
PCy3
PCy3
PCy3
PCy3
PCy3
PCy3
PCy3
PCy3
PCy3
K2CO3
NaOH
Et3N
DMSO
DMSO
DMSO
DMSO
Next, the palladiumꢀcatalyzed oxidative crossꢀcoupling reꢀ
actions of (4ꢀnitrophenyl)hydrazine hydrochloride (1n) with a
variety of aryl thiols were also examined and the results are
summarized in Scheme 3. Aryl thiols with a series of electronꢀ
donating groups, such as 4ꢀmethyl, 4ꢀethyl, 4ꢀtꢀbutyl, 3ꢀ
methoxy and 3,5ꢀdimethyl, could convert to the corresponding
products (3nbꢀ3ng) in good to high yields. Interestingly, the
DBU
Na2CO3 PhMe
Na2CO3 DMF
Na2CO3 CF3Ph
Na2CO3 PhMe
Na2CO3 PhMe
Na2CO3 PhMe
Scheme 3. Substrate Scope of Arenethiolsa
21 c Pd(OAc)2
22 d Pd(OAc)2
23 e Pd(OAc)2
aReaction condition: 1a (0.4 mmol), 2a (0.2 mmol), base (0.4 mmol),
Pd catalyst (5 mol %), ligand (10 mol %), solvent (2.0 mL) at 100 oC
for 12 h, with a O2 balloon. bIsolated yield. c60 oC. dUnder air. eUnder
N2.
With the optimized reaction conditions in hand (Table 1,
entry 18), we explored the scope of this oxidative crossꢀ
coupling reaction between various arylhydrazines and 4ꢀ
methoxybenzenethiol. As shown in Scheme 2, a broad range
of arylhydrazines with ortho, meta, or para alkyl substituents
reacted equally well with 4ꢀmethoxybenzenethiol 2a to afford
the corresponding products (3baꢀ3fa) in 77ꢀ84% yields. Even
the steric demanding dimethyl substituents were tolerated to
furnish the desired products (3ga and 3ha) in high yields. It
should be noted that the reaction could be conducted in the
presence of halogen substituents (3iaꢀ3la) and the carbonꢀ
halogen bonds, which are reactive under conventional palladiꢀ
um catalyzed crossꢀcoupling conditions, were intact. Moreover,
diaryl sulfides containing strong electronꢀwithdrawing (3na)
substituent could also be prepared by using this method. In
addition, (4ꢀ(trifluoromethoxy)phenyl)hydrazine and naphthaꢀ
lenꢀ2ꢀylhydrazine could afford the coupling products (3ma
and 3oa) in high yields. Disappointingly, no target products
were obtained when heterocyclic hydrazines were used.
aReaction conditions: 1n (0.4 mmol), 2 (0.2 mmol), Pd(OAc)2 (5
mol%), PCy3 (10 mol%), Na2CO3 (0.4 mmol), PhMe (2.0 mL) under
O2 balloon at 100 oC for 12 h.
halogen substituents such as ꢀCl, and ꢀBr, could be tolerated in
this reaction and afforded the diaryl sulfides products (3nh
and 3ni) in 79% and 83% yields, respectively, and thus offerꢀ
ing an advantage for further manipulation by conventional
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coupling reaction. Then, (4ꢀ(trifluoromethoxy)phenyl)ꢀ
ger (Scheme 5, eq 3). All of these experiments indicating that
a radical pathway was not likely to be involved in this reaction.
A possible reaction mechanism for the palladiumꢀcatalyzed
oxidative crossꢀcoupling reaction of arylhydrazines with areꢀ
nethiols was proposed in Scheme 6. Aryl palladium species A
was initially produced by the oxidative CꢀN bond cleavage of
arylhydrazine with Pd(OAc)2 under O2.13a On the other hand,
arenethiols reacted with base to yield the benzenethiolate inꢀ
termediate B. Then, the active palladium species C might be
formed through transmetallation of species A with intermediꢀ
ate B. Finally, reductive elimination affords the coupling
product D and regenerated the Pd catalyst to close the catalytic
cycle.
1
2
3
4
5
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hydrazine and naphthalenꢀ2ꢀylhydrazine were also converted
to the coupling products (3nj and 3nk) in good yields. Howꢀ
ever, no reaction occurred when 4ꢀnitrobenzenethiol (3nl) was
employed as substrate.
Scheme 4. Synthetic Application
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Scheme 6. Proposed Reaction Mechanism
The potential application of this oxidative crossꢀcoupling
reaction was illustrated in Scheme 4. The diaryl sulfide 3ka
could be prepared efficiently from the palladiumꢀcatalyzed
crossꢀcoupling of 1k and 2a (Scheme 4, path a). Interestingly,
the crossꢀcoupling of 2l and 1p could also offer the same diꢀ
aryl sulfide 3ka in good yield (Scheme 4, path b). Such feature
will be remarkably useful when one coupling partner is expenꢀ
sive or not available. Furthermore, product 3ka could effiꢀ
ciently undergo Hiyama reaction and Suzuki reaction to afford
the corresponding coupling product 6a in 77% and 85% yields,
respectively (Scheme 4, path c and d).
■ CONCLUSIONS
In summary, we have developed the first palladiumꢀcatalyzed
oxidative crossꢀcoupling of arylhydrazines and aryl thiols with O2
as the sole oxidant to afford diaryl sulfides in good to high yields.
A variety of functional groups including halide substituents which
are reactive under conventional transition metal catalyzed cross
coupling reaction conditions are tolerated. This method provides a
highly efficient approach to unsymmetrical diaryl sulfides.
Scheme 5. Control Experiments
■ EXPERIMENTAL SECTION
All reactions were carried out in ovenꢀdried glassware. All arꢀ
ylhydrazine hydrochloride and arenethiols were obtained from
commercial sources and used without further purification. All the
reactions were monitored by thinꢀlayer chromatography (TLC);
products were purified by using silica gel column chromatogꢀ
1
raphy. H/13C NMR spectra were recorded on Bruker avance 400
MHz and Bruker AMX 400 MHz spectrometer at 400/100 MHz,
respectively, in CDCl3. unless otherwise stated, using either TMS
or the undeuterated solvent residual signal as the reference.
Chemical shifts are given in ppm and are measured relative to
CDCl3 as an internal standard. Mass spectra were obtained by the
electrospray ionization timeꢀofꢀflight (ESIꢀTOF) mass spectromeꢀ
try. Flash column chromatography purification of compounds was
carried out by gradient elution using ethyl acetate (EA) in light
petroleum ether (PE).
To probe whether a transition metalꢀfree radical pathway
was involved in this reaction mechanism,15 several experiꢀ
ments were performed in Scheme 5. When 1a was treated with
2a in the absence of Pd catalyst, only small amount of the
desired product 3aa was obtained (Scheme 5, eq 1). A signifiꢀ
cant lower yield of 3aa was observed when disulfide 4a was
used under the standard conditions (Scheme 5, eq 2). Furtherꢀ
more, control experiment with 2,2,6,6ꢀtetramethylꢀ1ꢀ
piperidinyloxy (TEMPO) demonstrated that the reaction effiꢀ
ciency was kept intact in the presence of as the radical scavenꢀ
General procedure for the Preparation of unsym-
metrical diaryl sulfides: Arylhydrazine hydrochloride (0.4
mmol, 2.0 equiv), Pd(OAc)2 (1.1 mg, 0.01 mmol, 5 mol %), PCy3
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(5.6 mg, 0.02 mmol 10 mol %), and Na2CO3 (42.4 mg, 0.4 mmol,
13C NMR (100 MHz, CDCl3) δ 159.4, 137.4, 135.0, 134.4, 134.2,
130.8, 130.3, 127.1, 126.0, 114.9, 55.4, 19.7, 19.3; HRMS (ESIꢀ
TOF): calcd for C15H17OS [M + H]+: 245.0995, found: 245.0992.
(3,5ꢀDimethylphenyl)(4ꢀmethoxyphenyl)sulfane (3ha).17 Purifiꢀ
cation by chromatography (PE/EA = 100:1, v/v) afforded 3ha as a
2.0 equiv) were combined in an ovenꢀdried Schlenk tube equipped
with a stir bar. After the addition of all the solid reagent, the balꢀ
loon filled with O2 was connected to the Schlenk tube via a syꢀ
ringe. The Schlenk tube was heated at 100°C for 12 h. After the
reaction was completed (monitored by TLC), the contents were
cooled to room temperature and then the balloon gas was released.
The solvent was removed under reduced pressure to give crude
products, which were purified by column chromatography (inner
diameter: 3.0 cm and length: 30 cm) over silica gel (PE/ EA) to
afford pure products.
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colorless oil (37.6 mg, 77%); Rf = 0.50 (PE/EA = 50:1, v/v); IR
1
(KBr) ν
̃
2925, 2834, 1593, 1497, 1250, 1038, 832 cmꢀ1; H NMR
(400 MHz, CDCl3) δ 7.52−7.32 (m, 2H), 6.97−6.87 (m, 2H), 6.84
(s, 2H), 6.81 (d, J = 0.5 Hz, 1H), 3.83 (s, 3H), 2.25 (s, 6H); 13
C
NMR (100 MHz, CDCl3) δ 159.7, 138.6, 137.8, 135.0, 127.9,
126.3, 124.9, 114.9, 55.4, 21.2.
9
(4ꢀMethoxyphenyl)(phenyl)sulfane (3aa).16 Purification by
chromatography (PE/EA = 100:1, v/v) afforded 3aa as a pale yelꢀ
(4ꢀFluorophenyl)(4ꢀmethoxyphenyl)sulfane (3ia).17 Purification
by chromatography (PE/EA = 100:1, v/v) afforded 3ia as a colorꢀ
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low oil (35.4 mg, 82%); Rf = 0.40 (PE/EA = 50:1, v/v) ; IR (KBr)
less oil (33.2 mg, 71%); Rf = 0.60 (PE/EA = 50:1, v/v); IR (KBr)
1
2945, 2834, 1588, 1487, 1245, 1023, 826 cmꢀ1; H NMR (400
1
ν
̃
ν
̃
2940, 2834, 1588, 1493, 1420, 1033, 826; H NMR (400 MHz,
MHz, CDCl3) δ 7.41 (d, J = 8.8 Hz, 2H), 7.31−7.01 (m, 5H), 6.89
(d, J = 8.8 Hz, 2H), 3.80 (s, 3H). 13C NMR (100 MHz, CDCl3) δ
159.9, 138.6, 135.3, 128.9, 128.3, 125.8, 124.4, 115.0, 55.4.
(4ꢀMethoxyphenyl)(pꢀtolyl)sulfane (3ba).17 Purification by
chromatography (PE/EA = 100:1, v/v) afforded 3ba as a colorless
CDCl3) δ 7.35 (d, J = 8.8 Hz, 2H), 7.23−7.16 (m, 2H), 6.99−6.91
(m, 2H), 6.87 (d, J = 8.8 Hz, 2H), 3.80 (s, 3H); 13C NMR (100
MHz, CDCl3) δ 161.6 (d, JCF = 245.9 Hz), 159.7, 134.5, 133.1 (d,
JCF = 3.3 Hz), 131.1 (d, JCF = 8.0 Hz), 125.3, 116.1 (d, JCF = 22.0
Hz), 115.0, 55.4.
(4ꢀChlorophenyl)(4ꢀmethoxyphenyl)sulfane (3ja).17 Purification
by chromatography (PE/EA = 100:1, v/v) afforded 3ja as a colorꢀ
oil (35.4 mg, 77%); Rf = 0.60 (PE/EA = 50:1, v/v) ; IR (KBr) ν
̃
1
2936, 2839, 1593, 1497, 1244, 1032, 826 cmꢀ1; H NMR (400
MHz, CDCl3) δ 7.46−7.29 (m, 2H), 7.23−7.14 (m, 1H), 7.14−7.03
(m, 2H), 7.00 (d, J = 7.6, 1H), 6.95−6.82 (m, 2H), 3.82 (s, 3H),
less oil (37.0 mg, 74%); Rf = 0.60 (PE/EA = 50:1, v/v); IR (KBr)
1
ν
̃
3096, 2965, 1593, 1502, 1330, 1083, 851 cmꢀ1; H NMR (400
2.40 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 159.6, 137.2, 137.0,
134.5, 130.2, 129.2, 126.5, 126.2, 124.0, 115.01, 55.4, 20.3.
(4ꢀMethoxyphenyl)(mꢀtolyl)sulfane (3ca).17 Purification by
chromatography (PE/EA = 100:1, v/v) afforded 3ca as a colorless
MHz, CDCl3) δ 7.40 (d, J = 8.8 Hz, 2H), 7.19 (d, J = 8.7 Hz, 2H),
7.08 (d, J = 8.7 Hz, 2H), 6.91 (d, J = 8.8 Hz, 2H), 3.83 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 160.1, 137.4, 135.5, 131.7, 129.4,
129.0, 123.9, 115.2, 55.4.
(4ꢀBromophenyl)(4ꢀmethoxyphenyl)sulfane (3ka).17 Purification
by chromatography (PE/EA = 100:1, v/v) afforded 3ka as a yelꢀ
oil (38.7 mg, 79%); Rf = 0.45 (PE/EA = 50:1, v/v) ; IR (KBr) ν
̃
1
2925, 2834, 1588, 1497, 1250, 1028, 826 cmꢀ1; H NMR (400
MHz, CDCl3) δ 7.48−7.34 (m, 2H), 7.13 (t, J = 7.7 Hz, 1H), 7.03
(s, 1H), 6.97 (t, J = 6.7 Hz, 2H), 6.92−6.85 (m, 2H), 3.83 (s, 3H),
low oil (43.6 mg, 74%); Rf = 0.55 (PE/EA = 50:1, v/v); IR (KBr)
1
ν
̃
3091, 2960, 1593, 1502, 1335, 1084, 851 cmꢀ1; H NMR (400
2.28 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 159.8, 138.8, 138.2,
135.1, 129.1, 128.8, 126.8, 125.6, 124.7, 115.0, 55.4, 21.3.
(4ꢀMethoxyphenyl)(oꢀtolyl)sulfane (3da).16 Purification by
chromatography (PE/EA = 100:1, v/v) afforded 3da as a colorless
MHz, CDCl3) δ 7.41 (d, J = 8.8 Hz, 2H), 7.33 (d, J = 8.6 Hz, 2H),
7.01 (d, J = 8.6 Hz, 2H), 6.91 (d, J = 8.8 Hz, 2H), 3.83 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 160.1, 138.2, 135.6, 131.9, 129.5,
123.6, 119.4, 115.2, 55.4.
(4ꢀIodophenyl)(4ꢀmethoxyphenyl)sulfane (3la).18 Purification by
chromatography (PE/EA = 100:1, v/v) afforded 3la as a colorless
oil (41.2 mg, 84%); Rf = 0.50 (PE/EA = 50:1, v/v) ; IR (KBr) ν
̃
1
3011, 2920, 1593, 1492, 1244, 1028, 805 cmꢀ1; H NMR (400
MHz, CDCl3) δ 7.36 (d, J = 8.9 Hz, 2H), 7.14 (d, J = 8.2 Hz, 2H),
oil (56.3 mg, 77%); Rf = 0.60 (PE/EA = 50:1, v/v); IR (KBr) ν
̃
1
2936, 2830, 1593, 1492, 1250, 1033, 852 cmꢀ1; H NMR (400
7.07 (d, J = 8.1 Hz, 2H), 6.87 (d, J = 8.8 Hz, 2H), 3.81 (s, 3H),
2.31 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 159.5, 136.2, 134.3,
134.3, 129.8, 129.4, 125.7, 114.9, 55.4, 21.0.
(4ꢀEthylphenyl)(4ꢀmethoxyphenyl)sulfane (3ea). Purification by
chromatography (PE/EA = 100:1, v/v) afforded 3ea as a colorless
MHz, CDCl3) δ 7.52 (d, J = 8.5 Hz, 2H), 7.41 (d, J = 8.8 Hz, 2H),
6.89 (dd, J1 = 14.7, J2 = 8.7 Hz, 4H), 3.83 (s, 3H); 13C NMR (100
MHz, CDCl3) δ 160.2, 139.2, 137.8, 135.8, 129.6, 123.3, 115.2,
90.2, 55.4.
oil (41.2 mg, 84%); Rf = 0.60 (PE/EA = 50:1, v/v) ; IR (KBr) ν
̃
(4ꢀMethoxyphenyl)(4ꢀ(trifluoromethoxy)phenyl)sulfane
(3ma).17 Purification by chromatography (PE/EA = 100:1, v/v)
afforded 3ma as a colorless oil (48.0 mg, 80%); Rf = 0.60 (PE/EA
1
2965, 2839, 1593, 1492, 1245, 1032, 832 cmꢀ1; H NMR (400
MHz, CDCl3) δ 7.36 (d, J = 8.8 Hz, 2H), 7.14 (d, J = 8.3 Hz, 2H),
7.08 (d, J = 8.2 Hz, 2H), 6.86 (d, J = 8.8 Hz, 2H), 3.79 (s, 3H),
2.59 (q, J = 7.6 Hz, 2H), 1.20 (t, J = 7.6 Hz, 3H); 13C NMR (100
MHz, CDCl3) δ 159.5, 142.5, 134.7, 134.5, 129.3, 128.6, 125.6,
114.9, 55.4, 28.4, 15.5. HRMS (ESIꢀTOF): calcd for C15H17OS
[M + H]+: 245.0995, found: 245.0992
= 50:1, v/v); IR (KBr) ν̃ 2940, 2834, 1588, 1493, 1255, 1033,
1
832; H NMR (400 MHz, CDCl3) δ 7.42 (d, J = 8.8 Hz, 2H),
7.18−7.10 (m, 2H), 7.11−7.00 (m, 2H), 6.91 (d, J = 8.8 Hz, 2H),
3.82 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 160.2, 147.2, 137.7,
135.7, 129.1, 123.6, 121.5 (JCF = 256.0), 119.2, 115.2, 55.4.
(4ꢀMethoxyphenyl)(4ꢀnitrophenyl)sulfane (3na).17 Purification
by chromatography (PE/EA = 100:1, v/v) afforded 3na as a yelꢀ
(4ꢀ(tertꢀButyl)phenyl)(4ꢀmethoxyphenyl)sulfane (3fa).17 Purifiꢀ
cation by chromatography (PE/EA = 100:1, v/v) afforded 3fa as a
colorless oil (44.6 mg, 82%); Rf = 0.60 (PE/EA = 50:1, v/v) ; IR
low solid (39.2 mg, 74%); Rf = 0.60 (PE/EA = 50:1, v/v); mp
1
2965, 2899, 1593, 1492, 1250, 1032, 821 cmꢀ1; H NMR
o
(KBr) ν
̃
62−63 C; IR (KBr) ν
̃
2930, 2834, 1593, 1497, 1240, 1023, 751
cmꢀ1; 1H NMR (400 MHz, CDCl3) δ 8.03 (d, J = 9.0 Hz, 2H), 7.48
(d, J = 8.8 Hz, 2H), 7.09 (d, J = 9.0 Hz, 2H), 6.99 (d, J = 8.8 Hz,
2H), 3.86 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 161.1, 150.0,
145.1, 137.1, 125.6, 124.0, 120.2, 115.7, 55.5.
(400 MHz, CDCl3) δ 7.39 (d, J = 8.9 Hz, 2H), 7.26 (d, J = 8.6 Hz,
2H), 7.13 (d, J = 8.6 Hz, 2H), 6.87 (d, J = 8.9 Hz, 2H), 3.80 (s,
3H), 1.28 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 159.6, 149.2,
134.8, 134.7, 128.6, 126.0, 125.2, 114.9, 55.4, 34.4, 31.3.
(3,4ꢀDimethylphenyl)(4ꢀmethoxyphenyl)sulfane (3ga). Purificaꢀ
tion by chromatography (PE/EA = 100:1, v/v) afforded 3ga as a
(4ꢀMethoxyphenyl)(naphthalenꢀ2ꢀyl)sulfane (3oa).17 Purificaꢀ
tion by chromatography (PE/EA = 100:1, v/v) afforded 3oa as a
colorless oil (39.1 mg, 80%); Rf = 0.45 (PE/EA = 50:1, v/v) ; IR
white solid (41.9 mg, 80%); Rf = 0.40 (PE/EA = 50:1, v/v); mp
1
2940, 2834, 1587, 1497, 1239, 1033, 826 cmꢀ1; H NMR
o
(KBr) ν
̃
67−69 C; IR (KBr) ν
̃
2930, 2834, 1593, 1493, 1239, 1023, 826
cmꢀ1; 1H NMR (400 MHz, CDCl3) δ 7.80−7.74 (m, 1H),
7.74−7.64 (m, 2H), 7.61 (d, J = 1.3 Hz, 1H), 7.51−7.37 (m, 4H),
(400 MHz, CDCl3) δ 7.37 (d, J = 8.8 Hz, 2H), 7.16−6.94 (m, 3H),
6.88 (d, J = 8.8 Hz, 2H), 3.82 (s, 3H) , 2.23 (s, 3H) , 2.21 (s, 3H);
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7.31−7.30 (m, 1H), 6.99−6.88 (m, 2H), 3.84 (s, 3H); 13C NMR
13C NMR (100 MHz, CDCl3) δ 147.3, 145.7, 135.9, 133.2, 132.5,
(100 MHz, CDCl3) δ 159.9, 135.9, 135.2, 133.8, 131.8, 128.5,
127.7, 127.2, 126.8, 126.5, 126.5, 125.6, 124.5, 115.1, 55.4.
(4ꢀNitrophenyl)(phenyl)sulfane (3nb).16 Purification by chroꢀ
matography (PE/EA = 100:1, v/v) afforded 3nb as a yellow solid
130.0, 127.2, 124.2.
1
2
3
4
5
6
7
8
(4ꢀNitrophenyl)(4ꢀ(trifluoromethoxy)phenyl)sulfane (3nj).17 Puꢀ
rification by chromatography (PE/EA = 100:1, v/v) afforded 3nj
as a yellow solid (50.8 mg, 80%); Rf =0.40 (PE/EA = 50:1, v/v);
o
(37.9 mg, 82%); mp 55−56 oC; Rf = 0.40 (PE/EA = 50:1, v/v); IR
mp 84−86 C; IR (KBr) ν
̃
2940, 2834, 1588, 1493, 1255, 1033,
832; 1H NMR (400 MHz, CDCl3) δ 8.02 (d, J = 7.6 Hz, 2H), 7.49
(d, J = 7.3 Hz, 2H), 7.22 (d, J = 7.9 Hz, 2H), 7.14 (d, J = 7.6 Hz,
2H); 13C NMR (100 MHz, CDCl3) δ 150.1, 147.2, 145.8, 136.0,
129.4, 127.2, 124.2, 122.2, 120.4 (JCF = 257).
1
(KBr) ν
̃
3057, 2925, 1568, 1512, 1336, 1078, 847 cmꢀ1; H NMR
(400 MHz, CDCl3) δ 8.06 (d, J = 9.0 Hz, 2H), 7.55−7.53 (m, 2H),
7.46−7.45 (m, 3H), 7.18 (d, J = 9.0 Hz, 2H); 13C NMR (100 MHz,
CDCl3) δ 148.5, 145.4, 134.7, 130.6, 130.0, 129.7, 126.8, 124.0.
(4ꢀNitrophenyl)(pꢀtolyl)sulfane (3nc).16 Purification by chromaꢀ
tography (PE/EA = 100:1, v/v) afforded 3nc as a yellow solid
Naphthalenꢀ1ꢀyl(4ꢀnitrophenyl)sulfane (3nk).21 Purification by
chromatography (PE/EA = 100:1, v/v) afforded 3nk as a red solid
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
o
(40.2 mg, 82%); Rf = 0.50 (PE/EA = 50:1, v/v); mp 79−81 oC; IR
(40.5 mg, 72%); Rf =0.40 (PE/EA = 50:1, v/v); mp 84−86 C; IR
3445, 2920, 1578, 1508, 1341, 1084, 806 cmꢀ1; H NMR
(KBr) ν
̃
3445, 3091, 1572, 1497, 1331, 1084, 766 cmꢀ1; H NMR
1
1
(KBr) ν
̃
(400 MHz, CDCl3) δ 8.13 (d, J = 8.0 Hz, 1H), 7.93−7.75 (m, 5H),
7.42 (d, J = 7.4, 3H), 6.98−6.81 (m, 2H); 13C NMR (100 MHz,
CDCl3) δ 148.5, 145.2, 135.8, 134.6, 134.2, 131.5, 129.0, 127.8,
127.0, 126.8, 126.1, 126.0, 125.5, 124.0.
(400 MHz, CDCl3) δ 8.04 (d, J = 9.0 Hz, 2H), 7.43 (d, J = 8.1 Hz,
2H), 7.26 (d, J = 7.7 Hz, 2H), 7.13 (d, J = 9.0 Hz, 2H), 2.41 (s,
3H); 13C NMR (100 MHz, CDCl3) δ 149.3, 145.2, 140.2, 135.1,
130.9, 126.6, 126.2, 124.0, 21.3.
[1,1'ꢀBiphenyl]ꢀ4ꢀyl(4ꢀmethoxyphenyl)sulfane (6a).22 Purificaꢀ
tion by chromatography (PE/EA = 100:1, v/v) afforded 6a as a
white solid (40.5 mg, 72%); Rf = 0.30 (PE/EA = 50:1, v/v); mp
(4ꢀEthylphenyl)(4ꢀnitrophenyl)sulfane (3nd).18 Purification by
chromatography (PE/EA = 100:1, v/v) afforded 3nd as a yellow
solid (41.4 mg, 80%); Rf = 0.40 (PE/EA = 50:1, v/v); mp 87−88
o
137−138 C; 1H NMR (400 MHz, CDCl3) δ 7.45 (d, J = 7.2 Hz,
oC; IR (KBr) ν 3090, 2950, 1580, 1505, 1351, 1077, 850 cmꢀ1; 1H
̃
2H), 7.37 (dd, J1 = 8.6, J2 = 4.0 Hz, 4H), 7.32 (t, J = 7.6 Hz, 2H),
7.23−7.25 (m, 1H), 7.14 (d, J = 8.5 Hz, 2H), 6.83 (d, J = 8.8 Hz,
2H), 3.73 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 158.9, 139.4,
137.7, 136.7, 134.4, 127.8, 127.5, 126.6, 126.2, 125.8, 123.16,
114.0, 54.4.
NMR (400 MHz, CDCl3) δ 7.96 (d, J = 9.0 Hz, 2H), 7.38 (d, J =
8.2 Hz, 2H), 7.21 (d, J = 8.3 Hz, 2H), 7.06 (d, J = 9.1 Hz, 2H),
2.63 (q, J = 7.6 Hz, 2H), 1.20 (t, J = 7.6 Hz, 3H); 13C NMR
(100MHz, CDCl3) δ 148.3, 145.4, 144.2, 134.1, 128.6, 125.8,
125.2, 123.0, 27.6, 14.2.
(4ꢀ(tertꢀButyl)phenyl)(4ꢀnitrophenyl)sulfane (3ne).16 Purificaꢀ
tion by chromatography (PE/EA = 100:1, v/v) afforded 3ne as a
colorless solid (43.1 mg, 75%); Rf = 0.40 (PE/EA = 50:1, v/v); mp
■ ASSOCIATED CONTENT
o
65−66 C; IR (KBr) ν
̃
3097, 2945, 1578, 1508, 1331, 1078, 841
cmꢀ1; 1H NMR (400 MHz, CDCl3) δ 8.05 (d, J = 8.9 Hz, 2H), 7.47
(s, 4H), 7.16 (d, J = 9.0 Hz, 2H), 1.36 (s, 9H); 13C NMR (100
MHz, CDCl3) δ 153.3, 149.1, 145.2, 134.7, 127.1, 126.7, 126.4,
124.0, 34.9, 31.2.
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at http://pubs.acs.org.
Copies of 1H and 13C NMR spectra for all compounds
(3ꢀMethoxyphenyl)(4ꢀnitrophenyl)sulfane (3nf).16 Purification
by chromatography (PE/EA = 100:1, v/v) afforded 3nf as a yellow
solid (43.3 mg, 83%); Rf = 0.45 (PE/ EA = 50:1, v/v); mp 78−80
■ AUTHOR INFORMATION
oC; IR (KBr) ν 3445, 2961, 1583, 1502, 1331, 1078, 857 cmꢀ1; 1H
̃
Corresponding Author
NMR (400 MHz, CDCl3) δ 8.07 (d, J = 9.0 Hz, 2H), 7.36 (t, J =
8.0 Hz, 1H), 7.21 (d, J = 9.0 Hz, 2H), 7.12 (d, J = 7.7 Hz, 1H),
7.09−7.04 (m, 1H), 7.02−6.93 (m, 1H), 3.82 (s, 3H); 13C NMR
(100 MHz, CDCl3) δ 160.6, 148.2, 145.5, 131.6, 130.8, 126.9,
126.7, 124.1, 119.6, 115.6, 55.5.
*Eꢀmail: zhaojf@jxnu.edu.cn
ORCID
Junfeng Zhao: 0000ꢀ0003ꢀ4843ꢀ4871
Notes
The authors declare no competing financial interests.
(3,5ꢀDimethylphenyl)(4ꢀnitrophenyl)sulfane (3ng).19 Purificaꢀ
tion by chromatography (PE/EA = 100:1, v/v) afforded 3ng as a
■ ACKNOWLEDGMENT
yellow solid (39.9 mg, 77%); Rf = 0.5 (PE/ EA = 50:1, v/v); mp
o
98−100 C; IR (KBr) ν
̃
2930, 2829, 1593, 1493, 1245, 1028, 745
This work was supported by the National Natural Science Founꢀ
dation of China (21462023, 21762021) and the Natural Science
Foundation of Jiangxi Province (20143ACB20007, 20153BCB
23018, 20161BAB213069).
cmꢀ1; 1H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 9.0 Hz, 2H), 7.17
(s, 1H), 7.15 (d, J = 2.1 Hz, 3H), 7.08 (s, 1H), 2.34 (s, 6H); 13C
NMR (100 MHz, CDCl3) δ 149.1, 145.3, 139.8, 132.4, 131.5,
129.7, 126.6, 124.0, 21.2.
(4ꢀChlorophenyl)(3ꢀnitrophenyl)sulfane (3nh).20 Purification
by chromatography (PE/EA = 100:1, v/v) afforded 3nh as a yelꢀ
■ REFERENCES
low solid (41.9 mg, 79%); Rf = 0.40 (PE/EA = 50:1, v/v); mp
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o
87−88 C; IR (KBr) ν
̃
2930, 2830, 1588, 1487, 1245, 1028, 741
cmꢀ1; 1H NMR (400 MHz, CDCl3) δ 8.08 (d, J = 8.8 Hz, 2H), 7.47
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̃
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