DMSO/iodine-catalyzed oxidative C-Se/C-S bond formation: A regioselective synthesis of unsymmetrical chalcogenides with nitrogen- or oxygen-containing arenes

Article abstract of DOI:10.1039/c5cy01503k

A convenient metal-free and solvent-free iodine-catalyzed regioselective greener protocol to access different types of unsymmetrical chalcogenides with nitrogen- or oxygen-containing arenes through oxidative C-Se/C-S formation via direct C(sp²)-H bond activation was developed. The products were obtained in good to excellent yields using [O or N]-containing arenes, half equiv. of various odorless diorganyl dichalcogenides (S/Se), iodine (20 mol%) as the catalyst and 3 equiv. of DMSO as the oxidant, applying MW irradiation for 10 min.

Full text of DOI:10.1039/c5cy01503k

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ARTICLE
DMSO/Iodine-Catalyzed Oxidative C–Se/C–S Bond Formation: A
Regioselective Synthesis of Unsymmetrical Chalcogenides with
Nitrogen- or Oxygen-containing Arenes
Received 00th January 20xx,
Accepted 00th January 20xx
S. Saba, J. Rafique and A. L. Braga*
DOI: 10.1039/x0xx00000x
A convenient metal-free and solvent-free iodine-catalyzed regioselective greener protocol to access different types of
unsymmetrical chalcogenides with nitrogen- or oxygen-containing arenes, through oxidative C–Se/C–S formation via direct
C(sp2)–H bond activation was developed. The products were obtained in good to excellent yields using [O or N]-containing
arenes, half equiv. of various odorless diorganyl dichalcogenides (S/Se), iodine (20 mol%) as the catalyst and 3 equiv. of
DMSO as the oxidant, applying MW irradiation for 10 min.
www.rsc.org/
times, harsh reaction conditions with non-regioselective
protocols and oxygen-free techniques.
Recently, the I2/DMSO oxidative system has been
successfully applied in different types of greener organic
reactions.13
Introduction
In recent years, reactions under metal-free and solvent-free
conditions have been widely used in the functionalization of the
C-H bond,1,2 which is considered an important contribution to
the development and progress of green chemistry.3
Additionally, the use of microwave (MW) irradiation may open
new horizons in the field of modern sustainable organic
synthesis,4 since it significantly reduces the reaction time and
saves energy.5
Considering the significance of unsymmetrical diorganyl
chalcogenides, it would be advantageous and highly desirable
to develop a regioselective, ligand-free and metal-free protocol
in a solvent-free system for their preparation. In addition, this
new protocol should operate with a shorter reaction time and
be applicable to a broad range of selenylating and sulfenylating
species.14 To the best of our knowledge, no studies in which this
attractive strategy was applied to the synthesis of diorganyl
chalcogenides using arenes and diorganyl dichalcogenides have
been reported.
As part of our wider research program aimed at designing
and developing eco-friendly processes,15,16 as well as the use of
iodine/DMSO as a mild oxidizing agent, herein we report, for the
first time, C–Se/C-S coupling by C(sp2)–H bond activation, under
MW irradiation (Scheme 1). A less extensive study using aryl
thiols as sulfenylating agent, under conventional heating to
produce diaryl sulfides appeared in press during the
preparation of this manuscript.17 Our new regioselective,
broader, scalable and metal-free approach worked effectively
using a stoichiometric amount of arenes or heteroarenes with
diorganyl dichalcogenides as an odorless source of chalcogens.
The
biological
and
medicinal
properties
of
organochalcogenides (S, Se) are becoming increasingly
appreciated,6 mainly the antioxidant, antitumor, anti-
inflammatory and antiviral activity.7 Moreover, researchers in
the area of modern organic synthesis8,9 and catalysis10 have
been motivated by the potential applications of chalcogen
compounds in this field.6,9 Unsymmetrical organochalcogenides
with nitrogen-or oxygen-containing arenes and their derivatives
are a very important class of molecules, with different
applications in biological sciences. 6,9,11 Aryl-sulfides containing
these moieties are considered to be an important core structure
in many important drugs.6 However, studies on their
counterpart in selenium compounds are limited.
In relation to preparing this class of compounds, particularly
unsymmetrical diaryl chalcogenides containing OH and NH2
functionalities,12 few research articles are available on the
oxidative C–Se/C–S bond formation through C(sp2)–H bond
activation of arenes.12a-i However, some of them suffer from
limitations such as the use of non-greener solvents, pre-
functionalized coupling partners, transition metal catalysts,
stoichiometric or greater amounts of reagents, long reaction
Scheme 1
a. Departamento de Química, Universidade Federal de Santa Catarina, Florianopolis,
88040-900, SC-Brazil. http://labselen.jimdo.com/
† Fax: 55 48 3721 6427; Tel: 55 48 37216427; E-mail: braga.antonio@ufsc.br
Electronic Supplementary Information (ESI) available: See DOI: 10.1039/x0xx00000x
Results and discussion
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Table 2 Optimization of reaction conditions a
Table 1 Optimization of microwave parameters a
Entry
1
2
3
4
5
6
7
MW [W]
100
100
100
100
100
100
80
T [°C]
110
110
110
110
80
120
110
110
110
t [min]
3
Yield [%]b
Entry
1
2
3
4
I2 [mol%]
Oxidant [equiv.]
DMSO (3)
DMSO (3)
DMSO (3)
DMSO (3)
DMSO (3)
-
Yield [%]b
NR
45
47
69
95
96
53
96
79
91
65
-
5
5
10
15
10
10
10
10
8h
10
20
30
20
20
20
20
20
87
95
96
32
75
93
45
81
5
6
7
DMSO (2)
DMSO
DTBP (3)
H2O2
8
120
-
8 c
9
9 c
a Reaction conditions: 1a (0.125 mmol), 2a (0.25 equiv.), I2
10
b
(20 mol%), DMSO (3 equiv.) under MW irradiation.
Isolated yield. c Conventional heating in sealed tube .
a Reaction conditions: 1a (0.125 mmol), 2a (0.25 equiv.) in
the presence of catalyst (20 mol%) and oxidant (3 equiv.)
for 10 min at 110°C with 100 W of MW irradiation. b Isolated
yields. c Reaction performed using 250µl DMSO
The initial screening and optimization of the reaction conditions
were conducted with diphenyl diselenide 1a and N,N-
from 3 to 2 eq., the yield of 3a was reduced from 95 to 75%
(entry 4 vs 7), while in its absence the yield dramatically
decreased to 32% (entry 6). Using DMSO as solvent did not
showed any further positive influence on the yield on 3a (entry
8 vs 4). The use of other oxidants i.e. H2O2 and DTBP instead of
DMSO resulted in a less efficient transformation in 81 and 45%
yields, respectively (entry 9-10).
With the optimized conditions in hand, the applicability of
other arenes, e.g. anilines, anisoles etc., and various diorganyl
diselenides were screened (Tables 3 and 4). We first explored
the scope of the reaction with respect to the different arenes
2a-u while keeping diphenyl diselenide 1a constant, resulting in
the coupled product 3a-x in good to excellent yields (Table 3).
In general, N,N-disubstituted anilines afforded the selenated
product selectively at the para position of the anilines 3a-d in
excellent yields.
Furthermore, to our delight, when the reaction was carried
out with a secondary-amine (N-ethyl aniline) and a primary-
amine (aniline) only the coupled products 3e and 3f were
observed at the para position, in 83% and 80% yields,
respectively. In view of these results, ortho- and para-
substituted aryl amines 2g-l were reacted with 1a under
standard conditions. Ortho-substituted anilines resulted in
selenylation at the para-position, providing 3g-h in good yields.
Interestingly, an electron-withdrawing group at the ortho-
position afforded better yields (entry 3g vs 3h). When the para
position of the aniline was blocked by using 4-substituted
anilines 2i-l, the coupling took place at the ortho-position
forming 3i-l in 83-72% yields. The slight decrease in the yield of
3j-l as compare to 3g-i is most likely due to the steric effect.
dimethylaniline 2a as standard substrates, using
a
stoichiometric amount of oxidant and I2 as a catalyst under
microwave irradiation (Tables 1 and 2).
Firstly, the influence of the reaction time and microwave
parameters on the performance of the direct C(sp2)–H bond
selenylation of 2a was investigated (Tables 1). Initially, the
reaction time was varied (entries 1-4). Carrying out the reaction
for 3 min afforded the desired product 3a in only 47% yield
(entry 1). An increase in the reaction time to 10 min resulted in
a significant improvement and product 3a was accessed in 95%
yield (entry 3). However, no considerable alteration in the yield
was noted on applying a 15-min reaction time (96%, entry 4).
The influence of temperature on the reaction behavior was then
screened (entries 5–8) and the ideal conditions were observed
at 110 °C. We observed that by decreasing the temperature a
lower yield of 3a was obtained (entry 5) and a higher
temperature did not show any significant influence (entry 6).
We further investigated the reaction by investigating the effect
of applying MW irradiation. The best result was obtained using
100 W (entries 7 and 8 vs 3). In order to evaluate the influence
of the heating source, the reaction was also performed in a
conventional oil bath heating system (entry 9). However, 8 h of
heating were required to obtain 3a in 65 % yield, highlighting
the superiority of the MW method.
In the subsequent step, the influence of the catalyst loading
and the stoichiometric quantity of oxidant on the reaction
system was explored (Table 2). No product was observed in the
absence of catalyst, I2 (entry 1). By using 5 mol% of I2 3a was
obtained in 45% yield (entry 2). Increasing the catalyst loading
to 10 mol% led to an improvement in the yield (87%, entry 3),
which was further increased significantly to 95% when 20 mol%
of I2 was used (entry 4). Further increase in the catalyst loading
was not effective, giving 3a in 96% yield (entry 5).
Similarly, on using 3,4-(methylenedioxy)aniline 2m
, the
coupling took place at C6 instead of the C2 position, which is
most probably due to the steric effect and the selenated
product 3m was obtained in 82% yield.
The influence of oxidant on the selenylation of 2a was then
evaluated (entries 6-10). By decreasing the amount of DMSO
2 | J. Name., 2012, 00, 1-3
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Table 3 Scope and generality of the reaction using arenes 2a,b
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DOI: 10.1039/C5CY01503K
Table 4 Scope and generality of the reaction using diorganyl
diselenides 1a,b
a
Reaction conditions:
1 (0.125 mmol), 2 (0.25 mmol) in
the presence of I2 (20 mol%) and DMSO (3 equiv.) for 10
min at 110°C with 100 watts of MW irradiation. b Isolated
yields.
Table 5 Scope and generality of the reaction using diorganyl
disulfides 4a,b
a
Reaction conditions:
1 (0.125 mmol), 2 (0.25 mmol) in
the presence of I2 (20 mol%) and DMSO (3 equiv.) for 10
min at 110°C with 100 watts of MW irradiation. b Isolated
yields.
Promising results from anilines 2a-m motivated us to further
extend this new protocol to different heteroaromatic amines
2n-p. It is noteworthy that the compounds 2n-p are well
tolerated in this transformation and furnished exclusively the
para selenated product 3n-p, related to the amine, in 79-71%
yields. Similarly, in the case of 2-aminothiazole 2q, an
electrophilic attachment took place at the C5 position resulting
in 3q in 75% yield. We further tested this method with the
phenol and methoxy-arenes 2r-x under the optimized
conditions used for anilines. Encouragingly, the reactions
proceeded cleanly and furnished the corresponding aryl
selenides 3r-x in 75-88% yields.
a
Reaction conditions:
4 (0.125 mmol), 2 (0.25 mmol) in
the presence of I2 (20 mol%) and DMSO (3 equiv.) for 10
min at 110°C with 100 watts of MW irradiation. b Isolated
yields.
To extend the scope in terms of the substrate, the effects of
other diorganyl diselenides 1b-k were also investigated (Table
4). Interestingly, our protocol worked well for several
diselenides containing both electron-donating and electron-
withdrawing groups as well as bulky groups, verifying the
sensitivity and tolerance to the electronic effects and steric
effects of several different substituents. We observed that the
desired products, 3y-z and 3aa-ah, were obtained in good to
excellent yields. The results revealed that electron-withdrawing
(Table 4). This result is important since the alkyl group does not
usually furnish the product in C(sp2)-H bond activation.
The success in the iodine-catalyzed C-Se bond formation,
through C(sp2)–H bond activation, prompted us to expand this
methodology to diorganyl disulfides 4a-j as a way to access
unsymmetrical sulfides. The desired products 5a-j were
obtained in 77% to 97% yields (Table 5). It was observed that
the methodology used to prepared diorganyl disulfides
presented similar electronic and steric effects as that used to
obtain diorganyl diselenides Furthermore, diorganyl
disulfides afforded the coupling products in comparatively
better yields compared to diorganyl diselenides
4
groups at the phenyl ring of
1 gave fairly good yields (3y, 3z vs
1.
3aa, ab). We also noted a weaker influence on the yields
because of the steric hindrance of ortho-substituted aryl
substrates as compared to the corresponding para derivatives
4
1.
To check the versatility of this protocol, we have observed
that our methodology also worked efficiently by using
(
3ac vs 3y and 3ad vs 3z). In addition, we found that C-2
heteroaryl diselenide gave the desired selenide 3ag with 82%
yield. Interestingly, in the case of dibutyl diselenide, the
reaction produced the corresponding product 3ah in 78% yield
thiophenol
6 as another sulfenylating agent and N,N-
dimethylaniline 2a, affording the desired product in very good
yield, in a short reaction time using MW irradiation (Scheme 2).
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Scheme 2
In order to further explore the scope of this new
methodology we extended our study to sulfonyl hydrazides
7
(Scheme 3), applying the optimal reaction conditions (Table 1,
entry 3). Interestingly, the reaction of different arylsulfonyl
hydrazides
7 with N,N-dimethylaniline 2a proceeded smoothly
and afforded the corresponding coupled products 5a and 5b in
93% and 88% isolated yields, respectively (Scheme 3). This
demonstrates that our protocol is versatile, being applicable to
various kinds of organochalcogen sources.
Scheme 4 Investigation of the mechanism
is probably one of the intermediates of this transformation. It
was observed that on using NaI instead of HI the reaction did
not occur [Eq 4], demonstrating the importance of the presence
of HI.
Scheme 3
In order to demonstrate the potential of this protocol, a
series of reactions was carried out on different scales (Figure 1;
up to 10 mmol). For this, N,N-dimethylaniline 2a, diselenide 1a
and disulfide 5a were selected as the reagents to be tested
under optimized conditions, affording 3a and 5a with no major
decrease in yield. Thus, this procedure could be used as a robust
method for the synthesis of aryl chalcogenides on a larger scale.
Based on the above results and on previous reports,10b,13,18
a
plausible mechanism for the direct C(sp2)-H bond
chalcogenation of arenes under metal-free conditions is
illustrated in Scheme 5. Initially, the electrophilic chalcogen
species
A in the form an intermediate RYI (Y = Se, S) would be
formed by the reaction of diorganyl dichalcogenide RYYR with
the catalyst (I2). Subsequently, the electron-rich arenes would
attack the reactive RYI intermediates
form the species . This species would undergo proton
elimination and would furnish the expected chalcogenides
with the simultaneous formation of HI. In the next step, the by-
product HI would react with DMSO affording a protonated
A at the para-position, to
B
Yield with Se
96%
Yield with S
C
100%
90%
95% 95%
94%
92%
91%
92%
89%
Yield
sulfur species
iodine-dimethyl sulfide adduct
water.19 Lastly, the cycle would be completed by the
transformation of the species
to dimethyl sulfide (DMS)20 with
D
, which would be quickly converted to the
80%
70%
E
with the elimination of
0.5
2.5
5
10
E
the regeneration of the catalyst (I2).
Fig. 1 Results for the reaction on different scales.
Bearing in mind that the coupling reaction of diorganyl
chalcogenides and arenes under metal-free conditions is not
well understood, some control experiments were performed in
order to explain the mechanism (Scheme 4). Radical inhibitors,
e.g. TEMPO, hydroquinone, BHT, did not hamper the reaction
and the coupled product 3a was obtained in 84, 79 and 90 %
isolated yield, respectively [Eq. 1]. These experiments excluded
any possibility of a radical pathway, which also indicates that
the PhY radical species is not involved during the course of the
reaction. Compound 3a was obtained in 91% yield when 2a was
treated with one equiv. of PhSeBr instead of diphenyl diselenide
1a [Eq. 2], indicating that the reaction proceeds through a
phenylselenium cation species. Based on our previous
experience,16a using a catalytic amount of HI instead of iodine
[Eq. 3], the reaction afforded 3a with 82% yield, showing that HI
Scheme 5. Proposed mechanism for the reaction.
4 | J. Name., 2012, 00, 1-3
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GF254, 0.25 mm thickness. For visualization, TLCVipewlaAtreticslewOnelirnee
DOI: 10.1039/C5CY01503K
An important feature of this process is that the concentration either placed under ultraviolet light, or stained with iodine
of iodide in the reaction medium is low, since it is continuously vapor and acidic vanillin. Most reactions were monitored by TLC
consumed by the mild oxidant, DMSO, avoiding the nucleophilic for disappearance of starting material.
competition.
Unless otherwise stated, all reactions were carried out in
open atmosphere; all reagents and solvents were obtained from
commercial sources and used without any further purification.
All reactions were performed in 10-ml reaction vessels
(Borosilicate glass) with cap and septum (Silicon) in a
commercially available Microwave monomode CEM reactor
with IR monitoring and a non-invasive pressure transducer.
Reagents and solvents were handled using standard syringe
techniques. The yields are based on isolated compounds after
purification.
Conclusions
In summary, we have developed a regioselective, rapid and
greener iodine-catalyzed method for the synthesis of diorganyl
chalcogenides through oxidative C–Se/C–S formation via direct
C(sp2)-H bond cleavage from using [O or N]-containing arenes.
This regioselective procedure afforded the desired products in
good to excellent yields under metal and solvent-free
conditions, without the exclusion of air and moisture, applying
microwave irradiations for 10 min.
The important features of this protocol are: (1) metal-free
and solvent-free; (2) open to the air; (3) mild conditions; (4)
short reaction time and under microwave irradiation; (5)
regioselective; (6) applicable to different sources of
organochalcogenides. Additionally, by this protocol, we were
able to access biologically important Se/S containing
heteroarenes, such as, pyrimidines, pyridines, thiazole.
General procedure for the iodine-catalyzed synthesis of
unsymmetrical diorganyl chalocogenides
A mixture of appropriate arene
2 (0.25 mmol), diorganyl
dichalcogenide (0.125 mmol), iodine (20 mol %, 12 mg), and 3
equiv. of DMSO (0.75 mmol, 59 mg) were charged in a
microwave glass tube, which was sealed and placed in a CEM
Discover microwave apparatus. A maximum irradiation power
of 100 W and a temperature of 110 ºC were applied for 10 min.
When the reaction was finished, the homogenous reaction
mixture was dissolved in ethyl acetate (10 mL), and washed with
2 x 5 mL of an aqueous solution of 10% Na2S2O4. The organic
phase was separated, dried over MgSO4, and concentrated
under vacuum. The crude product was purified by flash
chromatography on silica gel using hexane or a mixture of
hexane/ ethyl acetate (99:1) as the eluent.
Experimental
Materials and methods
Proton nuclear magnetic resonance spectra (1H NMR) were
obtained at 200 MHz on a Bruker AC-200 NMR spectrometer or
at 400 MHz on a Varian AS-400 NMR spectrometer. Spectra
were recorded in CDCl3 solutions. Chemical shifts are reported
in ppm, referenced to the solvent peak of CDCl3 or
tetramethylsilane (TMS) as the external reference. Data are
reported as follows: chemical shift (δ), multiplicity, coupling
constant (J) in Hertz and integrated intensity. Carbon-13 nuclear
magnetic resonance spectra (13C NMR) were obtained either at
50 MHz on a Bruker AC-200 NMR spectrometer or at 100 MHz
on a Varian AS-400 NMR spectrometer. Spectra were recorded
in CDCl3 solutions. Chemical shifts are reported in ppm,
referenced to the solvent peak of CDCl3. Abbreviations to
denote the multiplicity of a particular signal are: s (singlet), d
(doublet), t (triplet), q (quartet), quint (quintet), sext (sextet)
and m (multiplet). Selenium-77 nuclear magnetic resonance
spectra (77Se NMR) at 38.14 MHz on a Bruker AC-200 NMR
spectrometer. Spectra were recorded in CDCl3 solutions.
Chemical shifts are reported in ppm, referenced to diphenyl
diselenide as the external reference (463.15 ppm). High
resolution mass spectra were recorded on a Bruker micrOTOF-
Q II ESI mass spectrometer equipped with an automatic syringe
pump for sample injection. Infrared spectra were recorded on a
Bruker Optics Alpha benchtop FT-IR spectrometer and are
reported in frequency of absorption (cm-1). The melting points
were determined in a Microquimica MQRPF-301 digital model
equipment with heating plate. Column chromatography was
performed using Silica Gel (230-400 mesh). Thin layer
chromatography (TLC) was performed using Merck Silica Gel
N,N-dimethyl-4-(phenylselanyl)aniline (3a)
Diphenyl diselenide 1a (0.125 mmol, 39 mg) and N,N-
dimethylaniline 2a (0.25 mmol, 30 mg) were used under
standard conditions; Yield: 94% (65 mg); yellow solid; mp 36–
38°C (lit.12b 35–38 °C); 1H NMR (200 MHz, CDCl3) δ = 7.48 (d, J =
9.0 Hz, 2H), 7.33–7.08 (m, 5H), 6.67 (d, J = 9.0 Hz, 2H), 2.97 (s,
6H); 13C NMR (50 MHz, CDCl3) δ = 150.6, 137.2, 134.7, 129.9,
129.1, 125.9, 113.8, 113.3, 40.4.77Se NMR (38.14 MHz, CDCl3): δ
391.4.
N,N-diethyl-4-(phenylselanyl)aniline (3b)
Diphenyl diselenide 1a (0.125 mmol, 39 mg) and N,N-
diethylaniline 2b (0.25 mmol, 37mg) were used under standard
conditions; Yield: 92% (70 mg); brown oil;12b 1H NMR (200 MHz,
CDCl3) δ = 7.45 (d, J = 9.0 Hz, 2H), 7.30–7.25 (m, 2H), 7.21–7.09
(m, 3H), 6.60 (d, J = 9.0 Hz, 2H), 3.34 (q, J = 7.1 Hz, 4H), 1.15 (t, J
= 7.1 Hz, 6H); 13C NMR (50 MHz, CDCl3) δ = 148.0, 137.5, 134.9,
129.7, 129.0, 125.7, 112.5, 112.2, 44.4, 12.6.
N,N-dibutyl-4-(phenylselanyl)aniline (3c)
Diphenyl diselenide 1a (0.125 mmol, 39 mg) and N,N-
dibutylaniline 2c (0.25 mmol, 37mg) were used under standard
conditions; Yield: 89% (80 mg); brown oil;12a 1H NMR (200 MHz,
CDCl3) δ = 7.43 (d, J = 9.0 Hz, 2H), 7.31–7.25 (m, 2H), 7.23–7.11
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(m, 3H), 6.57 (d, J = 9.0 Hz, 2H), 3.34–3.16 (m, 4H), 1.67–1.46 Diphenyl diselenide 1a (0.125 mmol, 39 mg) and 4-
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(m, 4H), 1.44–1.26 (m, 4H), 0.95 (t, J = 7.2 Hz, 6H); 13C NMR (50 methylaniline 2i (0.25 mmol, 27 mg) were used under standard
DOI: 10.1039/C5CY01503K
MHz, CDCl3) δ = 148.4, 137.5, 134.9, 129.8, 129.0, 125.8, 112.5, conditions; Yield: 72% (47 mg); brown oil;12a 1H NMR (200 MHz,
112.0, 50.8, 29.4, 20.4, 14.1.
CDCl3) δ = 7.39 (s, 1H), 7.27–7.09 (m, 5H), 7.09–6.95 (m, 1H),
6.69 (d, J = 8.1 Hz, 1H), 4.10 (bs, 2H), 2.22 (s, 3H); 13C NMR (50
MHz, CDCl3) δ = 146.2, 138.7, 131.9, 131.8, 129.4, 129.3, 128.2,
126.1, 115.1, 112.7, 20.2.
4-(4-(phenylselanyl)phenyl)morpholine (3d)
Diphenyl diselenide 1a (0.125 mmol, 39 mg) and 4-
phenylmorpholine 2d (0.25 mmol, 41mg) were used under
standard conditions; Yield: 87% (69 mg); white solid; mp 69-
4-chloro-2-(phenylselanyl)aniline (3j)
71°C (lit.12b 69–71 °C); 1H NMR (200 MHz, CDCl3) δ = 7.48 (d, J = Diphenyl diselenide 1a (0.125 mmol, 39 mg) and 4-chloroaniline
7.5 Hz, 2H), 7.39–7.27 (m, 2H), 7.27–7.04 (m, 3H), 6.83 (d, J = 2j (0.25 mmol, 32 mg) were used under standard conditions;
7.5 Hz, 2H), 3.92–3.73 (m, 4H), 3.26–3.03 (m, 4H); 13C NMR (50 Yield: 78% (55 mg); brown solid; mp 58-60°C (lit.12a 57–60 °C);
MHz, CDCl3) δ = 151.2, 136.4, 133.6, 130.7, 129.2, 126.4, 118.6, 1H NMR (200 MHz, CDCl3) δ = 7.54 (d, J = 2.4 Hz, 1H), 7.33–7.06
116.3, 66.9, 48.8. 77Se NMR (CDCl3,MHz): δ 397.7.
(m, 6H), 6.70 (d, J = 8.6 Hz, 1H), 4.26 (bs, 2H); 13C NMR (50 MHz,
CDCl3) δ = 147.1, 137.3, 130.9, 130.8, 129.9, 129.5, 126.8, 122.6,
115.9, 114.1
N-ethyl-4-(phenylselanyl)aniline (3e)
Diphenyl diselenide 1a (0.125 mmol, 39 mg) and N-ethylaniline
2e (0.25 mmol, 30mg) were used under standard conditions;
4-fluoro-2-(phenylselanyl)aniline (3k)
Yield: 83% (57 mg); brown oil; 1H NMR (400 MHz, CDCl3) δ = 7.43 Diphenyl diselenide 1a (0.125 mmol, 39 mg) and 4-fluoroaniline
(d, J = 8.7 Hz, 2H), 7.36–7.23 (m, 2H), 7.23–7.11 (m, 3H), 6.56 (d, 2k (0.25 mmol, 27 mg) were used under standard conditions;
1
J = 8.7 Hz, 2H), 3.78 (s, 1H), 3.17 (q, J = 7.1 Hz, 2H), 1.27 (t, J = Yield: 83% (55 mg); yellow solid; mp 56–58 °C; H NMR (200
7.1 Hz, 3H); 13C NMR (50 MHz, CDCl3) δ = 148.8, 137.4, 134.7, MHz, CDCl3) δ = 7.31–7.19 (m, 6H), 7.03–6.86 (m, 1H), 6.75–6.68
129.9, 129.1, 125.9, 114.6, 113.7, 38.4, 14.9; IR (KBr); 3406, (m, 1H), 4.09 (bs, 2H); 13C NMR (50 MHz, CDCl3) δ = 155.4 (d, Jc-
3054, 2925, 2669, 1594, 1502, 1321, 1180, 1021, 814, 734; f = 239.4 Hz),, 144.7 (d, Jc-f = 2.2 Hz), 130.9, 130.2, 129.5, 126.8,
HRMS m/z Calcd. for C14H16NSe [M+H]+ 278.04427; found: 123.69 (d, Jc-f = 22.3 Hz), 117.71 (d, Jc-f = 22.4 Hz), 115.74 (d, Jc-f
278.04429.
= 7.4 Hz), 113.85 (d, J Jc-f = 7.1 Hz); IR (KBr) 3456, 3358, 3053,
1608, 1596, 1487, 1194, 1022, 877, 802, 740; HRMS m/z Calcd.
for C12H11FNSe [M+H]+ 268.00355; found 268.00344.
4-(phenylselanyl)aniline (3f)
Diphenyl diselenide 1a (0.125 mmol, 39 mg) and aniline 2f (0.25
mmol, 23mg) were used under standard conditions; Yield: 80%
4-nitro-2-(phenylselanyl)aniline (3l)
(50 mg); yellow solid; mp 86-89°C (lit.12a 87–91 °C); 1H NMR (200 Diphenyl diselenide 1a (0.125 mmol, 39 mg) and 4-nitroaniline
MHz, CDCl3) δ = 7.39 (d, J = 8.5 Hz, 2H), 7.31–7.25 (m, 2H), 7.27– 2l (0.25 mmol, 35 mg) were used under standard conditions;
7.08 (m, 3H), 6.60 (d, J = 8.5 Hz, 2H), 3.72(s, 2H); 13C NMR (50 Yield: 81% (60 mg); yellow solid; mp 104–106 °C; H NMR (200
1
MHz, CDCl3) δ = 146.9, 137.1, 134.1, 130.2, 129.1, 126.1, 116.4, MHz, CDCl3) δ = 8.54 (d, J = 2.6 Hz, 1H), 8.10 (dd, J = 9.0, 2.6 Hz,
116.1.
1H), 7.36–7.15 (m, 5H), 6.75 (d, J = 9.0 Hz, 1H), 5.07 (bs, 2H); 13
C
NMR (50MHz, CDCl3) δ = 153.9, 138.8, 135.0, 130.2, 129.9,
129.7, 127.4, 127.3, 113.3, 112.0; IR (KBr) 3449, 3434, 3339,
1612, 1575, 1475, 1332, 1118, 1019, 907, 817, 740; HRMS m/z
Calcd. for C12H11N2O2Se [M+H]+ 294.99806; found 294.99810.
2-chloro-4-(phenylselanyl)aniline (3g)
Diphenyl diselenide 1a (0.125 mmol, 39 mg) and 2-chloroaniline
2g (0.25 mmol, 32 mg) were used under standard conditions;
Yield: 87% (62 mg); brown solid; mp 52-55°C (lit.12a 51–54 °C);
1H NMR (200 MHz, CDCl3) δ = 7.54 (d, J = 2.4 Hz, 1H), 7.31–7.06
6-(phenylselanyl)benzo[d][1,3]dioxol-5-amine (3m)
(m, 6H), 6.70 (d, J = 8.6 Hz, 1H), 4.27 (s, 2H); 13C NMR (50 MHz, Diphenyl diselenide 1a (0.125 mmol, 39 mg) and
CDCl3) δ = 143.2, 136.1, 135.1, 133.2, 130.8, 129.2, 126.6, benzo[d][1,3]dioxol-5-amine 2m (0.25 mmol, 34 mg) were used
119.6, 117.1, 116.5.
under standard conditions; Yield: 82% (59 mg); brown solid; mp
68–70°C; 1H NMR (200 MHz, CDCl3) δ = 7.26–7.15 (m, 5H), 7.04
(s, 1H), 6.40 (s, 1H), 5.89 (s, 2H), 4.13 (s, 2H). 13C NMR (50MHz,
CDCl3) δ 150.4, 144.7, 140.5, 132.4, 129.3, 129.0, 126.2, 117.1,
102.5, 101.1, 97.0; IR (KBr) 3454, 3354, 3049, 2897, 1629, 1589,
1502, 1470, 1257, 1219, 1194, 1033, 934, 826; HRMS m/z Calcd.
for C13H11NO2Se [M]+ 292.9950; found 292.9955.
2-methyl-4-(phenylselanyl)aniline (3h)
Diphenyl diselenide 1a (0.125 mmol, 39 mg) and 2-
methylaniline 2h (0.25 mmol, 27 mg) were used under standard
conditions; Yield: 78% (51 mg); brown soild; mp 55-57°C (lit.12a
56–59 °C); 1H NMR (200 MHz, CDCl3): δ 7.36–7.24 (m, 4H), 7.24–
7.11 (m, 3H), 6.62 (d, J = 8.0 Hz, 1H), 3.71 (bs, 2H), 2.14 (s, 3H);
13C NMR (50 MHz, CDCl3): δ 145.2, 138.1, 135.0, 134.4, 130.1,
129.1, 126.0, 123.5, 116.3, 115.8, 17.3.
5-(phenylselanyl)pyridin-2-amine (3n)
Diphenyl diselenide 1a (0.125 mmol, 39 mg) and pyridin-2-
amine 2n (0.25 mmol, 24 mg) were used under standard
conditions; Yield: 79% (49 mg); yellow solid; mp 110-114°C
4-methyl-2-(phenylselanyl)aniline (3i)
6 | J. Name., 2012, 00, 1-3
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Catalysis Science & Technology
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ARTICLE
(lit.12a 111–114 °C) 1H NMR (200 MHz, CDCl3) δ = 8.95 (d, J = 1.8 2-isopropyl-4-(phenylselanyl)phenol (3t)
Hz, 1H), 8.48–8.29 (m, 1H), 8.08–7.99 (m, 2H), 7.99–7.89 (m,
View Article Online
DOI: 10.1039/C5CY01503K
Diphenyl diselenide 1a (0.125 mmol, 39 mg) 2-isopropylphenol
2t (0.25 mmol, 34 mg) were used under standard conditions;
3H), 7.25 (d, J = 8.6 Hz, 1H), 5.27 (bs, 2H); 13C NMR (50MHz,
CDCl3) δ = 157.9, 152.7, 145.6, 132.7, 130.7, 129.3, 126.8, 113.8,
110.2.
1
Yield: 82% (60 mg); yellow oil; H NMR (200 MHz, CDCl3) δ =
7.48 – 7.14 (m, 7H), 6.69 (d, J = 8.2 Hz, 1H), 4.89 (s, 1H), 3.25–
3.11 (m, 1H), 1.23 (d, J = 6.9 Hz, 6H); 13C NMR (50MHz, CDCl3) δ
= 153.2, 136.0, 133.9, 133.8, 133.5, 130.6, 129.2, 126.4, 119.9,
4-methyl-5-(phenylselanyl)pyridin-2-amine (3o)
Diphenyl diselenide 1a (0.125 mmol, 39 mg) and 4- 116.6, 27.2, 22.5; IR (KBr) 3441, 3070, 3056, 2961,1636, 1577,
methylpyridin-2-amine 2o (0.25 mmol, 27 mg) were used under 1405, 1177, 1079, 813, 734; HRMS m/z Calcd. for C15H16OSe
standard conditions; Yield: 71% (47 mg); yellow soild; mp 85–87 [M]+ 292.0361; found 292.0362.
°C;1H NMR (200 MHz, CDCl3) δ = 8.29 (s, 1H), 7.25–7.13 (m, 5H),
6.45 (s, 1H), 4.59 (bs, 2H), 2.27 (s, 3H); 13C NMR (50 MHz, CDCl3) 2,6-dimethyl-4-(phenylselanyl)phenol (3u)
δ = 159.4, 155.8, 153.3, 132.9, 129.5, 129.3, 126.2, 115.3, 109.9,
22.5; IR (KBr) 3467, 3293, 3135, 3057, 1640, 1592, 1477, 1437,
1412, 1021, 730, 668; HRMS m/z Calcd. for C12H13N2Se [M+H]+
Diphenyl diselenide 1a (0.125 mmol, 39 mg) 2,6-
dimethylphenol3u (0.25 mmol, 52 mg) were used under
standard conditions; Yield: 75% (57 mg); yellow oil; 1H NMR (200
265.0239; found 265.0240.
MHz, CDCl3) δ = 7.35–7.17 (m, 7H), 4.74 (s, 1H), 2.21 (s, 6H); 13
C
NMR (50MHz, CDCl3) δ = 152.7, 135.7, 133.6, 130.8, 129.2,
126.4, 124.5, 119.1,15.8; IR (KBr) 3474, 3068, 3055, 2919, 2851,
5-(phenylselanyl)pyrimidin-2-amine (3p)
Diphenyl diselenide 1a (0.125 mmol, 39 mg) and pyrimidin-2- 1578, 1475, 1437, 1192, 1021, 869, 734; HRMS m/z Calcd. for
amine 2p (0.25 mmol, 24 mg) were used under standard C14H14OSe [M]+ 278.0205; found 278.0203.
conditions; Yield: 76% (48 mg); white solid; mp: 146–148 °C; 1H
NMR (200 MHz, DMSO-d6) δ = 8.41 (s, 2H), 7.62–7.18 (m, 5H), (4-methoxyphenyl)(phenyl)selane (3v)
7.08 (s, 2H); 13C NMR (50 MHz, DMSO-d6) δ = 164.1, 162.9,
Diphenyl diselenide 1a (0.125 mmol, 39 mg) and anisole 2v
132.6, 129.5, 129.4, 126.5, 109.3; IR (KBr); 3306, 3174, 3069,
(0.25 mmol, 27 mg) were used under standard conditions; Yield:
1659, 1574, 1543, 1490, 1213, 1066, 1020, 936, 796, 689; HRMS
88% (58 mg); yellow oil;12e 1H NMR (200 MHz, CDCl3) δ = 7.51 (d,
J = 8.8 Hz, 2H), 7.38–7.29 (m, 2H), 7.27–7.16 (m, 3H), 6.85 (d, J
= 8.8 Hz, 2H), 3.80 (s, 3H); 13C NMR (50MHz, CDCl3) δ = 159.9,
m/z Calcd. for C10H10N3Se [M+H]+ 252.0035; found 252.0038.
5-(phenylselanyl)thiazol-2-amine (3q)
136.6, 133.3, 131.0, 129.2, 126.5, 120.0, 115.2, 55.4.
Diphenyl diselenide 1a (0.125 mmol, 39 mg) and thiazol-2-
amine 2q (0.25 mmol, 25 mg) were used under standard phenyl(2,3,4-trimethoxyphenyl)selane (3w)
conditions; Yield: 75% (48 mg); brown solid; mp 120–122°C; 1H
Diphenyl diselenide 1a (0.125 mmol, 39 mg) and 1,2,3-
NMR (200 MHz, CDCl3) δ = 7.40–7.35 (m, 1H), 7.32–7.21 (m, 5H),
trimethoxybenzene 2w (0.25 mmol, 42 mg) were used under
5.47 (bs, 2H); 13C NMR (50 MHz, CDCl3) δ = 173.3, 148.2, 133.0,
1
standard conditions; Yield: 83% (67 mg); colorless oil; H NMR
129.5, 129.3, 126.8, 106.1; IR (KBr) 3378, 3272, 3163, 3087,
(200 MHz, CDCl3) δ = 7.51–7.46 (m, 2H), 7.28–7.25 (m, 3H), 6.87
1625, 1513, 1483, 1067, 1052, 726, 516; HRMS m/z Calcd. for
(d, J = 8.7 Hz, 1H), 6.57 (d, J = 8.7 Hz, 1H), 3.88 (s, 3H), 3.86 (s,
C9H9N2SSe [M+H]+ 256.9646; found 256.9645.
3H), 3.82 (s, 3H); 13C NMR (50MHz, CDCl3) δ = 153.7, 152.5,
142.6, 133.5, 130.4, 129.3, 127.5, 127.4, 117.3, 108.5, 61.0,
60.9, 56.1; IR (KBr) 3069, 3055, 2996, 2835, 1577, 1478, 1456,
4-(phenylselanyl)phenol (3r)
Diphenyl diselenide 1a (0.125 mmol, 39 mg) and phenol 2r (0.25 1292, 1092, 1012, 917, 847, 739; HRMS m/z Calcd. for
mmol, 25 mg) were used under standard conditions; Yield: 82% C15H16O3Se [M]+ 324.0260; found 324.0262.
(51 mg); brown oil;12e 1H NMR (200 MHz, CDCl3) δ = 7.46 (d, J =
8.6 Hz, 2H), 7.39–7.29 (m, 2H), 7.28–7.15 (m, 3H), 6.78 (d, J = phenyl(2,4,6-trimethoxyphenyl)selane (3x)
8.6 Hz, 2H), 5.12 (bs, 2H); 13C NMR (50MHz, CDCl3) δ = 155.9,
136.8, 133.1, 131.1, 129.3, 126.6, 120.3, 116.7.
Diphenyl diselenide 1a (0.125 mmol, 39 mg) and 1,3,5-
trimethoxybenzene 2x (0.25 mmol, 42 mg) were used as
substrates; Yield: 81% (66 mg); yellow oil;12g 1H NMR (200 MHz,
2-ethyl-4-(phenylselanyl)phenol (3s)
CDCl3) δ = 7.31–7.01 (m, 5H), 6.21 (s, 2H), 3.86 (s, 3H), 3.78 (s,
Diphenyl diselenide 1a (0.125 mmol, 39 mg) and 2-ethylphenol 6H); 13C NMR (50MHz, CDCl3) δ = 163.0, 162.0, 133.6, 128.9,
2s (0.25 mmol, 31 mg) were used under standard conditions; 128.7, 125.3, 97.2, 91.3, 56.4, 55.5.
Yield: 80% (55 mg); yellow oil; 1H NMR (200 MHz, CDCl3) δ = 7.53
– 7.09 (m, 7H), 6.71 (d, J = 8.2 Hz, 1H), 4.98 (s, 1H), 2.61 (q, J = N,N-dimethyl-4-(p-tolylselanyl)aniline (3y)
7.6 Hz, 2H), 1.21 (t, J = 7.6 Hz, 3H); 13C NMR (50MHz, CDCl3) δ =
= 153.8, 136.4, 134.2, 133.5, 131.5, 130.9, 129.2, 126.5, 120.0,
116.4, 22.9, 13.9; IR (KBr) 3417, 2965, 2929, 1578, 1491, 1264,
1119, 1021, 891, 735; HRMS m/z Calcd. for C14H14OSe [M]+
Bis(4-methylphenyl) diselenide 1b (0.125 mmol, 43 mg) and
N,N-dimethylaniline 2a (0.25 mmol, 30 mg) were used under
standard conditions; Yield: 86% (63 mg); yellow solid; mp 67–
69°C 1H NMR (200 MHz, CDCl3): δ = 7.45 (d, J = 9.0 Hz, 2H), 7.21
278.0205; found 278.0206.
(d, J = 8.2 Hz, 2H), 7.00 (d, J = 8.2 Hz, 2H), 6.64 (d, J = 9.0 Hz, 2H),
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ARTICLE
Journal Name
2.95 (s, 6H), 2.27 (s, 3H); 13C NMR (50MHz, CDCl3): δ = 150.4, N,N-dimethyl-4-((3-(trifluoromethyl)phenyl)selanyl)aniline (3ae)
View Article Online
Bis(3-(trifluoromethyl)phenyl) diselenideD1OhI: 1(00.1.103295/Cm5CmY0o1l5,0536K
mg) and N,N-dimethylaniline 2a (0.25 mmol, 30 mg) were used
136.6, 135.9, 130.6, 130.4, 129.9, 114.7, 113.3, 40.4, 21.1; IR
(KBr) 3068, 3016, 2915, 2884, 2810, 1597, 1504, 1442, 1224,
1064, 1014, 807, 799; HRMS m/z Calcd. for C15H18NSe [M+H]+
under standard conditions; Yield: 89% (77 mg); brown solid; mp
292.0599; found 292.0597.
1
47-50°C (lit.12a 48–52 °C); H NMR (200 MHz, CDCl3) δ = 7.48–
7.43 (m, 1H), 7.40 (d, J = 9.0 Hz, 2H), 7.32–7.24 (m, 2H), 7.23–
7.07 (m, 1H), 6.61 (d, J = 9.0 Hz, 2H), 2.90 (s, 6H); 13C NMR (50
4-((4-methoxyphenyl)selanyl)-N,N-dimethylaniline(3z)
Bis(4-methoxyphenyl) diselenide 1c (0.125 mmol, 47 mg) and MHz, CDCl3) δ = 150.7, 137.5, 136.3, 132.7, 131.3 (q, Jc-f = 32.2
N,N-dimethylaniline 2a (0.25 mmol, 30 mg) were used under Hz), 129.3, 126.0 (q, Jc-f = 3.9 Hz), 123.8 (q, Jc-f = 272.8 Hz), 122.6
standard conditions; Yield: 85% (65 mg); yellow solid; mp 98- (q, Jc-f = 3.8 Hz), 113.5, 112.8, 40.4.
102°C; 1H NMR (200MHz, CDCl3) δ = 7.41 (d, J = 8.8 Hz, 2H), 7.33
(d, J = 8.6 Hz, 2H), 6.77 (d, J = 8.6 Hz, 2H), 6.63 (d, J = 8.8 Hz, 2H), N,N-dimethyl-4-(naphthalen-1-ylselanyl)aniline (3af)
3.75 (s, 3H), 2.93 (s, 6H); 13C NMR (50MHz, CDCl3) δ = 158.8,
150.3, 135.7, 133.3, 123.7, 116.0, 114.9, 113.3, 55.4, 40.5; IR
(KBr) 3087, 3058, 2940, 2810, 1591, 1504, 1359, 1238, 1031,
808, 593; HRMS m/z Calcd. for C15H17NOSe [M+H]+ 308.0540;
Binaphthyl diselenide 1i (0.125 mmol, 52 mg) and N,N-
dimethylaniline 2a (0.25 mmol, 30 mg) were used under
standard conditions; Yield: 85% (69 mg); yellow soild; mp 122-
124°C; 1H NMR (200 MHz, CDCl3) δ = 8.24 (d, J = 8.7 Hz, 1H), 7.80
(d, J = 7.5 Hz, 1H), 7.67 (d, J = 7.9 Hz, 1H), 7.57–7.40 (m, 4H),
7.39–7.18 (m, 2H), 6.64 (d, J = 8.4 Hz, 2H), 2.93 (s, 6H); 13C NMR
(50MHz, CDCl3) δ = 150.5, 136.8, 134.0, 133.5, 132.9, 129.0,
found 308.0550.
4-((4-chlorophenyl)selanyl)-N,N-dimethylaniline (3aa)
Bis(4-chlorophenyl) diselenide 1d (0.125 mmol, 48 mg) and N,N- 128.5, 127.0, 126.5, 126.4, 126.2, 126.1, 113.7, 113.4, 40.4; IR
dimethylaniline 2a (0.25 mmol, 30 mg) were used under (KBr) 3044, 2901, 2812, 1595, 1557, 1372, 1194, 1081, 807, 768;
standard conditions; Yield: 92% (72 mg); white solid; mp 111- HRMS m/z Calcd. for C18H17NSe [M]+ 327.0521; found:
114°C (lit.12a 111–116 °C); 1H NMR (200 MHz, CDCl3) δ = 7.46 (d, 327.0521.
J = 9.0 Hz, 2H), 7.28–7.05 (m, 5H), 6.66 (d, J = 9.0 Hz, 2H), 2.97
(s, 3H); 13C NMR (50MHz, CDCl3) δ = 150.7, 137.2, 133.1, 131.9, N,N-dimethyl-4-(thiophen-2-ylselanyl)aniline (3ag)
131.1, 129.1, 113.4, 113.3, 40.3.
Di(thiophen-2-yl) diselenide 1j (0.125 mmol, 41 mg) and N,N-
dimethylaniline 2a (0.25 mmol, 30 mg) were used under
standard conditions; Yield: 82% (58 mg); yellow soild; mp 50-
4-((4-fluorophenyl)selanyl)-N,N-dimethylaniline (3ab)
Bis(4-fluorophenyl) diselenide 1e (0.125 mmol, 44 mg) and N,N- 53°C;1H NMR (200 MHz, CDCl3) δ = 7.42 (d, J = 9.0 Hz, 2H), 7.32
dimethylaniline 2a (0.25 mmol, 30 mg) were used under (dd, J = 5.3, 1.2 Hz, 1H), 7.20 (dd, J = 3.5, 1.2 Hz, 1H), 6.94 (dd, J
standard conditions; Yield: 90% (66 mg); yellow solid; mp 47- = 5.3, 3.5 Hz, 1H), 6.61 (d, J = 9.0 Hz, 2H), 2.93 (s, 6H); 13C NMR
50°C (lit.12b 49–52 °C); 1H NMR (200 MHz, CDCl3) δ= 7.44 (d, J = (50 MHz, CDCl3) δ = 150.1, 134.3, 133.9, 130.1, 127.8, 127.0,
8.8 Hz, 2H), 7.30–7.23 (m, 2H), 6.88 (t, J = 8.8 Hz, 2H), 6.64 (d, J 117.0, 113.0, 40.3; IR (KBr) 3439, 3287, 3093, 2810, 1661, 1591,
= 8.8 Hz, 2H), 2.95 (s, 6H); 13C NMR (50MHz, CDCl3) δ = 161.84 1502, 1437, 1233, 1066, 846, 730; HRMS m/z Calcd. for
(d, Jc-f = 245.2 Hz), 150.6, 136.7, 132.31 (d, Jc-f = 7.7 Hz), 128.78 C12H14NSSe [M+H]+ 284.0006; found 284.0009.
(d, Jc-f = 3.3 Hz), 116.19 (d, Jc-f = 21.6 Hz), 114.4, 113.3, 40.3.
4-(butylselanyl)-N,N-dimethylaniline (3ah)
N,N-dimethyl-4-(o-tolylselanyl)aniline (3ac)
Dibutyl diselenide 1k (0.125 mmol, 34 mg) and N,N-
Bis(2-methylphenyl) diselenide 1f (0.125 mmol, 43 mg) and N,N- dimethylaniline 2a (0.25 mmol, 30 mg) were used under
1
dimethylaniline 2a (0.25 mmol, 30 mg) were used under standard conditions; Yield: 78% (50 mg); colorless oil; H NMR
standard conditions; Yield: 83% (60 mg); yellow oil; 12b 1H NMR (200 MHz, CDCl3) δ = 7.42 (d, J = 8.9 Hz, 2H), 6.62 (d, J = 8.9 Hz,
(200 MHz, CDCl3) δ = 7.45 (d, J = 8.6 Hz, 2H), 7.29–6.90 (m, 5H), 2H), 2.93 (s, 6H), 2.87–2.64 (m, 2H), 1.79–1.55 (m, 2H), 1.48–
6.69 (d, J = 8.6 Hz, 2H), 2.98 (s, 6H), 2.38 (s, 3H); 13C NMR 1.30 (m, 2H), 0.88 (t, J = 7.2 Hz, 3H); 13C NMR (50MHz, CDCl3) δ
(50MHz, CDCl3) δ = 150.6, 137.4, 137.0, 135.4, 129.9, 129.4, = 150.0, 135.9, 115.0, 113.1, 40.5, 32.5, 29.1, 22.9, 13.7; IR (KBr)
126.5, 125.9, 113.4, 113.0, 40.4, 21.7.
3029, 2971, 2924, 2800, 1595, 1505, 1444, 1352, 1062, 945,
760; HRMS m/z Calcd. for C12H20NSe [M+H]+ 258.07558; found
258.07536.
4-((2-methoxyphenyl)selanyl)-N,N-dimethylaniline (3ad)
Bis(2-methoxyphenyl) diselenide 1g (0.125 mmol, 47 mg)and
N,N-dimethylaniline 2a (0.25 mmol, 30 mg) were used under
N,N-dimethyl-4-(phenylthio)aniline (5a)
standard conditions; Yield: 81% (62 mg); yellow solid; 12b mp 85- Diphenyl disulfide 4a (0.125 mmol, 27 mg) and N,N-
88°C (lit. 85–90 °C); 1H NMR (200 MHz, CDCl3) δ = 7.51 (d, J = 8.3 dimethylaniline 2a (0.25 mmol, 30 mg) were used under
Hz, 2H), 7.19–7.05 (m, 1H), 6.89–6.51 (m, 5H), 3.89 (s, 3H), 2.98 standard conditions; Yield: 97% (56 mg); yellow solid; mp 67-
1
(s, 6H); 13C NMR (50MHz, CDCl3) δ = 155.7, 150.8, 138.5, 128.5, 69°C (lit.17 68–69 °C); H NMR (200 MHz, CDCl3) δ = 7.39 (d, J =
126.4, 124.7, 121.6, 113.3, 111.2, 110.0, 55.8, 40.3.
7.5 Hz, 2H), 7.25–7.01 (m, 5H), 6.70 (d, J = 7.5 Hz, 2H), 2.98 (s,
8 | J. Name., 2012, 00, 1-3
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6H); 13C NMR (50MHz, CDCl3) δ = 150.7, 140.3, 136.2, 128.8, 1366, 1193, 1028, 945, 814, 746; HRMS m/VziewCAartliccdle.Onflioner
+
DOI: 10.1039/C5CY01503K
127.0, 125.1, 117.6, 113.1, 40.5.
C14H15ClNS [M+H] 264.06082; found 264.06091.
N,N-dimethyl-4-(p-tolylthio)aniline (5b)
N,N-dimethyl-4-(o-tolylthio)aniline (5g)
Bis(4-methylphenyl) disulfide 4b (0.125 mmol, 31 mg) and N,N- Bis(4-methylphenyl) disulfide 4g (0.125 mmol, 31 mg) and N,N-
dimethylaniline 2a (0.25 mmol, 30 mg) were used under dimethylaniline 2a (0.25 mmol, 30 mg) were used under
standard conditions; Yield: 90% (55 mg); yellow solid; mp 49- standard conditions; Yield 90% (55 mg); white solid; mp 112–
1
1
51°C (lit.17 51–52 °C); H NMR (400 MHz, CDCl3) δ = 7.42 (d, J = 114 °C; H NMR (200 MHz, CDCl3) δ = 7.33 (d, J = 8.9 Hz, 2H),
8.8 Hz, 2H), 7.20–6.99 (m, 5H), 6.74 (d, J = 8.8 Hz, 2H), 3.01 (s, 7.14–7.10 (m, 1H), 7.03–6.98 (m, 2H), 6.85–6.80 (m, 1H), 6.70
6H), 2.32 (s, 3H); 13C NMR (50MHz, CDCl3) δ = 150.3, 136.2, (d, J = 8.9 Hz, 2H), 2.97 (s, 6H); 2.38 (s, 3H); 13C NMR (50MHz,
135.4, 135.1, 129.6, 127.9, 118.9, 113.1, 40.4, 21.0.
CDCl3) δ = 150.6, 139.2, 135.9, 135.5, 130.0, 127.0, 126.4, 125.1,
117.3, 113.2, 40.4, 20.2; IR (KBr) 3084, 3056, 2925, 2813, 1597,
1509, 1440, 1194, 1057, 946, 809, 797; HRMS m/z Calcd. for
C15H18NS [M+H]+ 244.11545; found 244.11547
4-((4-methoxyphenyl)thio)-N,N-dimethylaniline (5c)
Bis(4-methoxyphenyl) disulfide 4c (0.125 mmol, 35 mg) and
N,N-dimethylaniline 2a (0.25 mmol, 30 mg) were used under
standard conditions; Yield: 87% (56 mg); yellow solid; mp 91–93
4-((3-chlorophenyl)thio)-N,N-dimethylaniline (5h)
°C; 1H NMR (200 MHz, CDCl3) δ = 7.30 (d, J = 9.0 Hz, 2H), 7.18 (d, Bis(3-chlorophenyl) disulfide 4h (0.125 mmol, 36 mg) and N,N-
J = 8.9 Hz, 2H), 6.78 (d, J = 8.9 Hz, 2H), 6.65 (d, J = 9.0 Hz, 2H), dimethylaniline 2a (0.25 mmol, 30 mg) were used under
3.74 (s, 3H), 2.93 (s, 6H); 13C NMR (50MHz, CDCl3) δ = 158.4, standard conditions;Yield: 90% (59 mg); white solid; mp 58–60
150.2, 134.3, 130.9, 129.6, 120.6, 114.6, 113.1, 55.4, 40.4; IR °C; 1H NMR (200 MHz, CDCl3) δ = 7.38 (d, J = 9.0 Hz, 2H), 7.20–
(KBr) 3091, 3060, 2942, 2836, 1880, 1872, 1592, 1506, 1358, 6.89 (m, 4H), 6.70 (d, J = 9.0 Hz, 2H), 2.99 (s, 6H); 13C NMR
1236, 1031, 827; HRMS m/z Calcd. for C15H18NOS [M+H]+ (50MHz, CDCl3) δ = 151.0, 143.0, 136.6, 134.8, 129.7, 126.1,
260.1104; found 260.1102.
125.0, 124.5, 115.9, 113.1, 40.3; IR (KBr) 3396, 3043, 2889,
2811, 1592, 1574, 1505, 1358, 1193, 1097, 943, 884, 770; HRMS
m/z Calcd. for C14H15ClNS [M+H]+ 264.06082; found 264.06069.
4-((4-(tert-butyl)phenyl)thio)-N,N-dimethylaniline (5d)
Bis(4-(tert-butyl)phenyl) disulfide 4d (0.125 mmol, 41 mg) and
N,N-dimethylaniline 2a (0.25 mmol, 30 mg) were used under
N,N-dimethyl-4-(thiophen-3-ylthio)aniline (5i)
standard conditions; Yield: 93% (53 mg); yellow solid; mp 86–88 Di(thiophen-2-yl) disulfide 4i (0.125 mmol, 29 mg) and N,N-
°C; 1H NMR (200 MHz, CDCl3) δ = 7.38 (d, J = 8.4 Hz, 2H), 7.23 (d, dimethylaniline 2a (0.25 mmol, 30 mg) were used under
J = 7.6 Hz, 2H), 7.06 (d, J = 7.6 Hz, 2H), 6.69 (d, J = 8.4 Hz, 2H), standard conditions; Yield: 86% (50 mg); yellow solid; mp 50–52
2.98 (s, 6H), 1.27 (s, 9H); 13C NMR (50MHz, CDCl3) δ = 150.5, °C; 1H NMR (200 MHz, CDCl3) δ = 7.33–7.25 (m, 3H), 7.12 (d, J =
148.3, 136.5, 135.8, 127.1, 125.8, 118.3, 113.0, 40.4, 34.4, 31.3; 3.5 Hz, 1H), 6.95–6.91 (m, 1H), 6.62 (d, J = 8.7 Hz, 2H), 2.91 (s,
IR (KBr) 3075, 2956, 2901, 2802, 1592, 1551, 1395, 1357, 1192, 6H); 13C NMR (50MHz, CDCl3) δ = 150.2, 136.8, 132.6, 132.0,
1061, 1008, 812; HRMS m/z Calcd. for C18H23NS [M+H]+ 128.8, 127.5, 122.2, 112.9, 40.9; IR (KBr) 3400, 3097, 3082,
286.16240; found 286.16236.
2884, 2810, 1599, 1507, 1362, 1190, 1062, 843, 713; HRMS m/z
Calcd. for C12H14NS2 [M+H]+ 236.05622; found 236.05625.
4-((4-bromophenyl)thio)-N,N-dimethylaniline (5e)
N,N-dimethyl-4-(propylthio)aniline (5j)
Bis(4-bromophenyl) disulfide 4e (0.125 mmol, 47 mg) and N,N-
dimethylaniline 2a (0.25 mmol, 30 mg) were used under Dibutyl disulfide 4j (0.125 mmol, 22mg) and N,N-
standard conditions; Yield: 95% (73 mg); yellow solid; mp 126– dimethylaniline 2a (0.25 mmol, 30 mg) were used under
128 °C( lit.17 127–128 °C); 1H NMR (200 MHz, CDCl3) δ = 7.35 (d, standard conditions; Yield: 77% (38 mg); colorless oil; 1H NMR
J = 9.0 Hz, 2H), 7.27 (d, J = 8.7 Hz, 2H), 6.93 (d, J = 8.7 Hz, 2H), (200 MHz, CDCl3) δ = 7.32 (d, J = 8.6 Hz, 2H), 6.66 (d, J = 8.6 Hz,
6.67 (d, J = 9.0 Hz, 2H), 2.96 (s, 6H); 13C NMR (50MHz, CDCl3) δ 2H), 2.94 (m, 6H), 2.83–2.64 (m, 2H), 1.73–1.43 (m, 2H), 0.97 (t,
= 150.8, 139.9, 136.3, 131.7, 128.3, 118.5, 116.5, 113.0, 40.3.
J = 7.3 Hz, 3H); 13C NMR (50MHz, CDCl3) δ = 149.9, 134.0, 121.3,
113.0, 40.6, 38.8, 22.9, 13.4; IR (KBr) 3444, 2959, 2929, 2870,
1596, 1504, 1443, 1352, 1061, 946, 812; HRMS m/z Calcd. for
C11H18NS [M+H]+ 196.10081 found 196.10089.
4-((2-chlorophenyl)thio)-N,N-dimethylaniline (5f)
Bis(4-chlorophenyl) disulfide 4f (0.125 mmol, 36 mg) and N,N-
dimethylaniline 2a (0.25 mmol, 30 mg) were used under
standard conditions; Yield: 93% (61 mg); white solid; mp 119–
Procedure for the iodine-catalyzed reactions of thiophenol with
N,N-dimethylaniline 2a
1
121°C; H NMR (200 MHz, CDCl3) δ = 7.40 (d, J = 8.9 Hz, 2H),
7.35–7.22 (m, 1H), 7.08–6.95 (m, 2H), 6.74 (d, J = 8.9 Hz, 2H), A mixture of N,N-dimethylaniline 2a (0.25 mmol, 30 mg), and
6.71–6.60 (m, 1H), 3.01 (s, 6H); 13C NMR (50MHz, CDCl3) δ = thiophenol
(0.25 mmol, 28mg) were used under standard
6
151.2, 140.3, 137.3, 130.2, 129.3, 127.0, 126.8, 125.4, 115.0, conditions. Yield: 5a 89% (51 mg).
113.2, 40.3; IR (KBr) 3054, 2987, 2900, 2810, 1592, 1509, 1441,
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Journal Name
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Edition 2; RSC Publishing: Cambridge, 2010; (b)VPie.wTA.rtAiclneaOsntlianse
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General Procedure for the iodine-catalyzed reactions of arylsulfonyl
hydrazides with N,N-dimethylaniline 2a
A mixture of phenylsulfonyl hydrazide 7a (0.25 mmol, 43 mg) or
p-tolylsulfonyl hydrazide 7b (0.25 mmol, 47 mg) and N,N-
dimethylaniline 2a (0.25 mmol, 30 mg) were used under
standard conditions. Yield: 5a, 93% (53 mg) and 5b, 88% (54
mg).
Control Experiments for the Study of Mechanism
Radical trapping study
A mixture of diphenyl diselenide 1a (0.125 mmol, 39 mg), N,N-
dimethylaniline 2a (0.25 mmol, 30 mg) and appropriate radical
inhibitor (0.25 mmol) i.e. TEMPO (39 mg), hydroquinone (28
mg), BHT (55 mg), were used under standard conditions. Yield
of 3a: 84% (58 mg) in case of TEMPO, 79% (55 mg) in case of
hydroquinone, 90% (62mg) in case of BHT.
2012, 7, 1184; (f) S. Santra and P. R. Andreana, Angew. Chem.
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dimethylaniline 2a
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2014; (b) F. A. Devillanova, W.-W. du Mont, Handbook of
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A mixture of phenylselenium bromide (0.25 mmol, 59 mg) and
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standard conditions. Yield of 3a: 91% (63 mg).
Org.
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Reaction catalyzed by HI and NaI
A mixture of diphenyl diselenide 1a (0.125 mmol, 39 mg), N,N-
dimethylaniline 2a (0.25 mmol, 30 mg), 3 equiv. of DMSO (0.75
mmol, 59 mg) and 20 mol% of catalyst i.e. HI (6 mg) or NaI (8
mg), were used under standard conditions. Yield of 3a: 82%
(57mg) in case of HI; no product was observed in case of NaI.
9
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Acknowledgements
We gratefully acknowledge CAPES, CNPq, FAPESP-GSK, INCT-
Catálise and FAPESC-Pronex for financial support. S.S. (doctoral
fellow) and J.R. (postdoctoral fellow) thank CNPq, CAPES and
TWAS for the fellowships. Authors are also thankful to CEBIME
for HRMS analysis.
7
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19 (a) M. Tamres and S. N. Bhat, J. Am. Chem. Soc. 1972, 94, 2577;
(b) S. J. Lo, M. Tamres, Can. J. Chem. 1983, 61, 1933.
20 A controlled experiment has been performed under the
reaction condition of Table
1 (entry 9) with some
modifications in order to capture the formed DMS. By using
cannula needle, it was possible to collect the formed gas
directly in the NMR tube (placed in ice cold water) containing
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