Copper-catalyzed direct arylselenation of anilines by C-H bond cleavage

Article abstract of DOI:10.1002/adsc.201400804

We describe here an efficient and regioselective synthesis of arylselanyl anilines by copper-catalyzed direct arylselenation of arylamines. Using a catalytic amount of copper iodide in dimethyl sulfoxide at 110 °C under an air atmosphere, a range of aryls

Full text of DOI:10.1002/adsc.201400804

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DOI: 10.1002/adsc.201400804
À
Copper-Catalyzed Direct Arylselenation of Anilines by C H
Bond Cleavage
Vanessa G. Ricordi,a Samuel Thurow,a Filipe Penteado,a Ricardo F. Schumacher,a
Gelson Perin,a Eder J. Lenard¼o,a and Diego Alvesa,*
a
Laboratꢀrio de Sꢁntese Orgꢂnica Limpa - LASOL, Universidade Federal de Pelotas, UFPel, P.O. Box 354, 96010-900,
Pelotas, RS, Brazil
Fax : (+55) 53 3275-7533; Phone: (+55) 53 3275-7533; e-mail: diego.alves@ufpel.edu.br
Received: August 13, 2014; Revised: December 2, 2014; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201400804.
À
Abstract: We describe here an efficient and regiose-
lective synthesis of arylselanyl anilines by copper-
catalyzed direct arylselenation of arylamines. Using
a catalytic amount of copper iodide in dimethyl
sulfoxide at 1108C under an air atmosphere,
a range of arylselanyl anilines was obtained directly
from substituted diaryl diselenides in moderate to
lyzed coupling processes through CAr Se bond forma-
tion under mild reaction conditions from diaryl disele-
nides and using aryl halides or aryl boronic acids as
coupling partner.[8,9] Additionally, diaryl selenides
were also synthesized by reactions of arenediazonium
salts with nucleophilic arylselenium species.[10]
In the context of CAr-functionalization, direct aryla-
tion reactions through C H bond cleavage are
À
À
good yields via C H bond cleavage of aryl amines.
straightforward transformations in organic synthe-
sis.[11] This approach has emerged as an attractive al-
ternative to more commonly employed cross-coupling
reactions and has had a tremendous impact on the
carbon–carbon and carbon–heteroatom bond forma-
tion.[11] One of the major motivations for the use of
direct arylation methods is to simplify syntheses, both
À
Keywords: anilines; catalysis; C H bond cleavage;
copper; selenium
The applicability and versatility of organoselenium in terms of reducing the number of steps and waste
compounds has been confirmed by renowned books[1] generation.[12]
and reviews,[2] and their use as ionic liquid,[3] asym-
Few examples on the formation of a carbon–chalco-
metric catalysts,[4] their fluorescent properties[5] and gen bonds (e. g. C S, C Se and C Te) through C H
biological activities,[1d,2f–j] have been widely described. bond cleavage has been reported before.[13] For in-
À
À
À
À
À
Diaryl selenides are certainly the most studied class stance, in the case of C Se bond formation starting
of molecules in organoselenium chemistry. They play from diaryl diselenides, Cheng and co-workers de-
a fundamental role in organic chemistry as intermedi- scribed an atom-economic procedure to synthesize se-
ate in total synthesis[1,2,6] and pharmacological studies lenides via C H bond cleavage of trimethoxybenzene
À
in GPx-like activity.[7] As a consequence, a large (Scheme 1, Eq. 1).[13k] In other study, Zhang and Li
number of methodologies have been reported for the developed an efficient regioselective synthesis of 4-se-
[1,2]
À
selective formation of C Se bonds.
In some cases, lanyl-substituted arylamines by the FeF3/I2 catalyzed
the described methodologies need a long reaction selenation of arylamines in moderate to good yields
time, harsh reaction conditions, and stoichiometric or (Scheme 1, Eq. 2).[13l] More recently, Kumar and co-
greater amount of metallic reagents, and sometimes workers described a transition-metal-free synthesis of
the products are generated in moderate yields.[1,2]
unsymmetrical diaryl selenides from arenes and di-
To overcome these limitations, much attention has phenyl diselenide under oxidative conditions by using
been recently focused on the use of transition metal- potassium persulfate at room temperature (Scheme 1,
based catalytic systems to reduce the environmental Eq. 3).[13m]
impact of these systems.[8] Most of these systems in-
volve a homogeneous process and specific ligands, and direct methodology for the C Se bond formation
Consequently, the development of a simple, general
À
À
which in some cases may increase the cost and limit through C H bond cleavage starting from diaryl dise-
the scope of the reaction.[8] Recently, diaryl selenides lenides and arenes remains a significant challenge in
were efficiently synthesized by copper or iron cata- organic synthesis. In this sense and according to our
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Table 1. Reaction conditions optimization using N,N-dime-
thylaniline 2a.[a]
Entry Copper Salt
[mol%]
Solvent/
T [8C]
Time Yield 3a [%][b]
[h]
1
2
3
4
5
6
7
8
CuI (10)
CuI (10)
CuI (10)
CuI (10)
CuI (10)
CuBr (10)
CuCl (10)
CuCl2 (10)
Cu(OAc)2 (10) DMSO/110 24
CuO NPs (10) DMSO/110 24
CuI (5)
CuI (3)
CuI (1)
–
DMF/120
24
20%
traces
traces
traces
90%
90%
53%
50%
75%
57%
90%
90%
66%
–
glycerol/110 24
toluene/110 24
dioxane/100 24
DMSO/110
DMSO/110
2
3
DMSO/110 24
DMSO/110 24
9
10
11
12
13
14
15[c]
Scheme 1. Examples of direct arylselenation of arenes by
DMSO/110
DMSO/110
DMSO/110 24
DMSO/110 24
DMSO/110 24
2
3
À
C H bond cleavage.
interest in the synthesis of nitrogen-functionalized or-
ganoselenium compounds[13k,14] and coupling reac-
tions,[9c,15] we describe herein our results on the direct
and regioselective synthesis of arylselanyl anilines by
the copper-catalyzed C H bond cleavage of aryl
amines (Scheme 1).
CuI (3)
traces
[a]
Reactions were performed in the presence of compounds
1a (0.25 mmol) and 2a (0.5 mmol) using 0.5 mL of sol-
vent, in an open atmosphere.
Yields are given for isolated product.
Reaction was performed in a N2 atmosphere.
À
[b]
[c]
Firstly, our attention was focused on the optimiza-
tion of the reaction conditions for the synthesis of ar-
ylselanyl aniline 3a starting from diphenyl diselenide served that the best results were obtained using
1a and N,N-dimethylaniline 2a (Table 1). Recently 10 mol% of CuI or CuBr, with the desired product
À
published work on the C H bond cleavage to accom- 3a being obtained in high yields. Unsatisfactory result
plish the arylselenation of di- or trimethoxybenzene was obtained when CuO NPS was used (Table 1;
with diaryl diselenides used CuI and DMF at entry 10). We observed that the reaction performed
1208C.[13k] Thus, we started studying the reaction of using CuI was faster than that with CuBr (Table 1;
substrates 1a (0.25 mmol) and 2a (0.5 mmol) in the entry 5 vs. 6). Therefore, CuI was chosen for further
presence of CuI (10 mol%) using DMF as solvent at studies on optimizing the reaction conditions. Fortu-
1208C in air. Under these reaction conditions, product nately, when the amount of catalyst was reduced from
3a was obtained only in 20% yield after 24 h 10 to 5 and 3 mol%, excellent yields of product 3a
(Table 1; entry 1).
were obtained (Table 1; entries 11 and 12). However,
Aiming to improve the yield of product 3a, a mix- in the reaction using 1 mol% of CuI, a great decrease
ture of diphenyl diselenide 1a, N,N-dimethylaniline in the yield of product 3a was observed, even after
2a and CuI (10 mol%) were reacted in air using dif- 24 h (Table 1; entry 13). In the absence of copper cat-
ferent solvents, such as DMSO, glycerol, toluene and alyst no reaction had taken place even after 24 h
1,4-dioxane (Table 1; entries 2-5). When the reactions (Table 1; entry 14). When the reaction was carried out
were performed using glycerol, toluene and 1,4-diox- under a nitrogen atmosphere, only traces of product
ane as solvents, only trace amounts of the phenylse- 3a was obtained and the starting materials were re-
lanyl aniline 3a were observed (Table 1; entries 2-4). covered (Table 1; entry 15).
Interestingly, when we carried out the reaction in
DMSO, the desired product 3a was obtained in 90% (0.25 mmol), N,N-dimethylaniline 2a (0.5 mmol), CuI
yield after 2 h (Table 1, entry 5). (3 mol%) were dissolved in DMSO (0.5 mL). The ho-
In an optimized reaction, diphenyl diselenide 1a
The reaction was then screened using different mogeneous reaction mixture was stirred for 3 h at
copper salts (Table 1; entries 6-10). Analyzing the va- 1108C under atmospheric air, affording N,N-dimeth-
riety of tested copper(I) and copper(II) salts, we ob- yl-4-(phenylselanyl)aniline 3a in 90% yield.
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Copper-Catalyzed Direct Arylselenation
Table 2. Scope and generality of the Reaction.[a]
Table 2. (Continued)
Entry
Substituted
Aniline
Time
[h]
Product
Yield
[%][b]
9
24
10
20
5
62
73
69
61
57
Entry
Substituted
Aniline
Time
[h]
Product
Yield
[%][b]
10
11
12
1
3
90
2
3
4
4
93
4
79
13
14
5
24
traces
[c]
24
24
–
15
–
5
6
2
3
73
84
[a]
Reactions were performed in the presence of diphenyl
diselenide 1a (0.25 mmol), anilines 2a–o (0.5 mmol), and
CuI (3 mol%), using 0.5 mL of DMSO, in an open at-
mosphere at 1108C.
Yields are given for isolated product.
A complex mixture of products was obtained.
[b]
[c]
The scope of our methodology was evaluated by re-
acting other N,N-disubstituted anilines (2b-g) with di-
phenyl diselenide 1a, and according to our results,
moderate to good yields were obtained for a variety
of substrates, including alicyclic ones (Table 2; en-
tries 2-6). When the reactions were performed using
N,N-diethylaniline 2b and N,N-dibutylaniline 2c, the
desired products 3b and 3c were obtained in 93 and
79% yields, respectively, both after 4 h (Table 2; en-
tries 2 and 3). Only traces of product 3d was observed
using N,N-dibenzylaniline 2d as substrate, even after
24 h of stirring at 1108C (Table 2; entry 4).
7
8
2
77
73
24
Reactions using alicyclic arylamines such as, 1-phe-
nylpyrrolidine 1e and 4-phenylmorpholine 1 f, were
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effectively performed with PhSeSePh 1a under CuI
catalysis, giving the respective selanylanilines 3e and
3 f in 73 and 84% yields (Table 2; entries 5-6).
Furthermore, to our delight, when the reaction was
performed with aniline 2g, only the formation of 4-
(phenylselanyl)aniline 3g was observed and in 77%
yield (Table 2; entry 7). In view of this result, substi-
tuted aryl amines 2h–2o were reacted with diphenyl
diselenide 1a using CuI as catalyst (Table 2; en-
tries 8–15). Reactions carried out with o- and p-tolui-
dine 2h and 2i afforded selectively the corresponding
products 3h and 3i in 53 and 52% yields, respectively
(Table 2; entries 8 and 9). Likewise, reactions per-
formed using 2-chloro- or 4-chloroaniline 2j and 2k
gave selectively the corresponding substituted phenyl-
selanyl anilines 3j and 3k in satisfactory yields
(Table 2; entries 10 and 11). It is important to note
that when p-toluidine and 4-chloroaniline were used,
the insertion of the PhSe group is on the ortho posi-
tion of the aniline. In addition, reaction performed
with 2-aminopyridine 2m furnished exclusively the re-
spective product 3m in 57% yield (Table 2; entry 13).
Unfortunately, when the reactions were carried out
with 3-aminopyridine 2n and 4-aminopyridine 2o, the
corresponding products 3n and 3o were not obtained,
even after 24 h (Table 2; entries 14 and 15).
Scheme 2. Scope using substituted diaryl diselenides.
Then the possibility of performing these reactions
with other diaryl diselenides (1b-e) was also investi-
gated. Different diaryl diselenides containing elec-
tron-donating and electron-withdrawing group at the
aromatic ring were reacted with N,N-dimethylaniline
2a, affording the respective N,N-dimethyl-4-arylselan-
yl anilines 3p–s in moderated to good yields, however
with higher reaction times compared to PhSeSePh 1a
(Scheme 2). The results revealed that the yield of re-
action is sensitive to the electronic effect of the aro-
matic ring of diaryl diselenide. For example, diaryl
diselenide 1b, bearing electron-donating group (Me)
Figure 1. A plausible mechanism of the reaction.
gave lower yields than the diaryl diselenides 1c–e, generating diaryl diselenide and CuI in the catalytic
bearing electron-withdrawing groups (Cl, F and cycle (Figure 1).
CF3).[16]
In summary, we have developed the copper-cata-
Based on recent publications involving copper-cata- lyzed direct arylselenation of arylamines. Using a cata-
lyzed carbon–chalcogen bond formation[8,9,13k] and re- lytic amount of CuI in DMSO at 1108C under air at-
actions using anilines as nucleophiles,[13j,13 L,17] a plau- mosphere, a range of arylselanyl anilines from substi-
sible mechanism for the arylselenation of anilines by tuted diaryl diselenides was directly obtained in good
À
À
C H bond cleavage is depicted on Figure 1.
yields via C H bond cleavage of aryl amines. This
We believe that, at first, the interaction of CuI with protocol affords an atom-economic and suitable
diaryl diselenide leads to the CuIII tetracoordinated method for the regioselective synthesis of arylselanyl
chalcogenolate A.[8a,18] After that, aniline 1 would anilines.
attack the intermediate A at the para-position to
form the intermediate B. A reductive elimination pro-
À
motes the C Se bond formation and an intermediary
iminium C and anionic complex ArSeCuI D were for-
Experimental Section
med.[8,9,13k] A proton elimination from intermediate C
prompted by anionic complex D releases the expected
General Information:
product 3 and the arylselenol species (ArSeH), which
is oxidized under the air atmosphere and DMSO, re- silica gel (60 F254) by using UV light as visualizing agent and
Reactions were monitored by TLC carried out on Merck
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Copper-Catalyzed Direct Arylselenation
5% vanillin in 10% H2SO4 and heat as developing agents.
Baker silica gel (particle size 0.040–0.063 mm) was used for
flash chromatography. Proton nuclear magnetic resonance
spectra (1H NMR) were obtained at 300 MHz on a Varian
Gemini NMR and at 400 MHz on Bruker DPX 400 spec-
trometers. Spectra were recorded in CDCl3 solutions. Chem-
ical shifts are reported in ppm, referenced to tetramethylsi-
lane (TMS) as the external reference. Hydrogen coupling
patterns are described as singlet (s), doublet (d), triplet (t),
quartet (q), double doublet (dd), broad singlet (bs) and mul-
tiplet (m). Coupling constants (J) are reported in Hertz.
Carbon-13 nuclear magnetic resonance spectra (13C NMR)
were obtained at 75 MHz on a Varian Gemini NMR and at
100 MHz on Bruker DPX 400 spectrometers. Chemical
shifts are reported in ppm, referenced to the solvent peak of
CDCl3. Low-resolution mass spectra were obtained with
a Shimadzu GC-MS-QP2010 mass spectrometer. High reso-
lution mass spectra (HRMS) were recorded on a Bruker
Micro TOF-QII spectrometer 10416. Column chromatogra-
phy was performed using Merck Silica Gel (230–400 mesh).
77(14); HRMS calcd. for C20H28NSe [M]+ 362.1387, found:
326.1207.
1-(4-(Phenylselanyl)phenyl)pyrrolidine
(3e):
Yield:
1
0.111 g (73%); yellow solid; mp 85–868C; H NMR (CDCl3,
400 MHz) d=7.46 (d, J=8.8 Hz, 2H), 7.26–7.24 (m, 2H),
7.16–7.08 (m, 3H), 6.49 (d, J=8.8 Hz, 2H), 3.27–3.24 (m,
4H), 1.99–1.96 (m, 4H); 13C NMR (CDCl3, 100 MHz) d=
147.9, 137.3, 134.9, 129.4, 128.8, 125.5, 112.5, 112.3, 47.4,
25.4; MS (relative intensity) m/z: 303 (26), 223 (110), 167
(16), 152 (11), 117 (9), 77 (21); HRMS calcd. for C16H17NSe
[M]+ 303.0526, found: 303.0515.
4-(4-(Phenylselanyl)phenyl)morpholine
(3 f):
Yield:
1
0.134 g (84%); white solid; mp 69–718C; H NMR (CDCl3,
400 MHz) d=7.46 (d, J=8.4 Hz, 2H), 7.32–7.30 (m, 2H),
7.19–7.13 (m, 3H), 6.80 (d, J=8.5 Hz, 2H), 3.82–3.80 (m,
4H), 3.14–3.12 (m, 4H); 13C NMR (CDCl3, 100 MHz) d=
151.0, 136.2, 133.4, 130.6, 128.9, 126.1, 118.4, 116.0, 66.6,
48.5; MS (relative intensity) m/z: 319 (38), 261 (8), 239
(100), 181 (90), 130 (5), 77 (17); HRMS calcd. for
C16H18NOSe [M]+ 320.0554, found: 320.0387.
4-(Phenylselanyl)aniline[19] (3g): Yield: 0.096 g (77%);
1
yellow solid; mp 87–918C; H NMR (CDCl3, 400 MHz) d=
7.39 (d, J=8.5 Hz, 2H), 7.30–7.28 (m, 2H), 7.20–7.13 (m,
3H), 6.61 (d, J=8.5 Hz, 2H), 3.75 (bs, 2H); 13C NMR
(CDCl3, 100 MHz) d=146.8, 137.0, 134.0, 130.1, 128.9, 126.0,
116.4, 115.9; MS (relative intensity) m/z: 249 (17), 247 (8),
169 (100), 92 (4), 77 (13).
2-Methyl-4-(phenylselanyl)aniline (3h): Yield: 0.096 g
(73%), brown solid, mp 56–598C; 1H NMR (CDCl3,
400 MHz) d=7.31–7.26 (m, 4H), 7.18–7.11 (m, 3H), 6.57 (d,
J=8.0 Hz, 1H), 3.67 (bs, 2H), 2.09 (s, 3H); 13C NMR
(CDCl3, 75 MHz) d=145.0, 137.8, 134.7, 134.2, 130.0, 128.9,
125.8, 123.3, 116.1, 115.6, 17.0; MS (relative intensity) m/z:
263 (24), 183 (100), 106 (16), 77 (14); HRMS calcd. for
C13H14NSe: [M + H]+ 264.0286, found: 264.0291.
General Procedure for the Copper-Catalyzed Direct
Arylselenation of Anilines:
To a 3 mL round-bottomed flask containing diaryl diselenide
(0.25 mmol), an appropriated aniline (0.5 mmol) and CuI
(3 mol%), DMSO (0.5 mL) was added. The homogeneous
reaction mixture was stirred at 1108C for the time indicated
in Table 2 and Scheme 2. After that time, the solution was
cooled to room temperature, diluted with ethyl acetate
(20 mL), and washed with water (3ꢄ20 mL). The organic
phase was separated, dried over MgSO4 and concentrated
under vacuum. The obtained products were purified by flash
chromatography on silica gel using hexane or a mixture of
ethyl acetate/hexane as the eluent.
4-Methyl-2-(phenylselanyl)aniline (3i): Yield: 0.082 g
1
N,N-Dimethyl-4-(phenylselanyl)aniline
(3a):
Yield:
(62%), brown oil; H NMR (CDCl3, 400 MHz) d=7.40–7.39
1
0.125 g (90%); yellow solid; mp 35–388C; H NMR (CDCl3,
400 MHz) d=7.46 (d, J=8.9 Hz, 2H), 7.27–7.25 (m, 2H),
7.15–7.06 (m, 3H), 6.62 (d, J=8.9 Hz, 2H), 2.90 (s, 6H);
13C NMR (CDCl3, 100 MHz) d=150.4, 136.9, 134.5, 129.7,
128.8, 125.7, 113.6, 113.0, 40.1; MS (relative intensity) m/z:
277 (25), 197 (100), 196 (53), 181 (11), 157 (3), 91 (3), 77
(12); HRMS calcd. for C14H15NSe: [M + Na]+ 300.0267,
found: 300.0368.
(m, 1H), 7.25–7.13 (m, 5H), 7.03–7.01 (m, 1H), 6.70 (d, J=
8.1 Hz, 1H), 4.12 (bs, 2H), 2.22 (s, 3H); 13C NMR (CDCl3,
100 MHz) d=146.1, 138.5, 131.8, 131.7, 129.3, 129.1, 128.1,
126.0, 115.0, 112.7, 20.1; MS (relative intensity) m/z: 263
(22), 261 (11), 183 (100), 167 (9), 106 (20), 91 (6), 77 (26);
HRMS calcd. for C13H14NSe: [M + H]+ 264.0286, found:
264.0288.
2-chloro-4-(phenylselanyl)aniline (3j): Yield: 0.104 g
(73%), brown solid, mp 51–548C; 1H NMR (CDCl3,
400 MHz) d=7.49 (d, J=1.9, 1H), 7.32–7.15 (m, 6H), 6.65
(d, J=8.2 Hz, 1H), 4.11 (bs, 2H); 13C NMR (CDCl3,
100 MHz) d=143.1, 135.9, 134.9, 133.1, 130.7, 129.1, 126.4,
119.5, 117.0, 116.3; MS (relative intensity) m/z: 283 (26), 278
(4), 203 (100), 167 (9), 114 (4), 77 (7); HRMS calcd. for
C12H11ClNSe: [M + H]+ 283.9737, found: 283.9738.
N,N-Diethyl-4-(phenylselanyl)aniline (3b): Yield: 0.142 g
1
(93%); brown oil; H NMR (CDCl3, 200 MHz) d=7.45 (d,
J=8.9 Hz, 2H), 7.31–7.24 (m, 2H), 7.23–7.11 (m, 3H), 6.62
(d, J=8.9 Hz, 2H), 3.36 (q, J=7.0 Hz, 4H), 1.17 (t, J=7.0,
6H); 13C NMR (CDCl3, 100 MHz) d=147.9, 137.5, 134.8,
129.5, 128.9, 125.6, 112.4, 112.0, 44.3, 12.5; MS (relative in-
tensity) m/z: 305 (61), 290 (100), 261 (18), 225 (53), 210
(56), 152 (20), 118 (23), 77 (26); HRMS calcd. for
C16H19NSe [M + Na]+ 328.0580, found: 328.0611.
4-Chloro-2-(phenylselanyl)aniline (3k): Yield: 0.097 g
(69%), brown solid, mp 57–608C. 1H NMR (CDCl3,
400 MHz) d=7.53 (d, J=2.4, 1H); 7.26–7.12 (m, 6H); 6.68
(d, J=8.5 Hz, 1H); 4.24 (bs, 2H). 13C NMR (CDCl3,
100 MHz) d=147.0, 137.0, 130.7, 130.6, 129.8, 129.3, 126.6,
122.4, 115.8, 113.9. MS (relative intensity) m/z: 283 (31), 281
(15), 203 (100), 167 (29), 125 (5), 99 (7), 77 (14). HRMS
N,N-Dibutyl-4-(phenylselanyl)aniline (3c): Yield: 0.142 g
1
(79%); brown oil; H NMR (CDCl3, 400 MHz) d=7.43 (d,
J=8.9 Hz, 2H), 7.30–7.28 (m, 2H), 7.19–7.11 (m, 3H), 6.57
(d, J=8.9 Hz, 2H), 3.28–3.24 (m, 4H), 1.61–1.53 (m, 4H),
1.40–1.30 (m, 4H); 0.96 (t, J=7.2 Hz, 6H); 13C NMR
(CDCl3, 100 MHz) d=148.4, 137.3, 134.8, 129.7, 128.9, 125.7,
112.5, 112.1, 50.7, 29.3, 20.3, 13.9; MS (relative intensity) m/
z: 361(63), 318 (99), 276 (100), 238(9), 181(26), 105(32),
calcd. for C12H11ClNSe: [M
283.9743.
+
H]+ 283.9737, found:
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2-Fluoro-4-(phenylselanyl)aniline (3l): Yield: 0.081 g
Acknowledgements
(61%), brown solid, mp 39–428C. 1H NMR (CDCl3,
400 MHz) d=7.34–7.31 (m, 2H); 7.23–7.15 (m, 5H); 6.69
(dd, J=9.1 and 8.1 Hz, 1H); 3,79 (bs, 2H). 13C NMR
(CDCl3, 100 MHz) d=151.3 (d, J (C-F)=243.0 Hz), 134.9
(d, J (C-F)=12.7 Hz), 133.0, 131.6 (d, J (C-F)=3.0 Hz),
130.9, 129.1, 126.5, 122.0 (d, J (C-F)=18.7 Hz), 117.3 (d, J
(C-F)=3.6 Hz), 116.8 (d, J (C-F)=6.0 Hz). MS (relative in-
tensity) m/z: 267 (21), 265 (11), 207 (12), 187 (100), 154
(14), 91 (5), 77 (32). HRMS calcd. for C12H11FNSe: [M +
H]+ 268.0035, found: 268.0051.
The authors are grateful to FAPERGS, CNPq, CAPES, and
FINEP for the financial support.
References
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2-Amino-5-(phenylselanyl)pyridine (3m): Yield: 0.071 g
(57%), yellow solid, mp 111–1148C. 1H NMR (CDCl3,
400 MHz) d=8.28 (dd, J=2.2 and 0.6 Hz, 1H), 7.61 (dd, J=
8.5 and 2.2 Hz, 1H), 7.31–7.28 (m, 2H), 7.21–7.15 (m, 3H),
6.42 (dd, J=8.5 and 0.6 Hz, 1H), 4.79 (bs, 2H). 13C NMR
(CDCl3, 100 MHz) d=158.34, 154.31, 144.98, 133.01, 130.21,
129.07, 126.35, 113.38, 109.45. MS (relative intensity) m/z:
250 (22), 207 (12), 170 (100), 154 (14), 143 (24), 92 (20), 77
(17). HRMS calcd. for C11H11N2Se: [M + H]+ 251.0082,
found: 251.0084.
N,N-Dimethyl-4-(o-tolylselanyl)aniline
(3p):
Yield:
1
0.067 g (46%), yellow oil. H NMR (CDCl3, 400 MHz) d=
7.43 (d, J=8.9 Hz, 2H); 7.12–6.96 (m, 4H); 6.67 (d, J=
8.9 Hz, 2H); 2.96 (s, 6H); 2.37 (s, 3H). 13C NMR (CDCl3,
100 MHz) 150.5, 137.2, 136.9, 135.2, 129.7, 129.4, 126.4,
125.7, 113.3, 113.0, 40.2, 21.5. MS (relative intensity) m/z:
291 (40), 211 (100), 196 (8), 121 (54), 91 (14), 77 (10).
HRMS calcd. for C15H17NSe [M + Na]+ 314.0424, found:
314.0381.
4-(4-Chlorophenylselanyl)-N,N-dimethylaniline
(3q):
1
Yield: 0.127 g (82%), white solid, mp 111–1168C. H NMR
(CDCl3, 400 MHz) d=7.45 (d, J=8.6 Hz, 2H), 7.19 (d, J=
8.5 Hz, 2H), 7.13 (d, J=8.5 Hz, 2H), 6.67 (d, J=8.6 Hz,
2H), 2.97 (s, 6H). 13C NMR (CDCl3, 100 MHz) d=150.5,
137.3, 137.0, 132.8, 131.9, 131.2, 129.0, 113.4, 40.3. MS (rela-
tive intensity) m/z: 311 (17), 308 (4), 233 (33), 231 (100), 200
(9), 152 (8), 115 (19), 77 (12); HRMS calcd. for
C14H14ClNSe [M + Na]+ 333.9878, found: 333.9865.
4-(4-Fluorophenylselanyl)-N,N-dimethylaniline
(3r):
Yield: 0.116 g (79%), gray solid, mp 49–528C. 1H NMR
(CDCl3, 400 MHz) d=7.44 (d, J=8.9 Hz, 2H), 7.29–7.26 (m,
2H), 6.89 (t, J=8.8 Hz, 2H), 6.64 (d, J=8.9 Hz, 2H), 2,96
(s, 6H); 13C NMR (CDCl3, 100 MHz) d=161.7 (d, J (C-F)=
245.1 Hz), 150.5, 136.6, 132.2 (d, J (C-F)=7.7 Hz), 128.6 (d,
J (C-F)=3.3 Hz), 116.1 (d, J (C-F)=21.6), 114.4, 113.2, 40.2;
MS (relative intensity) m/z: 295 (20), 293 (10), 215 (100),
199 (16), 184 (4), 170 (5), 107 (18), 77 (9); HRMS calcd. for
C14H14FNSe [M + Na]+ 318.0173, found: 318.0274.
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(3s): Yield: 0.135 g (77%), brown solid, mp 48–528C;
1H NMR (CDCl3, 400 MHz) d=7.52–7.51 (m, 1H), 7.48 (d,
J=8.9 Hz, 2H), 7.37–7.35 (m, 1H), 7.28–7.22 (m, 1H), 6.88
(d, J=8.9 Hz, 2H), 2.99 (s, 6H); 13C NMR (CDCl3,
100 MHz) d=150.8, 137.5, 136.3, 132.5, 131.1 (q, J (C-F)=
32.2 Hz), 129.1, 125.8 (q, J (C-F)=3.9 Hz), 123.8 (q, J (C-
F)=272.8 Hz), 122.4 (q, J (C-F)=3.8 Hz), 113.2, 112.2, 40.2;
MS (relative intensity) m/z: 345 (28), 265 (100), 249 (10),
200 (14), 132 (8), 77 (10); HRMS calcd. for C15H14F3NSe [M
+ Na]+ 368.0141, found: 368.0221.
6
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Adv. Synth. Catal. 0000, 000, 0 – 0
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COMMUNICATIONS
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ÞÞ
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COMMUNICATIONS
À
8 Copper-Catalyzed Direct Arylselenation of Anilines by C
H Bond Cleavage
Adv. Synth. Catal. 2015, 357, 1 – 8
Vanessa G. Ricordi, Samuel Thurow, Filipe Penteado,
Ricardo F. Schumacher, Gelson Perin, Eder J. Lenard¼o,
Diego Alves*
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