Copper-catalyzed: Ipso -selenation of aromatic carboxylic acids

Article abstract of DOI:10.1039/c7ob02066j

The copper-catalyzed decarboxylative selenation of aromatic carboxylic acids with diselenide is reported. This transformation tolerated a diverse set of functional groups on the substrates, including pentafluorobenzoic acid and heteroaromatic acids, delivering diaryl and methyl aryl selenides in good to excellent yields. Mechanistic studies indicated that the copper catalyst is essential in the activation of the Se-Se bond and the decarboxylation of aromatic acids. The utility of the products has been demonstrated in the facile synthesis of 10H-phenoselenazine and 11-methyldibenzo-(b,f)-1,4-selenazepine.

Full text of DOI:10.1039/c7ob02066j

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Copper-catalyzed ipso-selenation of aromatic
carboxylic acids†
Cite this: DOI: 10.1039/c7ob02066j
Jing Wang,a Hongchen Li,b Tao Leng,b Miaochang Liu,b Jinchang Ding,b
a,c
Xiaobo Huang, b Huayue Wu,*b Wenxia Gaob and Ge Wu
*
The copper-catalyzed decarboxylative selenation of aromatic carboxylic acids with diselenide is reported.
This transformation tolerated a diverse set of functional groups on the substrates, including pentafluoro-
benzoic acid and heteroaromatic acids, delivering diaryl and methyl aryl selenides in good to excellent
yields. Mechanistic studies indicated that the copper catalyst is essential in the activation of the Se–Se
bond and the decarboxylation of aromatic acids. The utility of the products has been demonstrated in the
facile synthesis of 10H-phenoselenazine and 11-methyldibenzo-(b,f )-1,4-selenazepine.
Received 18th August 2017,
Accepted 31st October 2017
DOI: 10.1039/c7ob02066j
rsc.li/obc
Introduction
The C–Se bond is an important motif in pharmaceutical and
biologically active compounds.1 For example, diaryl selenides
have been used in several applications, such as human cancer
cell growth inhibitors,2a TR inhibitors2a and tubulin polymer-
ization inhibitors2b (Scheme 1c). Additionally, aryl selenides
serve as spectroscopic tools for neuro-biological applications,3a
but they also function as key intermediates in the synthesis of
aryl selenones3b and selenoxides.3c Therefore, developing an
efficient and practical method for the synthesis of these useful
compounds is highly attractive.
Over the last few decades, the formation of transition-metal
catalyzed C–Se bonds via the cross-coupling of aryl halides or
boronic acid with selenols or diselenides has emerged as an
important tool for the rapid construction of aryl selenides
(Scheme 1a).4 However, one of the drawbacks among these
methods is that they require prefunctionalized substrates.
Subsequently, the regio-selective C–H selenation of arenes
with diselenides has been achieved under transition-metal cat-
alysis with a directing group on the substrates.5 Furthermore,
the metal-free radical selenation of aryl diazonium ions with
diphenyl diselenides has been reported.6 Despite these trans-
formations representing significant advancements toward the
formation of a new C–Se bond, there is still an urgent need to
Scheme 1 Representative aryl selenides and oxidative decarboxylative
C–Se coupling.
utilize the easily accessible substrates to construct the complex
selenium-containing compounds through an efficient and ver-
satile protocol, which remains a great challenge. In addition, a
structurally diverse, readily-available, and bench-stable starting
material is preferred, among which aromatic carboxylic acids
are good candidates.7 In our previous studies on copper-cata-
lyzed arylselenation reactions, we showed that PhSeCu inter-
mediates could be intercepted by nucleophiles such as indoles
and azoles to allow the C3-phenylselenation of indoles8a and
3-arylselanyl-azoles,8b respectively, or could react with electro-
philic epoxides to give β-hydroxy phenylselenides.8c We envi-
sioned that the PhSeCu intermediate generated in situ could
also react with aromatic carboxylic acids to afford the de-
aSchool of Pharmaceutical Science, Wenzhou Medical University, Wenzhou 325035,
People’s Republic of China. E-mail: wuge@wmu.edu.cn
bCollege of Chemistry and Materials Engineering, Wenzhou University, Wenzhou
325035, People’s Republic of China. E-mail: huayuewu@wzu.edu.cn
cState Key Laboratory of Structural Chemistry, Fujian Institute of Research on the
Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China
†Electronic supplementary information (ESI) available: Copies of 1H and 13C
NMR spectral data. See DOI: 10.1039/c7ob02066j
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carboxylative C–Se coupling products. Recently, Hoover and co- were used, 4-methoxy-2-nitrobenzoic acid was smoothly con-
workers reported the copper-catalyzed decarboxylative thiola- verted into the desired product (entries 4–6); further explora-
tion to synthesize aryl sulfides.7h Here, we report the copper- tion confirmed that Cu(OAc)2 was the most efficient catalyst.
catalyzed oxidative decarboxylative selenation of aromatic car- The poor activities of the Cu(I) salts are likely due to the sele-
boxylic acids with diselenides, affording the diaryl selenides nide compounds, which act as “soft” ligands, binding strongly
and methyl aryl selenides. The key features of this transform- to the low valent copper species and causing catalyst de-
ation are the use of oxygen as the oxidant and the dual roles of activation. K2CO3 was found to be the optimal base among all
the copper catalyst. The utility of this method was also demon- the bases examined, namely, Li2CO3, Na2CO3 and Cs2CO3
strated in the facile synthesis of 10H-phenoselenazine9a and (entries 7–9). It is worth noting that the efficiency of the
11-methyldibenzo-(b,f )-1,4-selenazepine.9b
reaction was dependent on their cations, probably because the
The potential issues in such transformations include the bases were involved in the activation of the Se–Se bond of the
deactivation of the copper species by excess selenium com- starting material and were required to promote anion
pounds,10 the copper-catalyzed protodecarboxylation of the exchange of the benzoate with the copper catalyst to trigger
aromatic acids11 or homo-coupling.12 To address these pro- the reaction. Subsequent investigation on the effect of
blems, our strategy was to identify a suitable bidentate ligand different solvents found that when the reaction was conducted
to modify the steric environment and electron density on the in a polar solvent, such as DMF or DMSO, or a weakly coordi-
copper, resulting in the formation of a copper intermediate nating solvent, such as THF (entries 10–12), only the protode-
that could favor coordination to the selenide and aryl groups. carboxylation by-product 3-nitroanisole was observed. It is
In addition, we reasoned that the “hardness” of high valent believed that coordinating solvents interfere with the selena-
copper might alleviate the problem of catalyst poisoning.
tion process by competing with the benzoate anion or
selenium atom at the copper center. Control experiments indi-
cated that the combination of copper and a ligand with a weak
base was required for the decarboxylative C–Se coupling
reaction (entries 14–16).
Results and discussion
With the optimal conditions in hand, we examined the
scope of aromatic benzoic acids 1 (Scheme 2). Both electron-
donating (3a, 3c) and electron-withdrawing (3d) groups on the
benzene ring of the aryl acid were well tolerated and afforded
the corresponding C–Se coupling products in good to excellent
yields. Sterically hindered substrates also provided the desired
At the onset of this project, we chose the reaction between
4-methoxy-2-nitrobenzoic acid and diphenyl diselenide as the
model system for screening a variety of reaction parameters. As
shown in Table 1, we observed that the choice of the copper
catalyst had a considerable impact on the reaction outcome.
When Cu(I) salts (entries 1–3) were used as catalysts, the sele-
nation did not proceed at all. In contrast, when Cu(II) salts
Table 1 Optimization of the reaction conditionsa
Entry
[Cu]
Base
Solvent
Yieldb, %
1
2
3
4
5
6
7
8
CuI
CuBr
CuCl
Cu(OAc)2
CuBr2
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
Li2CO3
Na2CO3
Cs2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
—
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
DMF
DMSO
THF
Toluene
Toluene
Toluene
Toluene
0
0
0
92
45
78
21
65
34
0
0
0
17
0
0
CuCl2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
—
9
10
11
12
13c
14
15d
16
Cu(OAc)2
Cu(OAc)2
Scheme 2 The scope of aryl acids. Reaction conditions unless
specified otherwise: aryl acid (0.2 mmol), diphenyl diselenide
(0.3 mmol), Cu(OAc)2 (15 mmol %), phen (15 mmol %) and K2CO3
(0.6 mmol) in toluene (2 mL) were stirred at 150 °C for 24 h under 1 atm
of O2, isolated yield. a Pentafluorobenzoic acid (0.4 mmol), diphenyl
diselenide (0.2 mmol).
0
a Reaction conditions unless stated otherwise: 1a (0.2 mmol), 2a
(0.3 mmol), [Cu] (15 mmol %), phen (15 mmol %), base (0.6 mmol),
solvent (2.0 mL), under O2, 150 °C, 24 h. b Isolated yield. c Under N2.
d In the absence of the phen ligand.
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products 3e and 3i in good yields. Moreover, halogen substi- verted into aryl methyl selenides (4f–4l) via the reaction with
tuted 2-nitrobenzoic acids were smoothly converted to the sele- dimethyl diselenide. Furthermore, a high selectivity for the
nation products (3f, 3g, 3h) with diphenyl diselenide, which arylselenation of benzo[b]thiophene (4m, 4n) and benzofuran
provides an opportunity for further late-stage derivatization of (4o–4q) was still achieved even when the substituents on the
selenium-containing compounds. In addition, 2-benzoylben- substrates were changed.
zoic acid (3k) was tolerated, although the yield was relatively
The application of our method is shown in Scheme 4. The
lower. It is worth noting that decarboxylative selenation is sen- phenylselenation product 3b was smoothly transformed into
sitive to the electronic effects of the substituents on the ortho 10H-phenoselenazine 5d in 68% yield by a PPh3-mediated
benzoic acids, and when 2-chlorobenzoic acid, o-toluic acid or reductive cyclization reaction.13 Furthermore, the nitro group
o-anisic acid was subjected to the optimal reaction conditions, was then converted into an amine, giving the substituted
the desired products were not observed. However, the difluoro diphenyl selenide. The presence of a primary amino group as
substituted benzoic acid could be converted to the difluoro-substi- a versatile synthetic handle is an advantage. When 2-(phenyl-
tuted diaryl selenide (3j). When pentafluorobenzoic acid was selanyl)aniline was treated with diphenyl diselenide under
employed under the standard reaction conditions, only the photo-catalytic conditions, the corresponding 1,2-bis(phenyl-
chemoselective selenation product (3l) was obtained in good selanyl)benzene (5a) was generated with 53% yield.6b For the
yield, and the by-product from SNAr substitution was not detected. classical Sandmeyer reaction, the diazotization of 5 with
Interestingly, in the case of picolinic acid N-oxide, ortho-disele- NaNO2 followed by the reaction with KI gave (2-iodophenyl)
nated product 3m was obtained, which suggested that the reac- (phenyl)selane (5b) with 86% yield. In addition, the bio-
tion works through both decarboxylative and ortho C–H selena- logically active 11-methyldibenzo-(b,f )-1,4-selenazepine (5c)
tion mechanisms. To our delight, benzofuran-2-carboxylic acid, was synthesized from 5 with 77% yield.14
benzo[b]thiophene-2-carboxylic acid and thiazole-5-carboxylic acid
were tolerated in this reaction and gave the desired products in mediate15 and the copper(II) benzoate complex16 were syn-
high selectivities and good yields (3n, 3o, 3p). thesized according to the literature. Firstly, we conducted the
To further understand the mechanism, the PhSeCu inter-
Next, we examined the scope of diselenide 2 (Scheme 3). stoichiometric reaction of 2-nitrobenzoic acid with PhSeCu
Diaryl diselenides containing either meta or para substituents under our optimized reaction conditions, which afforded the
on the benzene ring were found to be efficient coupling part- desired product 3b with 74% yield (eqn (1)). As shown in
ners and gave the corresponding selenation products. The eqn (2) (Scheme 5), PhSeCu is a chemically competent inter-
reaction conditions are compatible with common functional mediate, which is consistent with our tentative hypothesis.
groups such as bromide (4a, 4d), chloride (4b), methoxymethyl Strikingly, the stoichiometric reaction of complex 1 with diphe-
(4e) and trifluoromethoxy (4c). It was exciting to discover that nyl diselenide led to a decarboxylative cross-coupling product
dimethyl diselenide was also an active selenating agent, and, with almost quantitative yield (eqn (3)). However, when
accordingly, various aromatic carboxylic acids have been con- complex 1 was used catalytically, the yield of 3b decreased to
22% (eqn (4)). These data indicated that copper(II) played dual
roles in Se–Se activation and decarboxylation, both key steps to
generate the selenide–copper complex, followed by decarboxyl-
ation to generate the ipso-selenation product. Additionally, the
nature of the original selenide source affected the reaction
outcome (eqn (5)). When the selenation reaction was
attempted using benzeneselenol, no product was observed.
Most likely, PhSeH has strong proclivity for copper catalyst de-
activation. Finally, potassium 2-nitrobenzoate could be
smoothly converted into product 3b with diphenyl diselenide
(eqn (6)), which suggested that the base plays a critical role in
deprotonating the aryl acids and forming the copper(II) benzo-
Scheme 3 The scope of diselenides. Reaction conditions unless
specified otherwise: aryl acid (0.2 mmol), diselenide (0.3 mmol),
Cu(OAc)2 (15 mmol %), phen (15 mmol %) and K2CO3 (0.6 mmol) in
toluene (2 mL) were stirred at 150 °C for 24 h under 1 atm of O2, with an
isolated yield.
Scheme 4 Derivatization of the selenation product 3b.
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Conclusions
In summary, a protocol for the copper-catalyzed decarboxyla-
tive selenation of aromatic carboxylic acids with diselenide has
been developed. This protocol enables a variety of aromatic
carboxylic acids to be converted to diaryl selenides or aryl
methyl selenides under aerobic reaction conditions. In particu-
lar, the selenation products could easily be transformed into
valuable selenium-containing azaheterocycles. Further study
on the utility of the current strategy for late-stage functionali-
zation of pharmaceuticals and the expansion of the scope is
currently underway in our laboratory.
Experimental
General remarks
Diaryl diselenides1 were prepared according to the reported
procedures.18 The 1H and 13C spectra of the known com-
pounds were in accordance with those described in the litera-
ture. All other reagents were purchased from TCI, Sigma-
Aldrich, Alfa Aesar, Acros, and Meyer and were used without
further purification. Toluene was distilled from Na under
Scheme 5 Preliminary mechanism investigation.
1
nitrogen and stored under nitrogen. H NMR (500 MHz), 13C
NMR (125 MHz) and 19F NMR (470 MHz) spectra were
recorded in CDCl3 solutions using a Bruker AVANCE 500
spectrometer. High-resolution mass spectra were recorded on
an ESI-Q-TOF mass spectrometer. The analysis of the crude
reaction mixture was carried out on the Varian 4000 GC/MS
and 1200 LC. All reactions were conducted using standard
Schlenk techniques. Column chromatography was performed
using EM silica gel 60 (300–400 m).
ate complex. Finally, we performed a radical clock experiment
by adding 3.0 equiv. of radical scavengers (eqn (7)), for
example TEMPO did not significantly alter the efficiency of the
oxidative decarboxylative selenation process, which suggested
that a single electron transfer mechanism could be excluded.
Based on the above results and previous literature reports,
we proposed a mechanism to explain the reaction of benzoic
acid and diselenide (Scheme 6). The initial Se–Se activation of
diselenide produced Se–Cu intermediate A. Then, the aromatic
carboxylate was transferred to the copper center by base-pro-
moted anion exchange, which would be followed by de-
carboxylation to generate organocopper species B. Then,
copper(III) C 17 was formed either by disproportionation with
another Cu(II) species or by oxidation with O2. Finally, reduc-
tive elimination could afford the desired selenation product
and regenerate the copper catalyst to complete the catalytic
cycle.
General procedure for the copper-catalyzed decarboxylative
selenation of aromatic carboxylic acids with diselenide
A 25 mL Schlenk tube equipped with a stir bar was charged
with 2-nitrobenzoic acid (0.2 mmol), diphenyl diselenide
(0.3 mmol), Cu(OAc)2 (15 mol%), 1,10-phen (15 mol%), K2CO3
(0.6 mmol) and 2 mL toluene. The tube was fitted with a
rubber septum, then it was evacuated and refilled with dioxy-
gen three times, and then the septum was replaced by a Teflon
screwcap under an oxygen flow. The reaction mixture was
stirred at 150 °C for 24 h. After cooling down, the reaction
mixture was diluted with 10 mL of ethyl ether and filtered
through a pad of silica gel, followed by washing the pad of the
silica gel with the same solvent (20 mL) and concentrated
under reduced pressure. The residue was then purified by
flash chromatography on silica gel to provide the corres-
ponding product.
Characterization data of compounds 3, 4 and 5
(4-Methoxy-2-nitrophenyl)(phenyl)selane (3a). Following the
general procedure, using petroleum ether as the eluant
afforded a yellow liquid (56.8 mg, 92% yield). 1H NMR
(500 MHz, CDCl3): δ 7.80 (d, J = 2.8 Hz, 1H), 7.69–7.67 (m, 2H),
7.50–7.47 (m, 1H), 7.45–7.42 (m, 2H), 6.93 (dd, J = 9.0, 2.8 Hz,
Scheme 6 Proposed catalytic cycle.
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1H), 6.86 (d, J = 9.0 Hz, 1H), 3.83 (s, 3H). 13C NMR (125 MHz,
(5-Fluoro-2-nitrophenyl)(phenyl)selane (3h). Following the
CDCl3): δ 157.9, 146.1, 137.3, 131.1, 130.0, 129.7, 128.5, 126.1, general procedure, using petroleum ether as the eluant
122.2, 109.3, 55.9. HRMS (TIC): calcd for
[M + H]+ 309.9977, found 309.9976.
C
13H11NO3Se afforded a yellow solid (49.8 mg, 84% yield), mp 92–93 °C.
1H NMR (500 MHz, CDCl3): δ 8.37 (dd, J = 9.1, 5.1 Hz, 1H),
(2-Nitrophenyl)(phenyl)selane7h (3b). Following the general 7.71 (m, 2H), 7.56–7.53 (m, 1H), 7.51–7.48 (m, 2H), 6.97–6.93
procedure, using petroleum ether as the eluant afforded a (m, 1H), 6.62 (dd, J = 9.4, 2.7 Hz, 1H). 13C NMR (125 MHz,
yellow solid (47.9 mg, 86% yield), mp 79–80 °C. 1H NMR CDCl3): δ 164.3 (d, JF = 257.6 Hz), 141.8, 139.9 (d, JF = 8.7 Hz),
(500 MHz, CDCl3): δ 8.30 (d, J = 8.0 Hz, 1H), 7.70–7.69 (m, 2H), 137.4, 130.4, 128.7 (d, JF = 10.4 Hz), 127.7, 116.6 (d, JF
=
7.50 (t, J = 7.5 Hz, 1H), 7.45 (t, J = 7.5 Hz, 2H), 7.31–7.24 (m, 26.9 Hz), 113.4, 113.2. 19F NMR (470 MHz, CDCl3): δ −102.6 (s,
2H), 7.00 (d, J = 8.0 Hz, 1H). 13C NMR (125 MHz, CDCl3): 1F). HRMS (TIC): calcd for C12H8FNO2Se [M + H]+ 297.9777,
δ 145.6, 137.4, 135.8, 133.6, 130.3, 130.1, 129.9, 128.2, 126.0, found 297.9775.
125.7. HRMS (TIC): calcd for C12H9NO2Se [M + H]+ 279.9872,
found 279.9870.
(2-Fluoro-6-nitrophenyl)(phenyl)selane (3i). Following the
general procedure, using petroleum ether as the eluant
(5-Methyl-2-nitrophenyl)(phenyl)selane (3c). Following the afforded a yellow liquid (36.8 mg, 62% yield). 1H NMR
general procedure, using petroleum ether as the eluant (500 MHz, CDCl3): δ 7.80 (d, J = 8.1 Hz, 1H), 7.54 (d, J = 7.5 Hz,
afforded a yellow solid (52.7 mg, 90% yield), mp 100–101 °C. 2H), 7.41–7.37 (m, 1H), 7.33–7.27 (m, 3H), 7.20 (t, J = 8.1 Hz,
1H NMR (500 MHz, CDCl3): δ 8.20 (d, J = 8.4 Hz, 1H), 7.71–7.69 1H). 13C NMR (125 MHz, CDCl3): δ 162.5 (d, JF = 251.2 Hz),
(m, 2H), 7.51 (t, J = 7.2 Hz, 1H), 7.46 (t, J = 7.6 Hz, 2H), 7.05 (d, 152.4, 133.5, 129.9 (q, JF = 3.8 Hz), 129.3, 129.2, 129.0 (d, JF =
J = 8.4 Hz, 1H), 6.74 (s, 1H), 2.19 (s, 3H). 13C NMR (125 MHz, 9.0 Hz), 128.4, 120.3 (d, JF = 25.7 Hz), 116.9 (d, JF = 24.4 Hz).
CDCl3): δ 145.0, 143.6, 137.4, 135.8, 130.3, 130.0, 129.8, 128.2, 19F NMR (470 MHz, CDCl3): δ −93.8 (s, 1F). HRMS (TIC): calcd
126.8, 126.0, 21.6. HRMS (TIC): calcd for
C
13H11NO2Se for C12H8FNO2Se [M + H]+ 297.9777, found 297.9776.
[M + H]+ 294.0028, found 294.0027.
(2,6-Difluorophenyl)(phenyl)selane (3j). Following the
(2-Nitro-4-(trifluoromethyl)phenyl)(phenyl)selane (3d). general procedure, using petroleum ether as the eluant
Following the general procedure, using petroleum ether as the afforded a yellow liquid (29.7 mg, 55% yield). 1H NMR
eluant afforded a yellow solid (49.9 mg, 72% yield), mp (500 MHz, CDCl3): δ 7.44–7.42 (m, 2H), 7.36–7.30 (m, 1H),
1
79–80 °C. H NMR (500 MHz, CDCl3): δ 8.56 (s, 1H), 7.71–7.69 7.23–7.22 (m, 3H), 6.96–6.93 (m, 2H). 13C NMR (125 MHz,
(m, 2H), 7.57–7.54 (m, 1H), 7.51–7.48 (m, 3H), 7.13 (d, J = 8.5 CDCl3): δ 163.2 (d, JF = 247.1 Hz), 163.1 (d, JF = 247.1 Hz),
Hz, 1H). 13C NMR (125 MHz, CDCl3):δ 145.2, 141.3, 137.3, 131.9, 131.5, 131.3 (t, JF = 10.0 Hz), 130.0, 129.2, 127.3, 111.6
131.2, 130.4, 129.4 (d, JF = 3.3 Hz), 128.4 (q, JF = 34.4 Hz), (q, JF = 5.3 Hz), 105.8 (t, JF = 26.2 Hz). 19F NMR (470 MHz,
127.4, 126.9, 123.0 (d, JF = 272.2 Hz), 123.2 (q, JF = 4.1 Hz). 19F CDCl3): δ −98.5 (s, 2F). HRMS (TIC): calcd for C12H8F2Se
NMR (470 MHz, CDCl3): δ −62.8 (s, 3F). HRMS (TIC): calcd for [M + H]+ 270.9832, found 270.9833.
C13H8F3NO2Se [M + H]+ 347.9745, found 347.9744.
Phenyl(2-(phenylselanyl)phenyl)methanone (3k). Following
(2-Methyl-6-nitrophenyl)(phenyl)selane (3e). Following the the general procedure, using petroleum ether as the eluant
general procedure, using petroleum ether as the eluant afforded a yellow liquid (26.4 mg, 39% yield). 1H NMR
afforded a yellow solid (39.8 mg, 68% yield), mp 107–108 °C. (500 MHz, CDCl3): δ 7.80 (d, J = 7.4 Hz, 2H), 7.64 (d, J = 6.6 Hz,
1H NMR (500 MHz, CDCl3): δ 7.60–7.58 (m, 1H), 7.42–7.36 (m, 2H), 7.58–7.57 (m, 2H), 7.49–7.46 (m, 2H), 7.39–7.34 (m, 3H),
2H), 7.26–7.20 (m, 5H), 2.34 (s, 3H). 13C NMR (125 MHz, 7.27–7.19 (m, 3H). 13C NMR (125 MHz, CDCl3): δ 196.6, 137.7,
CDCl3): δ 145.2, 133.7, 131.3, 129.4, 129.1, 127.2, 124.2, 121.1, 137.5, 137.0, 136.1, 132.6, 131.8, 131.6, 131.5, 130.1, 129.5,
23.9. HRMS (TIC): calcd for C13H11NO2Se [M + H]+ 294.0028, 128.5, 128.3, 125.0. HRMS (TIC): calcd for C19H14OSe [M + H]+
found 294.0027.
339.0283, found 339.0284.
(4-Bromo-2-nitrophenyl)(phenyl)selane (3f). Following the
(Perfluorophenyl)(phenyl)selane (3l). Following the general
general procedure, using petroleum ether as the eluant afforded procedure, using petroleum ether as the eluant afforded a
a yellow liquid (52.8 mg, 74% yield). 1H NMR (500 MHz, CDCl3): yellow liquid (45.4 mg, 70% yield). 1H NMR (500 MHz, CDCl3):
δ 8.45 (d, J = 2.1 Hz, 1H), 7.70–7.68 (m, 2H), 7.54–7.51 (m, 1H), δ 7.53–7.52 (m, 2H), 7.32–7.25 (m, 3H). 13C NMR (125 MHz,
7.47 (t, J = 7.6 Hz, 2H), 7.39 (dd, J = 8.7, 2.1 Hz, 1H), 6.84 (d, J = CDCl3): δ 148.1–148.0 (m), 146.2–146.0 (m), 143.0–142.8 (m),
8.7 Hz, 1H). 13C NMR (125 MHz, CDCl3): δ 145.9, 137.4, 136.5, 140.9–140.8 (m), 138.7–138.4 (m), 136.6–136.3 (m), 133.4,
135.1, 131.6, 130.2, 130.1, 128.7, 127.7, 118.8. HRMS (TIC): 129.5, 128.5, 103.7–103.2 (m). 19F NMR (470 MHz, CDCl3):
calcd for C12H8BrNO2Se [M + H]+ 357.8977, found 357.8978.
δ −126.0 (d, JF = 26.5 Hz, 2F), −151.5 (t, JF = 21.3 Hz, 1F),
(3-Chloro-2-nitrophenyl)(phenyl)selane (3g). Following the −160.0–160.1 (m, 2F). HRMS (TIC): calcd for C19H14OSe
general procedure, using petroleum ether as the eluant [M + H]+ 324.9550, found 324.9551.
afforded a yellow liquid (41.9 mg, 67% yield). 1H NMR
2,6-Dipheylselanylpyridine (3m). Following the general pro-
(500 MHz, CDCl3): δ 7.61–7.59 (m, 2H), 7.43–7.40 (m, 1H), cedure, using petroleum ether as the eluant afforded a yellow
7.38–7.33 (m, 3H), 7.18 (t, J = 8.0 Hz, 1H), 7.14 (dd, J = 8.0, liquid (47.2 mg, 58% yield), mp 178–179 °C. 1H NMR
1.2 Hz, 1H). 13C NMR (125 MHz, CDCl3): δ 135.6, 131.7, 131.2, (500 MHz, CDCl3): δ 7.72 (d, J = 7.3 Hz, 4H), 7.51–7.48 (m, 2H),
129.9, 129.4, 129.3, 129.0, 128.2, 126.5. HRMS (TIC): calcd for 7.45–7.42 (m, 4H), 6.72 (t, J = 7.8 Hz, 1H), 6.40 (d, J = 7.9 Hz,
C12H8ClNO2Se [M + H]+ 313.9482, found 313.9484.
2H). 13C NMR (125 MHz, CDCl3): δ 150.8, 137.4, 130.1, 129.9,
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126.2, 125.5, 120.2. HRMS (TIC): calcd for C17H13NOSe2
[M + H]+ 391.9451, found 391.9455.
(4-Bromophenyl)(2-nitrophenyl)selane (4d). Following the
general procedure, using petroleum ether as the eluant
3-Methyl-2-(phenylselanyl)benzo[b]thiophene (3n). Following afforded a yellow solid (55.0 mg, 77% yield), mp 115–116 °C.
the general procedure, using petroleum ether as the eluant 1H NMR (500 MHz, CDCl3): δ 8.32 (dd, J = 8.1, 1.5 Hz, 1H),
afforded a yellow liquid (46.2 mg, 76% yield). 1H NMR 7.60–7.56 (m, 4H), 7.36–7.28 (m, 2H), 6.97 (dd, J = 8.0, 1.3 Hz,
(500 MHz, CDCl3): δ 7.53 (d, J = 7.6 Hz, 1H), 7.45 (d, J = 8.1 Hz, 1H). 13C NMR (125 MHz, CDCl3): δ 145.6, 138.9, 135.2, 133.8,
1H), 7.35–7.34 (m, 2H), 7.32–7.29 (m, 1H), 7.25–7.20 (m, 4H), 133.3, 130.1, 127.1, 126.2, 126.0, 124.9. HRMS (TIC): calcd for
2.36 (s, 3H). 13C NMR (125 MHz, CDCl3): δ 156.8, 140.5, 130.8, C12H8BrNO2Se [M + H]+ 357.8977, found 357.8976.
130.5, 129.4, 129.1, 126.9, 125.2, 124.7, 122.5, 119.7, 111.3, 9.9.
(4-Methoxy-2-nitrophenyl)(naphthalen-1-yl)selane (4e).
HRMS (TIC): calcd for C15H12SSe [M + H]+ 304.9898, found Following the general procedure, using petroleum ether as the
1
304.9897.
eluant afforded a yellow liquid (64.6 mg, 90% yield). H NMR
3-Methyl-2-(phenylselanyl)benzofuran (3o). Following the (500 MHz, CDCl3): δ 8.23 (d, J = 8.4 Hz, 1H), 8.05 (dd, J =
general procedure, using petroleum ether as the eluant 6.9 Hz, 1H), 8.01 (d, J = 8.2 Hz, 1H), 7.90 (d, J = 8.1 Hz, 1H),
afforded a yellow liquid (46.1 mg, 80% yield). 1H NMR 7.84 (s, 1H), 7.55–7.47 (m, 3H), 6.75–6.73 (m, 1H), 6.57 (d, J =
(500 MHz, CDCl3): δ 7.52 (d, J = 7.7 Hz, 1H), 7.45 (d, J = 8.2 Hz, 8.9 Hz, 1H), 3.79 (s, 3H). 13C NMR (125 MHz, CDCl3): δ 157.9,
1H), 7.35–7.33 (m, 2H), 7.31–7.28 (m, 1H), 7.24–7.23 (m, 1H), 146.1, 137.7, 135.2, 134.3, 131.4, 131.0, 128.8, 128.1, 127.6,
7.21–7.18 (m, 3H), 2.36 (s, 3H). 13C NMR (125 MHz, CDCl3): δ 127.5, 126.3, 125.6, 122.2, 109.4, 55.8. HRMS (TIC): calcd for
156.8, 140.6, 130.8, 130.5, 129.4, 129.2, 126.9, 125.2, 124.7, C17H13NO3Se [M + H]+ 360.0134, found 360.0133.
122.5, 119.7, 111.3, 9.9. HRMS (TIC): calcd for C15H12OSe [M +
H]+ 289.0126, found 289.0124.
Methyl (2-nitrophenyl)selane (4f). Following the general pro-
cedure, using petroleum ether as the eluant afforded a yellow
1
4-Methyl-2-phenyl-5-(phenylselanyl)thiazole (3p). Following liquid (36.5 mg, 84% yield). H NMR (500 MHz, CDCl3): δ 8.33
the general procedure, using petroleum ether as the eluant (s, 1H), 7.55–7.33 (m, 3H), 2.33 (s, 3H). 13C NMR (125 MHz,
afforded a yellow liquid (40.3 mg, 61% yield). 1H NMR CDCl3): δ 146.5, 134.4, 133.6, 128.4, 126.3, 125.1, 7.3. HRMS
(500 MHz, CDCl3): δ 7.91–7.89 (m, 2H), 7.43–7.41 (m, 3H), (TIC): calcd for C7H7NO2Se [M + H]+ 217.9715, found 217.9717.
7.32–7.30 (m, 2H), 7.25–7.19 (m, 3H), 2.58 (s, 3H). 13C NMR
Methyl (2-nitro-4-(trifluoromethyl)phenyl)selane (4g).
(125 MHz, CDCl3): δ 171.2, 159.8, 133.3, 132.3, 130.3, 129.9, Following the general procedure, using petroleum ether as the
129.4, 129.0, 126.9, 126.4, 113.3, 16.7. HRMS (TIC): calcd for eluant afforded a yellow solid (40.0 mg, 70% yield), mp
1
C12H19NSSe [M + H]+ 332.0007, found 332.0009.
80–81 °C. H NMR (500 MHz, CDCl3): δ 8.59 (s, 1H), 7.76 (d,
(3-Bromophenyl)(4-methoxy-2-nitrophenyl)selane (4a). J = 8.4 Hz, 1H), 7.63 (d, J = 8.4 Hz, 1H), 2.38 (s, 3H). 13C NMR
Following the general procedure, using petroleum ether as the (125 MHz, CDCl3): δ 146.2, 139.9, 129.5 (q, JF = 3.2 Hz), 129.3,
eluant afforded a yellow solid (61.1 mg, 79% yield), mp 128.0 (q, JF = 34.3 Hz), 123.0 (d, JF = 270.3 Hz), 123.5 (q, JF =
115–116 °C. H NMR (500 MHz, CDCl3): δ 7.83 (d, J = 2.7 Hz, 4.0 Hz), 7.80. 19F NMR (470 MHz, CDCl3): δ −62.7 (s, 3F).
1
1H), 7.81–7.80 (m, 1H), 7.77–7.56 (m, 1H), 7.37–7.32 (m, 2H), HRMS (TIC): calcd for C8H6F3NO2Se [M + H]+ 285.9589, found
6.98 (dd, J = 9.0, 2.8 Hz, 1H), 6.81 (d, J = 8.9 Hz, 1H), 3.86 (s, 3H). 285.9591.
13C NMR (125 MHz, CDCl3): δ 158.3, 146.4, 139.1, 133.8, 131.7,
(5-Fluoro-2-nitrophenyl)(methyl)selane (4h). Following the
131.6, 131.4, 130.9, 128.6, 124.3, 122.4, 109.4, 55.9. HRMS (TIC): general procedure, using petroleum ether as the eluant
calcd for C13H10BrNO3Se [M + H]+ 387.9082, found 387.9080. afforded a yellow liquid (24.9 mg, 53% yield). 1H NMR
(4-Chlorophenyl)(4-methoxy-2-nitrophenyl)selane (4b). (500 MHz, CDCl3): δ 8.39–8.36 (m, 1H), 7.14 (d, J = 9.2 Hz, 1H),
Following the general procedure, using petroleum ether as the 7.01 (t, J = 7.8 Hz, 1H), 2.31 (s, 3H). 13C NMR (125 MHz,
eluant afforded a yellow solid (51.4 mg, 75% yield), mp CDCl3): δ 165.4 (q, JF = 258.0 Hz), 142.7, 138.4 (q, JF = 8.9 Hz),
97–98 °C. 1H NMR (500 MHz, CDCl3): δ 7.82 (d, J = 2.7 Hz, 1H), 129.0 (d, JF = 10.4 Hz), 115.1 (q, JF = 26.0 Hz), 112.6 (q, JF
=
7.62–7.61 (m, 2H), 7.42–7.40 (m, 2H), 6.96 (dd, J = 9.0, 2.9 Hz, 23.6.0 Hz), 7.83. 19F NMR (470 MHz, CDCl3): δ −102.9 (s, 1F).
1H), 6.84 (d, J = 9.0 Hz, 1H), 3.85 (s, 3H). 13C NMR (125 MHz, HRMS (TIC): calcd for C7H6FNO2Se [M + H]+ 235.9621, found
CDCl3): δ 158.1, 146.2, 138.6, 136.3, 130.9, 130.3, 126.7, 125.4, 235.9623.
122.3, 109.3, 55.9. HRMS (TIC): calcd for C13H10ClNO3Se
[M + H]+ 343.9587, found 343.9588.
(4-Methoxy-2-nitrophenyl)(methyl)selane (4i). Following the
general procedure, using petroleum ether as the eluant
(4-Methoxy-2-nitrophenyl)(4-(trifluoromethoxy)phenyl)selane afforded a yellow liquid (46.9 mg, 95% yield). 1H NMR
(4c). Following the general procedure, using petroleum ether (500 MHz, CDCl3): δ 7.84 (d, J = 2.8 Hz, 1H), 7.36 (d, J = 8.9 Hz,
as the eluant afforded a yellow liquid (55.0 mg, 70% yield). 1H), 7.18 (dd, J = 8.9, 2.8 Hz, 1H), 3.88 (s, 3H), 2.38 (s, 3H).
1H NMR (500 MHz, CDCl3): δ 7.82 (s, 1H), 7.72 (d, J = 7.8 Hz, 13C NMR (125 MHz, CDCl3): δ 157.6, 146.9, 129.1, 124.7, 122.3,
2H), 7.27 (d, J = 7.8 Hz, 2H), 7.74 (d, J = 7.9 Hz, 1H), 6.98 (d, J = 109.7, 55.9, 7.3. HRMS (TIC): calcd for C8H6F3NO2Se [M + H]+
8.7 Hz, 1H), 6.85 (d, J = 8.9 Hz, 1H), 3.85 (s, 3H). 13C NMR 285.9821, found 285.9823.
(125 MHz, CDCl3): δ 158.2, 150.4, 146.3, 138.9, 132.6, 132.1,
(2-(Methylselanyl)phenyl)(phenyl)methanone (4j). Following
130.9, 126.8, 125.1, 122.3, 122.2, 120.3 (q, JF = 257.9), 109.5, the general procedure, using petroleum ether as the eluant
55.9. 19F NMR (470 MHz, CDCl3): δ −57.7 (s, 3F). HRMS (TIC): afforded a yellow liquid (24.8 mg, 45% yield). 1H NMR
calcd for C14H10F3NO3Se [M + H]+ 377.9851, found 377.9852.
(500 MHz, CDCl3): δ 7.77–7.75 (m, 2H), 7.59–7.52 (m, 3H),
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7.48–7.43 (m, 3H), 7.24 (t, J = 7.5 Hz, 1H), 2.28 (s, 3H). 13C afforded a colorless liquid (43.2 mg, 59% yield). 1H NMR
NMR (125 MHz, CDCl3): δ 196.8, 137.8, 136.3, 132.5, 131.7, (500 MHz, CDCl3): δ 7.53 (d, J = 7.7 Hz, 1H), 7.45 (d, J = 8.2 Hz,
131.6, 130.0, 129.5, 128.3, 124.7, 124.5, 7.24. HRMS (TIC): 1H), 7.33–7.30 (m, 3H), 7.26–7.25 (m, 1H), 7.20 (d, J = 8.1 Hz,
calcd for C14H12OSe [M + H]+ 277.0126, found 277.0124.
2H), 2.35 (s, 3H). 13C NMR (125 MHz, CDCl3): δ 156.8, 139.9,
3-Methyl-2-(methylselanyl)benzo[b]thiophene (4k). Following 132.4, 132.0, 129.8, 129.0, 125.4, 124.9, 122.6, 121.2, 119.8,
the general procedure, using petroleum ether as the eluant 111.3, 9.9. HRMS (TIC): calcd for C15H11BrOSe [M + H]+
afforded a yellow liquid (37.2 mg, 77% yield). 1H NMR 366.9231, found 366.9230.
(500 MHz, CDCl3): δ 7.75 (d, J = 7.8 Hz, 1H), 7.64 (d, J = 7.8 Hz,
1,2-Bis(phenylselanyl)benzene6b (5a). To an 25 mL Schlenk
1H), 7.36–7.28 (m, 2H), 2.47 (s, 3H), 2.33 (s, 3H). 13C NMR reaction tube charged with 2-(phenylselanyl)aniline (0.5 mmol),
(125 MHz, CDCl3): δ 141.7, 139.9, 135.6, 124.3, 124.1, 123.1, diphenyl diselenide (1.0 mmol), tBuONO (1.1 mmol), eosin Y
121.9, 121.8, 13.7, 10.3. HRMS (TIC): calcd for C10H10SSe (0.01 mmol) and 2 ml DMSO was stirred under blue-LED
[M + H]+ 242.9741, found 242.9743.
light at room temperature for 2 hours (TLC) and the product
3-Methyl-2-(methylselanyl)benzofuran (4l). Following the was extracted with ethyl acetate. The extract was washed
general procedure, using petroleum ether as the eluant with water (10 mL) and brine (10 mL). Then the organic phase
afforded a yellow liquid (38.4 mg, 85% yield). 1H NMR was dried over Na2SO4 and evaporated to leave the crude
(500 MHz, CDCl3): δ 7.46–7.41 (m, 2H), 7.26–7.20 (m, 2H), 2.32 product, and the crude product was extracted with EtOAc
(s, 3H), 2.30 (s, 3H). 13C NMR (125 MHz, CDCl3): δ 156.5, and purified by flash chromatography (petroleum ether) to
141.4, 129.5, 124.3, 122.3, 121.1, 119.1, 110.8, 9.6, 8.1. HRMS obtain a yellow solid (41.3 mg, 53% yield), mp 90–91 °C.
(TIC): calcd for C10H10OSe [M + H]+ 226.9970, found 226.9971.
1H NMR (500 MHz, CDCl3): δ 7.52–7.51 (m, 4H), 7.31–7.31
4-(3-Methylbenzo[b]thiophen-2-ylselanyl)benzonitrile (4m). (m, 6H), 7.20–7.18 (m, 2H), 7.06–7.04 (m, 2H). 13C NMR
Following the general procedure, using petroleum ether as the (125 MHz, CDCl3): δ 135.9, 134.1, 134.0, 133.0, 130.7, 129.5,
eluant afforded a yellow solid (42.7 mg, 65% yield), mp 127.9, 127.9. HRMS (TIC): calcd for C8H14Se2 [M + H]+
1
125–126 °C. H NMR (500 MHz, CDCl3): δ 7.82–7.78 (m, 2H), 390.9499, found 390.9498.
7.43–7.43 (m, 4H), 7.28–7.27 (m, 2H), 2.51 (s, 3H). 13C NMR
(2-Iodophenyl)(phenyl)selane19 (5b). A 25 mL Schlenk tube
(125 MHz, CDCl3): δ 142.9, 140.5, 140.4, 139.3, 132.5, 128.9, equipped with a stir bar was charged with p-TsOH·H2O
125.7, 124.5, 122.9, 122.2, 118.9, 118.6, 109.8, 13.9. HRMS (1.5 mmol), 2-(phenylselanyl) aniline (0.5 mmol) and MeCN
(TIC): calcd for C16H11NSSe [M
329.9851.
+
H]+ 329.9850, found (2.0 mL). The resulting suspension of amine salt was cooled to
5–10 °C and to this was added, gradually, a solution of NaNO2
2-(4-Chlorophenylselanyl)-3-methylbenzo[b]thiophene (4n). (1.0 mmol) and KI (1.25 mmol) in H2O (0.3 mL). The reaction
Following the general procedure, using petroleum ether as the mixture was stirred for 10 min, then allowed to cool to room
1
eluant afforded a yellow liquid (48.0 mg, 71% yield). H NMR temperature and stirred for 30 min. The crude product was
(500 MHz, CDCl3): δ 7.76 (d, J = 7.7 Hz, 1H), 7.70 (d, J = 7.7 Hz, extracted with EtOAc and purified by flash chromatography
1H), 7.39–7.33 (m, 2H), 7.23 (d, J = 7.7 Hz, 2H), 7.15 (d, J = (petroleum ether) to obtain a brown solid (61.9 mg, 86%
1
7.7 Hz, 2H), 2.49 (s, 3H). 13C NMR (125 MHz, CDCl3): δ 142.6, yield), mp 76–77 °C. H NMR (500 MHz, CDCl3): δ 7.65 (d, J =
139.6, 138.8, 133.0, 131.6, 130.4, 129.4, 125.2, 124.3, 122.7, 7.7 Hz, 1H), 7.62 (d, J = 7.3 Hz, 2H), 7.45–7.36 (m, 3H), 7.11 (t,
122.1, 121.4, 13.9. HRMS (TIC): calcd for C15H11ClSSe [M + H]+ J = 7.4 Hz, 1H), 6.89–6.83 (m, 2H). 13C NMR (125 MHz, CDCl3):
338.9508, found 338.9510.
δ 140.6, 139.4, 135.8, 130.4, 130.3, 129.9, 128.8, 128.7, 127.5,
4-(3-Methylbenzofuran-2-ylselanyl)benzonitrile (4o). Following 99.6. HRMS (TIC): calcd for C15H11BrOSe [M + H]+ 360.8987,
the general procedure, using petroleum ether as the eluant found 360.8988.
afforded a yellow liquid (50.7 mg, 81% yield). 1H NMR
11-Methyldibenzo-(b,f )-1,4-selenazepine (5c). A 25 mL
(500 MHz, CDCl3): δ 7.58–7.57 (m, 1H), 7.49–7.45 (m, 3H), Schlenk tube equipped with a stir bar was charged with 2-
7.38–7.35 (m, 1H), 7.33–7.28 (m, 3H), 2.37 (s, 3H). 13C NMR (phenylselanyl)aniline (0.5 mmol), and acetyl chloride
(125 MHz, CDCl3): δ 157.0, 138.9, 132.6, 129.5, 128.8, 126.4, (1.5 mmol) was added slowly to the solution, and then the
125.8, 122.9, 119.9, 118.5, 111.4, 110.2, 9.9. HRMS (TIC): calcd temperature was increased spontaneously to ambient tempera-
for C16H11NOSe [M + H]+ 314.0079, found 314.0077.
ture, and monitored by TLC. Then, water (20 mL) was added to
2-(4-Chlorophenylselanyl)-3-methylbenzofuran (4p). Following the mixture. The organic layer was washed with brine (1 ×
the general procedure, using petroleum ether as the eluant 30 mL), dried with anhydrous Na2SO4, and concentrated
afforded a colorless liquid (56.0 mg, 87% yield). 1H NMR in vacuo. Polyphosphoric acid (PPA) (2.0 g) and phosphorus
(500 MHz, CDCl3): δ 7.52 (d, J = 7.7 Hz, 1H), 7.45 (d, J = 8.2 Hz, oxychloride (1.5 mmol) were added to the residue. The reac-
1H), 7.33–7.30 (m, 1H), 7.28–7.25 (m, 3H), 7.17 (d, J = 8.3 Hz, tion mixture was heated at 120 °C for 3 h and poured into ice-
2H), 2.35 (s, 3H). 13C NMR (125 MHz, CDCl3): δ 156.8, 140.0, cold water, then treated with aqueous ammonia and extracted
133.2, 131.8, 129.5, 129.0, 128.9, 125.4, 124.9, 122.7, 119.8, with CH2Cl2 (3 × 10 mL), dried with anhydrous Na2SO4, and
111.4, 9.9. HRMS (TIC): calcd for C15H11BrOSe [M + H]+ concentrated under vacuum. The crude product was extracted
366.9231, found 366.9230.
with EtOAc and purified by flash chromatography (petroleum
2-(4-Bromophenylselanyl)-3-methylbenzofuran (4q). Following ether : EtOAc = 2 : 98) to obtain a colorless solid (42.0 mg, 77%
1
the general procedure, using petroleum ether as the eluant yield), mp 125–126 °C. H NMR (500 MHz, CDCl3): δ 7.98–7.97
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(m, 1H), 7.56 (d, J = 7.4 Hz, 1H), 7.29–7.23 (m, 3H), 6.99–6.98
(m, 1H), 6.83 (d, J = 8.0 Hz, 1H), 6.75 (t, J = 7.4 Hz, 1H), 2.69 (s,
3H). 13C NMR (125 MHz, CDCl3): δ 198.8, 149.5, 139.2, 138.1,
134.3, 132.8, 131.9, 131.5, 128.8, 124.9, 119.0, 114.8, 113.6,
27.1. HRMS (TIC): calcd for C14H11NSe [M + H]+ 274.0130,
found 274.0129.
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10H-Phenoselenazine20 (5d).
A 25 mL Schlenk tube
equipped with a stir bar was charged with 2-(phenylselanyl)
aniline (0.5 mmol), triphenylphosphine (1.25 mmol) and 2 mL
1,2-dichlorobenzene. The tube was fitted with a rubber
septum, and then it was evacuated and refilled with N2 three
times, then the septum was replaced by a Teflon screwcap
under a N2 flow. The reaction mixture was stirred at 180 °C for
24 h. The crude product was extracted with EtOAc and purified
by flash chromatography (petroleum ether : EtOAc = 2 : 98) to
obtain a colorless solid (33.6 mg, 68% yield), mp 194–195 °C.
1H NMR (500 MHz, CDCl3): δ 8.59 (s, 1H), 7.09 (d, J = 7.5 Hz,
2H), 7.03 (t, J = 7.7 Hz, 2H), 6.78–6.75 (m, 4H). 13C NMR
(125 MHz, CDCl3): δ 142.1, 128.8, 127.8, 122.1, 115.1, 111.5.
HRMS (TIC): calcd for C12H9NSe [M + H]+ 247.9973, found
247.9972.
Conflicts of interest
The authors declare no competing financial interest.
Acknowledgements
Financial support from the National Natural Science
Foundation of China (21602158, 21372177, and 21472140), the
State Key Laboratory of Structural Chemistry (no. 20170037),
the Zhejiang Provincial Natural Science Foundation (LY16B0-
20011), the Wenzhou Medical University start-up funding
(QTJ15026) and the Granted from the Opening Project of
Zhejiang Provincial Top Key Discipline of Pharmaceutical
Sciences (201723) is greatly appreciated.
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