Metal-Free Synthesis of Unsymmetrical Aryl Selenides and Tellurides via Visible Light-Driven Activation of Arylazo Sulfones

Article abstract of DOI:10.1002/ejoc.202001386

A protocol for the visible light driven preparation of unsymmetrical (hetero)aryl selenides and tellurides is described herein. The method exploits the peculiar photoreactivity of arylazo sulfones that act as thermally stable, precursors of aryl radicals under both photocatalyst- and additive-free conditions. The method developed shows an impressive versatility (more than fifty compounds isolated).

Full text of DOI:10.1002/ejoc.202001386

European Journal of Organic Chemistry
Accepted Article
Accepted Article
Title: Metal-free synthesis of unsymmetrical aryl selenides and
tellurides via visible light-driven activation of arylazo sulfones.
Authors: Junjie Liu, Miaomiao Tian, Yuxuan Li, Xiwen Shan, Ankun Li,
Kui Lu, Maurizio Fagnoni, Stefano Protti, and Xia Zhao
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using the Digital Object Identifier (DOI) given below. The VoR will be
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content of this Accepted Article.
To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.202001386
Link to VoR: https://doi.org/10.1002/ejoc.202001386
01/2020

10.1002/ejoc.202001386
European Journal of Organic Chemistry
FULL PAPER
Metal-free synthesis of unsymmetrical aryl selenides and
tellurides via visible light-driven activation of arylazo sulfones.
Junjie Liu,[a], § Miaomiao Tian,[a], § Yuxuan Li,[a],[c] Xiwen Shan,[a] Ankun Li,[a] Kui Lu,[b] Maurizio
Fagnoni,[c] Stefano Protti[c]* and Xia Zhao[a]*
[a]
Tianjin Key Laboratory of Structure and Performance for Functional Molecules, MOE Key Laboratory of Inorganic-Organic Hybrid Functional Materials
Chemistry, College of Chemistry, Tianjin Normal University, Tianjin 300387, P. R. China. http://hxxy.tjnu.edu.cn/info/1057/2161.htm
E-mail: hxxyzhx@tjnu.edu.cn
[b]
[c]
College of Biotechnology, Tianjin University of Science & Technology, Tianjin 300457, China.
PhotoGreen Lab, Department of Chemistry, University of Pavia, V. Le Taramelli 12, Pavia, Italy. http://www-2.unipv.it/photogreenlab/
Email: stefano.protti@unipv.it
§These authors contributed equally to this work.
Supporting information for this article is given via a link at the end of the document
Abstract: A protocol for the visible light driven preparation of
unsymmetrical (hetero)aryl selenides and tellurides is described
herein. The method exploits the peculiar photoreactivity of arylazo
sulfones that act as thermally stable, precursors of aryl radicals under
both photocatalyst- and additive-free conditions. The method
developed shows an impressive versatility (more than fifty compounds
isolated).
trapped by
dichalcogenide).
a
chalcogenide derivative (e.g. an organic
Introduction
Organo-chalcogens are present as a structural motif in a wide
range of derivatives that find application in several research fields,
including agrochemistry,[1] pharmacology,[2-6] organic synthesis[7]
and material sciences (e.g. in the development of luminescent
molecular probes).[8] The interest for (hetero)aryl chalcogenides
relies on their biological properties, including antioxidant,[9,10]
cytotoxic[11] and antitumoral[12,13] activities.
For this aim, the development of an efficient and versatile
synthetic protocol for the preparation of aryl selenides and
tellurides is a challenge in organic chemistry, and in most cases,
the intermediacy of a transition metal catalyst is required.[14] An
overview of the recent literature pointed out that such derivatives
can be obtained from a variety of aromatic substrates including
haloarenes (mainly aryl iodides)[15-20] aryltrialkoxysilanes,[21]
triarylbismuthanes[22,23] aryl boronic acids,[24-27] and even
unfunctionalized aromatics[28] under Cu-,[15-18, 20-25] Pd-,[26] Ni-,[21]
Fe-,[21] Ru-[19] and Ag-[26,27] catalysis (an example in Scheme 1a).
As for the chalcogen source, apart from elemental selenium,[22,23]
selenolate and tellurolate anions,[29] diselenides and ditellurides
are considered as the elective choice,[30] also in view (in the case
of diselenides) of the rather low toxicity and instability.[31]
However, the claim for arylation procedures adopting metal-free
conditions recently emerged when fine chemicals, for which metal
contamination must be strictly avoided, are the target
compounds.[32] Accordingly, the preparation of heteroaryl
selenides and tellurides under oxidative (e.g. in the presence of
Oxone or iodine, an example in Scheme 1b)[33-36] or basic[37-39]
conditions, has been reported. In this regards, great attention has
been given to the development of protocols based on the
generation of an aryl radical as the key-intermediate that is
Scheme 1. Synthesis of aryl selenides via a) silver catalyzed functionalization
of aryl boronic acid, b) direct functionalization of heteroaromatics, c) the
1
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10.1002/ejoc.202001386
European Journal of Organic Chemistry
FULL PAPER
intermediacy of aryl radicals photogenerated from aryl diazonium salts, d)
photocatalyst- and additive free conditions starting from arylazo sulfones.
Aryl radicals were generally released from aromatic hydrazines
(in the presence of a large excess of LiOH)[40] or from aryl
diazonium salts prepared in situ, under photoorganocatalyzed
conditions (Scheme 1c).[41-43] In the latter case, a photoexcited
organic catalyst (e.g. a xanthene dye) is responsible for the
monoelectronic reduction of the diazonium salts and the
subsequent formation of the aryl radicals.[41]
Table 1. Synthesis of unsymmetrical selenides 2. Arylazo sulfone
scope.[a]
On the other hand, only few attentions were given to synthetic
protocols relying on both (photo)catalyst- and additive-free
conditions. To the best of our knowledge, this field is limited to the
photochemical
preparation
of
aryl
selenides
from
triarylbismuthines[44] and the arylation of diazonium salts by
having recourse to mechanochemical activation of the
substrates.[45]
In the last years we were intrigued by the potentialities of arylazo
sulfones in organic synthesis.[46] Such bench-stable derivatives of
diazonium salts bear a dyedauxiliary moiety (the -N2SO2CH3
group) that imparts both color and reactivity to the molecule
allowing for the release of an aryl radical upon visible light
irradiation.[46] Such behavior was exploited in the development of
several metal-free arylation protocols for the preparation, among
the others, of aromatic stannanes,[47] phosphonates,[48]
boranes,[49,50] sulfides[50] and arylated heterocycles.[51,52]
We thus considered the opportunity of developing a visible light-
driven procedure for the synthesis of aryl selenides and tellurides
where neither catalyst nor additives were adopted (Scheme 1d).
Results and Discussion
In order to test the feasibility of our proposal, we started to
investigate
the
reaction
between
ethyl
4-
((methylsulfonyl)diazenyl)benzoate (1a) and diphenyldiselenide
(PhSe)2. The best reaction conditions found were as follows: 1a
(1.0 equiv, 0.1 M), (PhSe)2 (1.2 equiv) in nitrogen saturated MeCN,
irradiated overnight by a 21 W blue LED lamp, (see Table S1,
Supporting Information for further details), that afforded aryl
selenide 2a in 91% yield.
[a] A 0.1 M solution of arylazo sulfone 1 in Ar-saturated MeCN, in the presence
of (PhSe)2 (1.2 equiv) irradiated overnight with a 21 W LED lamp (456 nm). [b]
reaction carried out on a 1 mmol scale.
With this promising results in our hand, we embarked in the
preparation of a wide range of unsymmetrical aryl selenides by
tuning the structure of both arylazo sulfones (Table 1) and of the
diselenides (Table 2). Phenyl aryl selenides 2a-m have been
obtained always in good to highly satisfactory yields,
independently from the nature (whether electron-donating or
electron-withdrawing) and the position of the aromatic
substituents in arylazo sulfones. The synthesis of 2a was also
successfully carried out on a 1 mmol scale (88% yield). Even
phenyl selenides having two (compounds 2i-k, 2m) or three
(compound 2l) aromatic substituents have been isolated in up to
91% yield. Analogously, heteroaromatic azosulfones have been
also efficiently converted into diaryl selenides including, among
the others, pyridine (2n-w), quinoline (2x-y), thiophene (2z), 1H-
indazole (2aa) and benzo[d]thiazole (2ab) derivatives. Finally, the
reaction was extended with good results to naphthylazo sulfones
(see products 2ac, 2ad).
We also successfully extended the scope of the protocol to
diselenides different from (PhSe)2 as depicted in Table 2.
Interestingly, the presence of electron-withdrawing substituents
on the selenating agent (ArSe)2 was found noxious for the
outcome of the process (see the low yield of compounds 2ag and
2ah) compared to electron-rich substituents (see the case of
compounds 2ai-2al). Noteworthy, our method can be successfully
applied to dialkyl (benzyl, and n-butyl) diselenides to afford alkyl
arylselenides 2am-2at where the arylation yields were only little
affected by the nature of the aryl group (aromatic, heteroaromatic
or naphthyl).
Finally, we focused on the preparation of unsymmetrical tellurides,
that have been isolated in discrete yields (mostly around 50-60%)
except the case of the ethoxycarbonyl 3a, the methoxy- and
chloro-derivatives 3d,e (> 70% yield) and the heptyl telluride 3i
(35% yield, Table 3).
2
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10.1002/ejoc.202001386
European Journal of Organic Chemistry
FULL PAPER
Table 3. Visible light induced synthesis of unsymmetrical
tellurides 3.[a]
Table 2. Synthesis of unsymmetrical selenides 2. Organo-
diselenide scope.[a]
[a] A 0.1 M solution of arylazo sulfone 1 in Ar-saturated MeCN, in the presence
of (RTe)2 (1.2 equiv) irradiated overnight with a 21 W LED lamp (456 nm).
[a] A 0.1 M solution of arylazo sulfone 1 in Ar-saturated MeCN, in the presence
of (RSe)2 (1.2 equiv) irradiated overnight with a 21 W LED lamp (456 nm).
A tentative mechanism is proposed in Scheme 2. Recent studies
on the photoreactivity of arylazo sulfones[46] suggested that, upon
visible light irradiation, a homolytic cleavage of the N-S bond
occurs from the singlet excited state (n*, Scheme 2 path a) to
release, after nitrogen loss from the early generated diazenyl
•
radical ArN2 , the corresponding aryl radical (Ar•, path b).[53] Such
intermediate reacts efficiently with the chosen dichalcogenides as
previously described.[37,44] The formation of the desired products
2,3 (path c) is accompanied by the release of a RX• radical that
upon homodimerization may restore the starting dichalcogenide
(path d).[44]
3
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10.1002/ejoc.202001386
European Journal of Organic Chemistry
FULL PAPER
Scheme 2. Proposed mechanism for the visible light driven
preparation of organoselenides and tellurides via arylazo sulfones.
In a 50 mL round-bottom flask, the suspension of the prepared
arenediazonium tetrafluoroborate (10 mmol) in CH2Cl2 (10 mL)
was stirred at 0 °C, then sodium methanesulfinate (1.12 g, 1.1
equiv) was added to the reaction mixture in one portion. The
reaction was allowed to warm to room temperature and the
solution stirred overnight. The resulting mixture was then filtered,
and the filtrate was concentrated to give a crude product that was
thus purified by dissolution in CH2Cl2 and precipitation by adding
cold petroleum ether.
Conclusions
In conclusion, we devised a green protocol for the synthesis of
unsymmetrical (hetero)aryl selenides and tellurides at room
temperature. The approach made use of colored shelf stable
arylazo sulfones that upon visible-light exposure readily liberated
an aryl radical prone to attack dialkyl or diaryl chalcogenides for
the forging of Ar-Se and Ar-Te bonds in a smooth way. Neither
photocatalyst nor additive were required to promote the reaction
and the versatility of the method is witnessed by the large number
of compounds prepared (more than fifty).
Ethyl-4-((methylsulfonyl)diazenyl)benzoate (1a).[49] Yield: 92%.
Yellow solid, 1H NMR (400 MHz, CDCl3) δ 8.25 (d, J = 8.8 Hz, 2H),
7.99 (d, J = 8.8 Hz, 2H), 4.44 (q, J = 7.2 Hz, 2H), 3.25 (s, 3H),
1.43 (t, J = 7.2 Hz, 1H).
1-(Methylsulfonyl)-2-(4-nitrophenyl)diazene (1b).[49] Yield:
1
89%. Yellow solid, H NMR (400 MHz, CDCl3) δ 8.44 (d, J = 8.8
Hz, 2H), 8.11 (d, J = 8.8 Hz, 2H), 3.28 (s, 3H).
1-(4-((Methylsulfonyl)diazenyl)phenyl)ethan-1-one
(1c).[49]
Yield: 75%. Yellow solid, 1H NMR (400 MHz, CDCl3) δ 8.13 (d, J
= 8.4 Hz, 2H), 8.00 (d, J = 8.4 Hz, 2H), 3.24 (s, 3H), 2.67 (s, 3H).
4-((Methylsulfonyl)diazenyl)phenyl)(phenyl)methanone (1d).
Yield: 94%. Yellow solid, mp (dec) = 130 °C. 1H NMR (400 MHz,
CDCl3) δ 8.05 (d, J = 8.4 Hz, 2H), 7.97 (d, J = 8.4 Hz, 2H), 7.81
(d, J = 8.0 Hz, 2H), 7.67-7.62 (m, 1H), 7.52 (t, J = 8.0 Hz, 2H),
3.27 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 195.1, 150.6, 142.8,
136.4, 133.2, 131.0, 130.0, 128.5, 124.2, 34.8. IR (neat, υ cm-1):
3413, 1659, 1617, 1340, 1276, 1159, 1069, 954, 861, 700; HRMS
(ESI) m/z calcd for C14H13N2O3S [M+H]+ 289.0638; found
289.0641.
Experimental Section
General information. All solvents were distilled prior to use. For
chromatography, 200-300 mesh silica gel (Qingdao, China) was
1
employed. H, 13C and 19F NMR spectra were recorded at 400
MHz, 100 MHz and 376 MHz with Brucker ARX 400 spectrometer.
Chemical shifts are reported in ppm using tetramethylsilane as
internal standard. Mass spectra were obtained on a Bruker
SCION 436-GC SQ mass spectrometer. MeCN was dried over
CaH2 before use.
Ethyl (E)-3-(4-((E)-(methylsulfonyl)diazenyl)phenyl)acrylate
1
(1e).[47] Yield: 92%. Yellow solid, H NMR (400 MHz, CDCl3) δ
7.95 (d, J = 8.4 Hz, 2H), 7.72-7.68 (m, 3H), 6.57 (d, J = 16.2 Hz,
1H), 4.28 (q, J = 7.2 Hz, 2H), 3.22 (s, 3H), 1.34 (t, J = 7.2 Hz, 3H).
Preparation of arylazo sulfones 1a-1c, 1e, 1g-1k, 1y, 1aa-1ac,
1ae, 1ag. [47-49]
1-(Methylsulfonyl)-2-(4-(methylthio)phenyl)diazene
(1f).
o
1
Yield: 91%. Yellow solid, mp (dec) = 130-132 C. H NMR (400
MHz, CDCl3) δ 7.87 (d, J = 8.8 Hz, 2H), 7.35 (d, J = 8.8 Hz, 2H)
3.20 (s, 3H), 2.58 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 150.0,
145.8, 125.4, 124.9, 34.8, 14.7. IR (neat, υ cm-1): 3413, 1614,
1486, 1337, 1137, 949, 617, 502; HRMS (ESI) m/z calcd for
C8H11N2O2S2 [M+H]+ 231.0257; found 231.0256.
a) In a 50 mL round-bottom flask, the chosen aromatic amine (10
mmol) was dissolved in a mixture of H2O (5 mL) and HBF4 (48%aq,
4 mL). After cooling the reaction mixture to 0 °C, sodium nitrite
(760 mg in 4 mL of water) was added dropwise in 5 min. The
mixture was stirred for another 60 min at 0 °C. Then, the
arenediazonium tetrafluoroborate was removed by filtration,
washed with diethyl ether (2×10 mL), dried in vacuo for 20 min
and directly used without any further purification.
b) To a cooled (0 °C) suspension of the appropriate diazonium
salt in CH2Cl2 (10 mL) was added sodium methanesulfinate (1.22
g, 1.2 equiv) in one portion. The reaction was allowed to warm to
room temperature and the solution stirred overnight. The resulting
mixture was then filtered, and the filtrate was concentrated to give
a crude product that was thus purified by dissolution in CH2Cl2
and precipitation by adding cold petroleum ether.
1-(Methylsulfonyl)-2-(3-nitrophenyl)diazene (1g).[47] Yield:
91%. Yellow solid, 1H NMR (400 MHz, CDCl3) δ 8.78 (s, 1H), 8.53
(d, J = 8.2 Hz, 1H), 8.29 (d, J = 8.2 Hz, 1H), 7.83 (t, J = 8.2 Hz,
1H), 3.29 (s, 3H).
1-(2-methoxyphenyl)-2-(methylsulfonyl)diazene (1h). [47] Yield:
1
95%. Yellow solid, H NMR (400 MHz, CDCl3) δ 7.70 (d, J = 8.2
Hz, 1H), 7.61 (t, J = 8.6 Hz, 1H), 7.11 (d, J = 8.6 Hz, 1H), 7.01 (t,
J = 7.6 Hz, 1H), 3.99 (s, 3H), 3.19 (s, 3H).
1-(3,4-Dichlorophenyl)-2-(methylsulfonyl)diazene
(1i).[47]
Yield: 89%. Yellow solid, 1H NMR (400 MHz, CDCl3) δ 8.05 (d, J
= 2.0 Hz, 1H), 7.82 (dd, J = 8.8, 2.0 Hz, 1H), 7.68 (d, J = 8.6 Hz,
1H), 3.23 (s, 3H).
Preparation of arylazo sulfones 1d-1f, 1l-1r, 1t, 1v, 1x, 1z, 1ad,
1af. [47,48]
In a 50 mL round-bottom flask, the suspension of the prepared
arenediazonium tetrafluoroborate (10 mmol) in CH2Cl2 (10 mL)
was stirred at 0 °C, then sodium methanesulfinate (1.12 g, 1.1
equiv) was added to the reaction mixture in one portion. The
reaction was allowed to warm to room temperature and the
solution stirred overnight. The resulting mixture was then filtered.
and the filtrate was concentrated to give the crude product that
was thus purified by dissolution in CH2Cl2 and precipitation by
adding cold petroleum ether.
1-(2-Methoxy-4-nitrophenyl)-2-(methylsulfonyl)diazene
1
(1j).[47] Yield: 91%. Orange solid, H NMR (400 MHz, CDCl3) δ
7.98 (d, J =2.2 Hz, 1H), 7.88 (dd, J = 8.8, 2.2 Hz, 1H), 7.78 (d, J
= 8.8 Hz, 1H), 4.11 (s, 3H), 3.24 (s, 3H).
1-(4-chloro-3-nitrophenyl)-2-(methylsulfonyl)diazene (1k).[48]
Yield: 94%. Yellow solid, 1H NMR (400 MHz, CDCl3) δ 8.47 (d, J
= 2.2 Hz, 1H), 8.12 (dd, J = 8.6, 2.2 Hz, 1H), 7.81 (d, J = 8.6 Hz
1H), 3.27 (s, 3H).
Preparation of arylazo sulfones 1u, 1s, 1w, 1ah.[48]
4
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10.1002/ejoc.202001386
European Journal of Organic Chemistry
FULL PAPER
1-(methylsulfonyl)-2-(3,4,5-trimethoxyphenyl)diazene (1l).[54]
Hz, 1H), 8.56 (d, J = 2.0 Hz, 1H), 8.35 (d, J = 8.4 Hz, 1H), 8.21-
8.13 (m, 2H), 7.57-7.54 (m, 1H), 3.28 (s, 3H).
o
1
Yield: 95%. Pale yellow solid, mp (dec) = 122-124 C. H NMR
(400 MHz, CDCl3) δ 7.26 (s, 2H), 4.00 (s, 3H), 3.94 (s, 6H), 3.22
(s, 3H). 13C NMR (100 MHz, CDCl3) δ 153.5, 144.4, 102.5, 61.1,
56.3, 34.9. IR (neat, υ cm-1): 3413, 1614, 1486, 1338, 1137, 949,
617, 502; HRMS (ESI) m/z calcd for C10H15N3O5S [M+H]+
275.0696; found 275.0696.
Methyl 3-((methylsulfonyl)diazenyl)thiophene-2-carboxylate
1
(1z).[47] Yield: 93%. Orange solid, H NMR (400 MHz, CDCl3) δ
7.56 (d, J = 5.4 Hz, 1H), 7.43 (d, J = 5.4 Hz, 1H), 3.95 (s, 3H),
3.22 (s, 3H).
3-((Methylsulfonyl)diazenyl)-1H-benzoindazole (1aa).[47] Yield:
95%. Yellow solid, 1H NMR (400 MHz, DMSO-d6) δ 14.87 (s, 1H),
8.10 (d, J = 8.2 Hz, 1H), 7.76 (d, J = 8.4 Hz, 1H), 7.59 (t, J = 7.4
Hz, 1H), 7.48 (t, J = 7.6 Hz, 1H), 3.46 (s, 3H).
1-(Benzo[d][1,3]dioxol-5-yl)-2-(methylsulfonyl)diazene (1m).
o
1
Yield: 89%. Green solid, mp (dec) = 113-114 C. H NMR (400
MHz, CDCl3) δ 7.69 (dd, J = 8.2, 2.0 Hz, 1H), 7.34 (d, J = 2.0, Hz,
1H), 6.99 (d, J = 8.2 Hz, 1H), 6.14 (s, 2H), 3.18 (s, 3H). 13C NMR
(100 MHz, CDCl3) δ 154.4, 149.5, 144.8, 129.3, 108.4, 102.8,
98.8, 34.9. IR (neat, υ cm-1): 3414, 1617, 1477, 1414, 1152, 618;
HRMS (EI) m/z calcd for C8H9N2O4S [M+H]+ 229.0278; found
229.0281.
2-Methyl-5-((methylsulfonyl)diazenyl)benzo[d]thiazole
1
(1ab).[47] Yield: 88%. Brown solid, H NMR (400 MHz, CDCl3) δ
8.50 (d, J = 1.8 Hz, 1H), 7.97-7.94 (m, 1H), 7.91-7.89 (m, 1H),
3.25 (s, 3H), 2.88 (s, 3H).
1-(Methylsulfonyl)-2-(naphthalen-2-yl)diazene (1ac).[47] Yield:
95%. Yellow solid, 1H NMR (400 MHz, CDCl3) δ 8.56 (s, 1H), 8.03-
8.01 (m, 1H), 7.91-7.89 (m, 3H), 7.69-7.59 (m, 2H), 3.27 (s, 3H).
1-(Methylsulfonyl)-2-(4-nitronaphthalen-1-yl)diazene (1ad).[48]
Yield: 90%. Yellow solid, 1H NMR (400 MHz, CDCl3) δ 8.76-8.74
(m, 1H), 8.51-8.49 (m, 1H), 8.20 (d, J = 8.4 Hz, 1H), 7.92 (d, J =
8.4 Hz, 1H), 7.88-7.84 (m, 2H), 3.39 (s, 3H).
3-((Methylsulfonyl)diazenyl)pyridine (1n).[48] Yield: 90%.
Yellow solid, 1H NMR (400 MHz, CDCl3) δ 9.24 (d, J = 2.2 Hz, 1H),
8.88 (dd, J = 1.4, 4.8 Hz, 1H), 8.14-8.17 (m, 1H), 7.54 (dd, J = 8.4,
4.8 Hz, 1H), 3.27 (s, 3H).
2-Chloro-5-((methylsulfonyl)diazenyl)pyridine (1o).[48] Yield:
1
87%. Yellow solid, H NMR (400 MHz, CDCl3) δ 9.04 (d, J = 2.4
Hz, 1H), 8.12 (dd, J = 8.6, 2.4 Hz, 1H), 7.55 (d, J = 8.6, 1H), 3.25
(s, 3H).
1-(4-Methoxyphenyl)-2-(methylsulfonyl)diazene
(1ae).[49]
Yield: 93%. Yellow solid, 1H NMR (400 MHz, DMSO-d6) δ 7.97 (d,
J = 9.0 Hz, 2H), 7.22 (d, J = 9.0 Hz, 2H), 3.93 (s, 3H), 3.36 (s, 3H).
1-(Methylsulfonyl)-2-(4-(trifluoromethyl)phenyl)diazene
2-Methyl-5-((methylsulfonyl)diazenyl)pyridine (1p).[48] Yield:
90%. Orange solid, 1H NMR (400 MHz, CDCl3) δ 9.09 (d, J = 2.4
Hz, 1H), 8.02 (dd, J = 8.4, 2.4 Hz, 1H), 7.35 (d, J = 8.4 Hz, 1H),
3.22 (s, 3H), 2.68 (s, 3H).
1
(1af).[49] Yield: 90%. Yellow solid, H NMR (400 MHz, CDCl3) δ
8.05 (d, J = 8.4 Hz, 2H), 7.85 (d, J = 8.4 Hz, 2H), 3.26 (s, 3H). 19
NMR (376 MHz, CDCl3): δ -63.13, (s, 3F).
F
2-Methoxy-5-((methylsulfonyl)diazenyl)pyridine (1q).[48] Yield:
1
92%. Yellow solid, H NMR (400 MHz, CDCl3) δ 8.79 (d, J = 2.4
1-(Methylsulfonyl)-2-(o-tolyl)diazene (1ag).[49] Yellow solid,
1
Hz, 1H), 7.98 (dd, J = 2.6, 9.1 Hz, 1H), 6.82 (d, J = 9.1 Hz, 1H),
4.01 (s, 3H), 3.17 (s, 3H).
Yield: 93%. H NMR (400 MHz, DMSO-d6) δ 7.67 (t, J = 7.3 Hz,
1H), 7.62 (d, J = 8.0 Hz, 1H), 7.55 (d, J = 7.6 Hz, 1H), 7.41 (t, J =
Methyl 5-((methylsulfonyl)diazenyl)nicotinate (1r).[48] Yield:
8.0, Hz, 1H), 3.41 (s, 3H), 2.64 (s, 3H).
1
91%. Yellow solid, H NMR (400 MHz, CDCl3) δ 9.46 (d, J = 1.8
N-(4-((methylsulfonyl)diazenyl)phenyl)acetamide
(1ah).[49]
1
Hz, 1H), 9.38 (d, J =2.4 Hz, 1H), 8.73 (t, J = 2.2 Hz, 1H), 4.01 (s,
3H), 3.28 (s, 3H).
Yield: 84%. Yellow solid, H NMR (400 MHz, DMSO-d6) δ 10.57
(s, 1H), 7.95 (d, J = 9.0 Hz, 2H), 7.88 (d, J = 9.0 Hz, 2H), 3.36 (s,
3H), 2.13 (s, 3H).
3-Fluoro-5-((methylsulfonyl)diazenyl)pyridine (1s).[48] Yield:
95%. Yellow solid, 1H NMR (400 MHz, CDCl3) δ 9.11 (s, 1H), 8.77
(d, J = 2.8 Hz, 1H), 7.84-7.87 (m, 1H), 3.26 (s, 3H). 19F NMR (376
MHz, CDCl3): δ -122.71, (s, F).
General procedure for the synthesis of diselenides and
ditellurides.[55,56] To a stirred solution of selenium powder or
tellurium powder (20 mmol, 2.0 equiv) and the aryl/aliphatic iodide
(10 mmol, 1.0 equiv) in dry DMSO (20 mL) were added CuO
nanoparticles (79.6 mg, 0.1 equiv) followed by KOH (1.12 g, 2.0
equiv) under argon atmosphere at 90 °C. After the reaction was
completed, the reaction mixture was allowed to cool to room
temperature and then quenched with water. The mixture was
extracted with EtOAc (2×50 mL). The combined organic layers
were dried over anhydrous MgSO4 and concentrated to give a
residue which was purified by flash chromatography on a silica
gel column chromatography (n-hexane) to give the pure
diselenide or ditelluride.
3-Bromo-5-((methylsulfonyl)diazenyl)pyridine (1t).[47] Yield:
1
93%. Yellow solid, H NMR (400 MHz, CDCl3) δ 9.17 (d, J = 2.0
Hz, 1H), 8.94 (d, J = 2.0 Hz, 1H), 8.30 (t, J = 2.0 Hz, 1H), 3.26 (s,
3H).
3-Methyl-5-((methylsulfonyl)diazenyl)pyridine (1u).[47] Yield:
1
93%. Yellow solid, H NMR (400 MHz, CDCl3) δ 9.00 (d, J = 2.2
Hz, 1H), 8.67 (d, J = 1.6 Hz, 1H), 7.92-7.91 (m, 1H), 3.21 (s, 3H),
2.43 (s, 3H).
[47]
2-Chloro-3-((methylsulfonyl)diazenyl)pyridine (1v).
Yield:
89%. Yellow solid, 1H NMR (400 MHz, CDCl3) δ 8.67 (dd, J = 4.8,
1.8 Hz, 1H), 8.06 (dd, J = 8.0, 1.8 Hz, 1H), 7.47-7.44 (m, 1H), 3.25
(s, 3H).
1,2-Diphenyldiselane.[55] Yield: 73%. Pale yellow solid. 1H NMR
(400 MHz, CDCl3) δ 7.62-7.60 (m, 4H), 7.29-7.23 (m, 6H).
2-Chloro-4-((methylsulfonyl)diazenyl)pyridine (1w).[47] Yield:
1,2-bis(3-Bromophenyl)diselane.[57a] Yield: 47%. Yellow oil, H
1
1
91%. Yellow solid, H NMR (400 MHz, CDCl3) δ 8.69 (d, J = 5.2
NMR (400 MHz, CDCl3) δ 7.75-7.62 (m, 2H), 7.52-7.37 (m, 4H),
7.15 (q, J = 7.7 Hz, 2H).
Hz, 1H), 7.78-7.77 (m, 1H), 7.66 (dd, J = 5.2, 1.8 Hz, 1H), 3.27 (s,
3H).
1,2-bis(4-Methoxyphenyl)diselane.[55] Yield: 44%. Yellow oil, 1H
NMR (400 MHz, CDCl3) δ 7.22-7.16 (m, 6H), 6.81-6.77 (m, 2H),
3.77 (s, 6H).
3-((Methylsulfonyl)diazenyl)quinoline (1x).[47] Yield: 86%.
Yellow solid, 1H NMR (400 MHz, CDCl3) δ 9.40 (d, J = 2.4 Hz, 1H),
8.74 (d, J = 2.0 Hz, 1H), 8.20 (d, J = 2.4 Hz, 1H), 8.02 (d, J = 8.2
Hz, 1H), 7.94-7.90 (m, 1H), 7.72-7.68 (m, 1H), 3.30 (s, 3H).
6-((Methylsulfonyl)diazenyl)quinoline (1y).[47] Yield: 90%.
Orange solid, 1H NMR (400 MHz, CDCl3) δ 9.06 (dd, J = 4.2, 1.6
1,2-Diphenylditellane.[55] Yield: 55%. Yellow solid, 1H NMR (400
MHz, CDCl3) δ 7.59-7.62 (m, 4H), 7.28-7.23 (m, 6H).
5
This article is protected by copyright. All rights reserved.

10.1002/ejoc.202001386
European Journal of Organic Chemistry
FULL PAPER
1
1,2-di(Pyridin-3-yl)ditellane.[55] Yield: 52%. Yellow oil, H NMR
(400 MHz, CDCl3) δ 8.87 (s, 2H), 7.53-7.52 (m, 2H), 7.99-7.97 (m,
2H), 7.17-7.14 (m, 2H).
2H), 7.39-7.32 (m, 5H), 4.35 (q, J = 7.2 Hz, 2H), 1.37 (t, J = 7.2
Hz, 3H). 13C NMR (100 MHz, CDCl3): δ 166.3, 139.3, 134.8, 130.5,
130.1, 129.6, 128.9, 128.7, 128.4, 60.9, 14.3.
1,2-Diheptylditellane.[55] Yield: 39%. Yellow oil, 1H NMR (400
MHz, CDCl3) δ 3.09 (t, J = 7.6 Hz, 2H), 2.61 (t, J = 7.6 Hz, 2H),
1.76-1.67 (m, 4H), 1.36-1.27 (m, 16H), 0.89-0.86 (m, 6H).
(4-Nitrophenyl)(phenyl)selane (2b).[62] Compound 2b (yellow
solid, 72.6 mg, 87% yield) was purified via column
chromatography (PE : EA = 30 : 1, Rf = 0.20). 1H NMR (400 MHz,
CDCl3): δ 8.03 (d, J = 9.0 Hz, 2H), 7.65-7.62 (m, 2H), 7.47-7.39
(m, 3H), 7.36 (d, J = 9.0 Hz, 2H). 13C NMR (100 MHz, CDCl3): δ
146.1, 143.9, 135.9, 130.0, 129.7, 129.3, 127.2, 123.9.
Synthesis of 1,2-bis(4-(trifluoromethyl)phenyl)diselane.[58]
A
round bottom flask equipped with a magnetic stir bar was charged
with 4-trifluoromethylphenylboronic acid (1.90 g, 10 mmol),
selenium dioxide (1.11 g, 1.0 equiv), I2 (2.54 g, 1.0 equiv), and 2-
Me-THF (20 mL). The resulting reaction mixture was stirred at
60 °C for 4 h, then sodium thiosulphate (aq.) was added and the
resulting mixture was extracted with ethyl acetate (3×50 mL) and
saturated brine solution. The combined organic layers were dried
over anhydrous MgSO4 and concentrated to give a residue which
was purified by flash chromatography (petroleum ether/ethyl
acetate, 100:0 to 95:5) to give the desired product (Yield: 50%,
Yellow oil). 1H NMR (400 MHz, CDCl3) δ 7.70 (d, J = 8.2 Hz, 4H),
7.52 (d, J = 8.2 Hz, 4H). 19F NMR (376 MHz, CDCl3): δ -62.68, (s,
6F).
Synthesis of 1,2-dibenzyldiselane.[59] In a 100 mL round bottom
flask, purged with a nitrogen gas, a rubber septa and magnetic
stirring, selenium powder (0.79 g, 10 mmol), NaBH4 (0.23 g, 0.6
equiv) and ethanol (40 mL) were added. This mixture was stirred
for 120 min at 70 °C and a reddish-brown solution was formed.
The reaction mixture was then cooled at room temperature and
benzyl chloride (1.2 mL, 1.0 equiv) was added. After stirring for
1h, the mixture was filtered, and the filtrate diluted with water (40
mL) and extracted with n-hexane (3×50 mL). The organic phases
were reunited, dried with anhydrous Na2SO4 and the solvent
removed by evaporation in vacuo. The crude product was then
recrystallized by ethanol to afford the desired product (Yield: 72%.
Yellow solid).[59] 1H NMR (400 MHz, CDCl3) δ 7.31-7.28 (m, 4H),
7.24-7.20 (m, 6H), 3.83 (s, 4H).
Synthesis of 1,2-dibutyldiselane.[60] Selenium (0.4 g, 5 mmol)
was added to a stirred solution of NaBH4 (0.38 g, 2.0 equiv) in
ethanol (40 mL) at 0 °C. The mixture was stirred for 30 min, then
additional Selenium (0.4 g, 1.0 equiv) was added to the reaction
mixture and stirred for another 30 min at 0 °C. Finally, iodobutane
(2.0 mL, 3.5 equiv) was added dropwise. After stirring for a 1 h at
room temperature, the reaction mixture was extracted with n-
hexane and washed with water, dried over sodium sulfate, and
concentrated in vacuo. The crude product was purified over silica
gel column chromatography (n-hexane/toluene = 20/1) to give the
desired product (Yield: 36%. Yellow oil). 1H NMR (400 MHz,
CDCl3) δ 2.92 (t, J = 7.4 Hz, 4H), 1.75-1.67 (m, 4H), 1.46-1.37 (m,
4H)), 0.92 (t, J = 7.4 Hz, 6H). [60]
1-(4-(Phenylselanyl)phenyl)ethan-1-one (2c).[62] Compound 2c
(yellow oil, 71.8 mg, 87% yield) was purified via column
chromatography (PE : EA = 30 : 1, Rf = 0.20). 1H NMR (400 MHz,
CDCl3): δ 7.79 (d, J = 8.4 Hz, 2H), 7.60-7.58 (m, 2H), 7.39-7.33
(m, 5H), 2.55 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 197.2, 140.2,
135.2, 135.0, 130.3, 129.7, 128.9, 128.6, 128.5, 29.7.
Phenyl(4-(phenylselanyl)phenyl)methanone
(2d).[63]
Compound 2d (yellow oil, 84.0 mg, 83% yield) was purified via
1
column chromatography (PE : EA = 20 : 1, Rf = 0.25). H NMR
(400 MHz, CDCl3): δ 7.77 (d, J = 7.2 Hz, 2H), 7.66 (d, J = 8.4 Hz,
2H), 7.63-7.61 (m, 2H), 7.59-7.56 (m, 1H), 7.47 (t, J = 7.8 Hz, 2H),
7.42-7.34 (m, 5H). 13C NMR (100 MHz, CDCl3): δ 195.9, 139.4,
137.5, 135.5, 135.1, 132.3, 130.7, 130.1, 129.9, 129.7, 128.6,
128.5, 128.2.
Ethyl (E)-3-(4-(phenylselanyl)phenyl)acrylate (2e). Compound
2e (yellow oil, 63.6 mg, 64% yield) was purified via column
chromatography (PE : EA = 30 : 1, Rf = 0.25). 1H NMR (400 MHz,
CDCl3): δ 7.62 (d, J = 16.0 Hz, 1H), 7.56-7.53 (m, 2H), 7.38 (s,
4H), 7.34-7.32 (m, 3H) 6.40 (d, J = 16.0 Hz, 1H), 4.26 (q, J = 7.2
Hz, 2H), 1.33 (t, J = 7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ
166.9, 143.7, 135.3, 134.2, 132.9, 131.7, 129.5, 129.5, 128.6,
128.1, 118.1, 60.5, 14.3. HRMS (ESI) m/z calcd for
C17H16O2SeNa [M+H]+355.0208; found 355.0207.
Methyl(4-(phenylselanyl)phenyl)sulfane (2f).[64] Compound 2f
(yellow oil, 40.2 mg, 48% yield) was purified via column
chromatography (PE : EA = 50 : 1, Rf = 0.50). 1H NMR (400 MHz,
CDCl3): δ 7.42-7.39 (m, 4H), 7.25-7.23 (m, 3H), 7.15 (d, J = 8.4
Hz, 2H), 2.45 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 138.4, 134.0,
132.3, 131.6, 129.3, 127.2, 127.1, 126.7, 15.6.
(3-Nitrophenyl)(phenyl)selane (2g).[65] Compound 2g (yellow
solid, 74.3 mg, 89% yield) was purified via column
chromatography (PE : EA = 30 : 1, Rf = 0.30). 1H NMR (400 MHz,
CDCl3): δ 8.20 (s, 1H), 8.05 (d, J = 8.2 Hz, 1H), 7.65 (d, J = 7.4
Hz, 1H), 7.58 (d, J = 7.4 Hz, 2H), 7.41-7.35 (m, 4H). 13C NMR
(100 MHz, CDCl3): δ 148.5, 136.8, 134.7, 131.5, 129.8, 129.7,
128.7, 128.3, 125.6, 121.5.
(2-Methoxyphenyl)(phenyl)selane (2h).[66] Compound 2h
(yellow oil, 61.6 mg, 78% yield) was purified via column
chromatography (PE : EA = 100 : 1, Rf = 0.50).1H NMR (400 MHz,
CDCl3): δ 7.60-7.58 (m, 2H), 7.35-7.32 (m, 3H), 7.21-7.16 (m, 1H),
6.95 (dd, J = 7.8, 1.6 Hz, 1H), 6.85 (d, J = 8.2 Hz, 1H), 6.81-6.77
(m, 1H), 3.88 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 156.5, 135.4,
130.7, 129.4, 128.2, 128.1, 127.6, 121.8, 121.6, 110.3, 55.8.
(3,4-Dichlorophenyl)(phenyl)selane (2i).[67] Compound 2i
(yellow oil, 82.5 mg, 91% yield) was purified via column
chromatography (PE, Rf = 0.65). 1H NMR (400 MHz, CDCl3): δ
General procedure for the synthesis of asymmetric selenides
and tellurides 2,3. The chosen arylazo sulfone (1, 0.3 mmol) and
a diselenide or a ditelluride (0.36 mmol, 1.2 equiv) were placed
into a flame dried 10 mL Shleck tube and dry MeCN (3 mL) was
added under argon. The resulting solution was argon saturated
and then stirred and irradiated at room temperature under argon
by means of a 21 W blue LED for 21-24 h. The reaction mixture
was then concentrated under reduced pressure and the crude
residue was purified by silica gel column chromatography to afford
the pure product.
7.53-7.49 (m, 3H), 7.34-7.29 (m, 4H), 7.22 (d, J = 8.4 Hz, 1H). 13
C
NMR (100 MHz, CDCl3): δ 133.9, 133.3, 133.1, 131.5, 131.3,
131.2, 130.8, 129.6, 129.4, 128.2.
Ethyl 4-(phenylselanyl)benzoate (2a).[61] Compound 2a (yellow
oil, 83.3 mg, 91% yield) was purified via column chromatography
(2-Methoxy-4-nitrophenyl)(phenyl)selane (2j). Compound 2j
(yellow solid, 74.9 mg, 81% yield mp. = 91-92 oC) was purified via
1
(Petroleum Ether, PE : Ethyl Acetate, EA = 30 : 1, Rf = 0.3) H
1
NMR (400 MHz, CDCl3): δ 7.88 (d, J = 8.4 Hz, 2H), 7.58-7.56 (m,
column chromatography (PE : EA = 30 : 1, Rf = 0.22). H NMR
6
This article is protected by copyright. All rights reserved.

10.1002/ejoc.202001386
European Journal of Organic Chemistry
FULL PAPER
(400 MHz, CDCl3): δ 7.68-7.61 (m, 4H), 7.51-7.42 (m, 3H), 6.81
(d, J = 8.4 Hz, 1H), 4.02 (s, 3H). 13C NMR (100 MHz, CDCl3): δ
155.4, 146.8, 137.1, 134.8, 130.0, 129.6, 127.6, 125.3, 116.5,
104.2, 56.3. HRMS (ESI) m/z calcd for C13H12NO3Se [M+H]+
309.9977; found 309.9978.
CDCl3): δ 9.04 (d, J = 2.0 Hz, 1H), 8.84 (d, J = 2.0 Hz, 1H), 8.31
(t, J = 2.0 Hz, 1H), 7.52-7.50 (m, 2H), 7.32-7.26 (m, 3H). 13C NMR
(100 MHz, CDCl3): δ 165.1, 155.7, 148.9, 140.3, 134.0, 129.7,
129.2, 128.5, 128.4, 126.5, 52.5. HRMS (ESI) m/z calcd for
C13H12NO2Se [M+H]+ 294.0028; found 294.0030.
(4-Chloro-3-nitrophenyl)(phenyl)selane (2k). Compound 2k
(yellow oil, 81.6 mg, 87% yield) was purified via column
chromatography (PE : EA = 50 : 1, Rf = 0.35). 1H NMR 400 MHz,
CDCl3): δ 7.77 (d, J = 2.0 Hz, 1H), 7.59-7.56 (m, 2H), 7.44-7.42
(m, 1H), 7.41-7.35 (m, 4H). 13C NMR (100 MHz, CDCl3): δ 148.1,
135.2, 134.9, 133.2, 132.1, 130.0, 129.1, 127.9, 127.2, 124.9.
HRMS (ESI) m/z calcd for C12H9ClNO2Se [M+H]+ 313.9482; found
313.9487.
Phenyl(3,4,5-trimethoxyphenyl)selane (2l). Compound 2l
(white solid, 54.3 mg, 56% yield mp. = 160-161 oC) was purified
via column chromatography (PE : EA = 15 : 1, Rf = 0.25). 1H NMR
(400 MHz, CDCl3): δ 7.43 (d, J = 7.6 Hz, 2H), 7.27-7.26 (m, 3H),
6.45 (s, 2H), 3.84 (s, 3H), 3.79 (s, 6H). 13C NMR (100 MHz,
CDCl3): δ 153.5, 137.8, 135.5, 131.9, 129.2, 127.0, 124.3, 111.0,
60.8, 56.1. HRMS (ESI) m/z calcd for C15H17O3Se [M+H]+
325.0337; found 325.0340.
3-Fluoro-5-(phenylselanyl)pyridine (2s). Compound 2s (yellow
oil, 39.3 mg, 52% yield) was purified via column chromatography
(PE : EA = 30 : 1, Rf(PE:EA 20:1) = 0.22). 1H NMR (400 MHz, CDCl3):
δ 8.41 (s, 1H), 8.30 (d, J = 2.4 Hz, 1H), 7.57-7.54 (m, 2H), 7.39-
7.32 (m, 4H). 19F NMR (376 MHz, CDCl3): δ -125.04, (s, 1F). 13
C
NMR (100 MHz, CDCl3): δ 159.3 (d, J = 259.4 Hz, 1C), 147.3,
136.2 (d, J = 23.1 Hz, 1C), 134.5, 130.6, 128.7, 128.0, 125.6 (d,
J = 14.9 Hz, 1C). HRMS (ESI) m/z calcd for C11H9FNSe [M+H]+
253.9879; found 253.9894.
3-Bromo-5-(phenylselanyl)pyridine (2t). Compound 2t (yellow
oil, 54.5 mg, 68% yield) was purified via column chromatography
(PE : EA = 30 : 1, Rf = 0.25). 1H NMR (400 MHz, CDCl3): δ 8.51
(s, 2H), 7.80 (t, J = 2.0 Hz, 1H), 7.55-7.53 (m, 2H), 7.36-7.26 (m,
3H). 13C NMR (100 MHz, CDCl3): δ 149.9, 148.9, 141.2, 134.3,
130.8, 129.9, 128.7, 128.3, 121.2. HRMS (ESI) m/z calcd for
C11H9BrNSe [M+H]+313.9078; found 313.9088.
5-(Phenylselanyl)benzo[d][1,3]dioxole (2m).[68] Compound 2m
(yellow oil, 75.7 mg, 91% yield) was purified via column
chromatography (PE : EA = 30 : 1, Rf = 0.35). 1H NMR (400 MHz,
CDCl3): δ 7.38-7.35 (m, 2H), 7.24-7.19 (m, 3H), 7.07 (dd, J = 8.0,
1.6 Hz, 1H), 7.00 (d, J = 1.6 Hz, 1H), 7.65 (d, J = 8.0 Hz, 1H), 5.93
(s, 2H). 13C NMR (100 MHz, CDCl3): δ 148.3, 147.8, 132.6, 131.4,
129.2, 128.5, 126.7, 121.3, 114.9, 109.2, 101.2.
3-(Phenylselanyl)pyridine (2n).[69] Compound 2n (yellow oil,
40.7 mg, 58% yield) was purified via column chromatography
(PE : EA = 15 : 1, Rf = 0.20). 1H NMR (400 MHz, CDCl3): δ 8.67
(s, 1H), 8.48 (d, J = 4.0 Hz, 1H), 7.73 (d, J = 8.0 Hz, 1H), 7.50-
7.48 (m, 2H), 7.31-7.29 (m, 3H), 7.20-7.17 (m, 1H). 13C NMR (100
MHz, CDCl3): δ 152.7, 148.2, 140.0, 133.5, 133.4, 129.5, 128.8,
127.9, 124.0.
3-Methyl-5-(phenylselanyl)pyridine (2u). Compound 2u (yellow
oil, 40.2 mg, 54% yield) was purified via column chromatography
(PE : EA = 20 : 1, Rf = 0.20). 1H NMR (400 MHz, CDCl3): δ 8.48
(s, 1H), 8.32 (s, 1H), 7.57 (s, 1H), 7.48-7.45 (m, 2H), 7.30-7.26
(m, 3H), 3.27 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 150.0, 148.9,
140.7, 133.9, 133.1, 129.8, 129.4, 127.8, 127.7, 18.2. HRMS
(ESI) m/z calcd for C12H12NSe [M+H]+ 250.0129; found 250.0131.
2-Chloro-3-(phenylselanyl)pyridine (2v).[41] Compound 2v
(yellow oil, 66.1 mg, 82% yield) was purified via column
chromatography (PE : EA = 30 : 1, Rf(= 0.35) 1H NMR (400 MHz,
CDCl3): δ 8.13 (dd, J = 4.6, 1.4 Hz, 1H), 7.65 (d, J = 6.8 Hz, 2H),
7.49-7.40 (m, 3H), 7.09 (dd, J = 7.8, 1.4 Hz, 1H), 6.99-6.96 (m,
1H). 13C NMR (100 MHz, CDCl3): δ 148.9, 146.4, 137.9, 136.6,
132.5, 130.1, 129.6, 126.4, 123.0.
2-Chloro-5-(phenylselanyl)pyridine (2o). Compound 2o (yellow
oil, 71.7 mg, 89% yield) was purified via column chromatography
(PE : EA = 20 : 1, Rf = 0.25). 1H NMR (400 MHz, CDCl3): δ 8.41
(d, J = 2.4 Hz, 1H), 7.64 (dd, J = 2.4, 8.4 Hz, 1H), 7.50-7.47 (m,
2H), 7.33-7.28 (m, 3H), 7.20 (d, J = 8.2 Hz, 1H). 13C NMR (100
MHz, CDCl3): δ 152.2, 150.4, 142.5, 133.6, 129.7, 129.1, 128.2,
127.6, 124.9. HRMS (ESI) m/z calcd for C11H9ClNSe [M+H]+
269.9583; found 269.9594.
2-Chloro-4-(phenylselanyl)pyridine (2w). Compound 2w
(yellow oil, 55.6 mg, 69% yield) was purified via column
chromatography (PE : EA = 30 : 1, Rf = 0.25). 1H NMR (400 MHz,
CDCl3): δ 8.07 (d, J = 5.4 Hz, 1H), 7.65-7.63 (m, 2H), 7.50-7.40
(m, 3H), 7.07 (d, J = 1.4 Hz, 1H), 6.99 (dd, J = 5.4, 1.4 Hz, 1H) .
13C NMR (100 MHz, CDCl3): δ 151.8, 149.2, 149.1, 148.9, 136.4,
130.1, 129.8, 125.3, 123.3, 122.2. HRMS (ESI) m/z calcd for
C11H9ClNSe [M+H]+269.9583; found 269.9593.
3-(Phenylselanyl)quinoline (2x).[69] Compound 2x (yellow solid,
45.2 mg, 53% yield mp. = 91-92 oC) was purified via column
chromatography (PE : EA = 20 : 1, Rf = 0.20). 1H NMR (400 MHz,
CDCl3): δ 8.92 (d, J = 1.4 Hz, 1H), 8.24 (d, J = 1.4 Hz, 1H), 8.08
(d, J = 8.8 Hz, 1H), 7.72-7.68 (m, 2H), 7.55-7.50 (m, 3H), 7.30-
7.29 (m, 3H). 13C NMR (100 MHz, CDCl3): δ 153.5, 146.8, 139.5,
133.2, 129.9, 129.6, 129.6, 129.4, 128.6, 127.9, 127.2, 127.1,
125.3.
2-Methyl-5-(phenylselanyl)pyridine (2p). Compound 2p (yellow
oil, 45.4 mg, 61% yield) was purified via column chromatography
(PE : EA = 30 : 1, Rf = 0.25). 1H NMR (400 MHz, CDCl3): δ 8.61
(d, J = 2.0 Hz, 1H), 7.67 (dd, J = 8.0, 2.0 Hz, 1H), 7.43-7.41 (m,
2H), 7.26-7.24 (m, 3H) 7.07 (d, J = 8.0 Hz, 1H), 2.53 (s, 3H). 13
C
NMR (100 MHz, CDCl3): δ 157.6, 1529, 141.4, 132.5, 130.6,
129.4, 127.4, 124.4, 124.0, 24.0. HRMS (ESI) m/z calcd for
C12H12NSe [M+H]+ 250.0129; found 250.0131.
2-Methoxy-5-(phenylselanyl)pyridine (2q).[70] Compound 2q
(yellow solid, 64.0 mg, 77% yield) was purified via column
chromatography (PE : EA = 20 : 1, Rf = 0.25). 1H NMR (400 MHz,
CDCl3): δ 8.36 (d, J = 2.2 Hz, 1H), 7.72 (dd, J = 8.4, 2.2 Hz, 1H),
7.35-7.33 (m, 2H), 7.25-7.20 (m, 3H), 6.70 (d, J = 8.4 Hz, 1H),
3.93 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 164.0, 152.3, 145.1,
132.0, 131.2, 129.2, 126.9, 117.8, 112.1, 53.5.
6-(Phenylselanyl)quinoline (2y).[41] Compound 2y (pale brown
oil, 45.2 mg, 53% yield) was purified via column chromatography
(PE : EA = 20 : 1, Rf = 0.22). 1H NMR (400 MHz, CDCl3): δ 8.87-
8.86 (m, 1H), 7.98 (t, J = 9.0 Hz, 2H), 7.85 (d, J = 1.8 Hz, 1H),
7.69 (dd, J = 8.8, 1.8 Hz, 1H), 7.55-7.53 (m, 2H), 7.37-7.34 (m,
1H), 7.32-7.30 (m, 3H). 13C NMR (100 MHz, CDCl3): δ 150.4,
147.2, 135.2, 133.7, 133.3, 130.5, 130.3, 130.1, 130.1, 129.5,
128.8, 127.8, 121.5.
Methyl 5-(phenylselanyl)nicotinate (2r). Compound 2r (yellow
solid, 60.5 mg, 69% yield) was purified via column
chromatography (PE : EA = 20 : 1, Rf = 0.20). 1H NMR (400 MHz,
Methyl
3-(phenylselanyl)thiophene-2-carboxylate
(2z).
Compound 2z (yellow solid, 81.1 mg, 91 % yield, mp = 66-67 oC)
7
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10.1002/ejoc.202001386
European Journal of Organic Chemistry
FULL PAPER
was purified via column chromatography (PE : EA = 20 : 1, Rf =
0.25). 1H NMR (400 MHz, CDCl3): δ 7.73 (d, J = 6.8 Hz, 2H), 7.46-
7.37 (m, 3H), 7.30 (d, J = 5.2 Hz, 1H), 6.35 (d, J = 5.2 Hz, 1H),
3.92 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 163.0, 140.5, 136.8,
131.0, 129.6, 129.3, 129.2, 128.3, 122.4, 52.1. HRMS (ESI) m/z
calcd for C12H11O2SSe [M+H]+298.9639; found 298.9645.
3-(Phenylselanyl)-1H-indazole (2aa).[71] Compound 2aa (yellow
solid, 66.4 mg, 81% yield) was purified via column
chromatography (PE : EA = 15 : 1, Rf = 0.22). 1H NMR (400 MHz,
CDCl3): δ 13.29 (s, 1H), 7.81 (d, J = 8.4 Hz, 1H), 7.69 (d, J = 8.4
Hz, 1H), 7.46-7.44 (m, 2H), 7.41 (t, J = 4.8 Hz, 1H), 7.20-7.17 (m,
4H). 13C NMR (100 MHz, CDCl3): δ 141.3, 132.8, 130.8, 130.7,
129.2, 127.3, 126.8, 126.3, 121.7, 120.9, 111.1.
CDCl3): δ -62.73, (s, 3F). 13C NMR (100 MHz, CDCl3): δ 166.0,
136.5, 135.4, 133.0, 132.5, 130.5, 130.2 (q, J = 15.3 Hz, 1C),
129.8, 126.2 (q, J = 3.7 Hz, 1C), 123.9 (q, J = 271.3 Hz, 1C), 61.1,
14.3.
(4-Methoxyphenyl)(4-(trifluoromethyl)phenyl)selane (2ah).[73]
Compound 2ah (white solid, 16.9 mg, 17% yield) was purified via
1
column chromatography (PE : EA = 30 : 1, Rf = 0.50). H NMR
(400 MHz, CDCl3): δ 7.56 (d, J = 8.8 Hz, 2H), 7.42 (d, J = 8.2 Hz,
2H), 7.32 (d, J = 8.2 Hz, 2H), 6.91 (d, J = 8.8 Hz, 2H), 3.84 (s, 3H).
19F NMR (376 MHz, CDCl3): δ -62.53, (s, 3F). 13C NMR (100 MHz,
CDCl3): δ 160.4, 139.5, 137.7, 129.4, 128.1 (q, J = 32.3 Hz, 1C),
125.7 (q, J = 3.7 Hz, 1C), 124.2 (q, J = 270.0 Hz, 1C), 117.9, 115.5,
55.3.
2-Methyl-5-(phenylselanyl)benzo[d]thiazole (2ab). Compound
2ab (yellow oil, 62.1 mg, 68% yield) was purified via column
chromatography (PE : EA = 30 : 1, Rf = 0.25). 1H NMR (400 MHz,
CDCl3): δ 8.02 (d, J = 1.4 Hz, 1H), 7.68 (d, J = 8.4 Hz, 1H), 7.50-
7.48 (m, 2H), 7.43 (dd, J = 8.4, 1.4 Hz, 1H), 7.26-7.25 (m, 3H),
2.79 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 167.8, 154.1, 134.7,
133.2, 130.7, 129.3, 129.1, 128.7, 127.5, 126.5, 121.8, 20.1.
HRMS (ESI) m/z calcd for C14H12NSSe [M+H]+ 305.98503; found
305.9852.
Naphthalen-2-yl(phenyl)selane (2ac).[27] Compound 2ac
(yellow solid, 46.7 mg, 55% yield) was purified via column
chromatography (PE : EA = 100 : 1, Rf(PE:EA 50:1) = 0.42). 1H NMR
(400 MHz, CDCl3): δ 7.99 (s, 1H), 7.81-7.89 (m, 1H), 7.73 (d, J =
8.0 Hz, 2H), 7.50-7.46 (m, 4H) 7.28-7.27 (m, 3H). 13C NMR (100
MHz, CDCl3): δ 134.0, 132.9, 132.4, 132.0, 131.2, 130.4, 129.3,
128.8, 128.4, 127.7, 127.4, 127.3, 126.5, 126.2.
Ethyl 4-((4-methoxyphenyl)selanyl)benzoate (2ai). Compound
2ai (yellow oil, 70.4 mg, 70% yield) was purified via column
chromatography (PE : EA = 30 : 1, Rf = 0.25). 1H NMR (400 MHz,
CDCl3): δ 7.88 (d, J = 8.4 Hz, 2H), 7.39 (d, J = 8.4 Hz, 2H), 7.24
(t, J = 7.8 Hz, 1H), 7.14-7.12 (m, 1H), 7.11-7.10 (m, 1H), 6.90-
6.87 (m, 1H), 4.35 (q, J = 7.2 Hz, 2H), 3.77 (s, 3H), 1.37 (t, J = 7.2
Hz, 3H). 13C NMR (100 MHz, CDCl3): δ 166.2, 139.1, 130.6, 130.1,
129.7, 128.6, 126.8, 119.7, 114.3, 60.9, 55.3, 14.2. HRMS (ESI)
m/z calcd for C16H17O3Se [M+H]+ 337.0337; found 337.0333.
(4-Methoxyphenyl)(o-tolyl)selane (2aj).[72] Compound 2aj
(yellow oil, 36.1 mg, 53% yield) was purified via column
chromatography (PE : EA = 50 : 1, Rf = 0.30). 1H NMR (400 MHz,
CDCl3): δ 7.48 (d, J = 8.8 Hz, 2H), 7.18 (d, J = 7.2 Hz, 1H), 7.14-
7.08 (m, 2H), 7.04-7.00 (m, 1H), 6.88 (d, J = 8.8 Hz, 2H), 3.83 (s,
3H), 2.40 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 159.7, 137.8,
136.6, 133.9, 130.7, 130.0, 126.5, 126.5, 119.2, 115.2, 55.2, 21.8.
(4-nitronaphthalen-1-yl)(phenyl)selane (2ad). Compound 2ad
(yellow solid, 77.8 mg, 79% yield mp = 86-87 oC) was purified via
column chromatography (PE : EA = 30 : 1, Rf = 0.30). H NMR
2-Chloro-5-((4-methoxyphenyl)selanyl)pyridine
Compound 2ak (yellow oil, 69.9 mg, 78% yield) was purified via
column chromatography (PE : EA = 30 : 1, Rf = 0.25). H NMR
(2ak).
1
1
(400 MHz, CDCl3): δ 8.62 (d, J = 9.0 Hz, 1H), 8.32 (d, J = 9.0 Hz,
1H), 7.99 (d, J = 8.2 Hz, 1H), 7.76 (t, J = 7.4 Hz, 1H), 7.68 (t, J =
8.2 Hz, 1H), 7.62-7.60 (m, 2H), 7.45-7.38 (m, 3H), 7.30 (d, J = 8.2
(400 MHz, CDCl3): δ 8.31 (d, J = 2.0 Hz, 2H), 7.53-7.48 (m, 3H),
7.14 (d, J = 8.4, 0.4 Hz, 1H), 6.87 (d, J = 8.8 Hz, 2H), 3.81 (s, 3H).
13C NMR (100 MHz, CDCl3): δ 160.3, 150.7, 149.7, 140.9, 136.8,
Hz, 1H). 13C NMR (100 MHz, CDCl3): δ 145.4, 142.3, 135.4, 132.9, 129.3, 124.7, 118.1, 115.5, 55.3. HRMS (ESI) m/z calcd for
131.5, 130.0, 129.7, 129.1, 127.7, 127.7, 126.6, 125.2, 123.8,
123.6. HRMS (ESI) m/z calcd for C16H12NO2Se [M+H]+330.0028;
found 330.0028.
C12H11ClNOSe [M+H]+ 299.9689; found 299.9696.
2-Methoxy-5-((4-methoxyphenyl)selanyl)pyridine
(2al).
Compound 2al (yellow oil, 43.2 mg, 49% yield) was purified via
1
ethyl 4-((3-bromophenyl)selanyl)benzoate (2ae). Compound
2ae (yellow oil, 99.1 mg, 86% yield) was purified via column
chromatography (PE : EA = 30 : 1, Rf = 0.35). 1H NMR (400 MHz,
CDCl3): δ 7.92 (d, J = 8.0 Hz, 2H), 7.68 (t, J = 1.8 Hz, 1H), 7.47-
7.41 (m, 4H), 7.19 (t, J = 8.0 Hz, 1H), 4.36 (q, J = 7.2 Hz, 2H),
1.38 (t, J = 7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ 166.0,
137.7, 136.4, 132.5, 131.3, 131.2, 130.8, 130.3, 129.2, 123.2,
61.0, 14.3. HRMS (ESI) m/z calcd for C15H14BrO2Se
[M+H]+384.9337; found 384.9340.
column chromatography (PE : EA = 30 : 1, Rf = 0.30). H NMR
(400 MHz, CDCl3): δ 8.27-8.26 (m, 1H), 7.64 (dd, J = 8.4, 2.4 Hz,
1H), 7.40 (d, J = 8.8 Hz, 2H), 6.80 (d, J = 8.8 Hz, 2H), 6.65 (dd, J
= 8.4, 0.4 Hz, 1H), 3.91 (s, 3H) 3.77 (s, 3H). 13C NMR (100 MHz,
CDCl3): δ 163.6, 159.4, 150.7, 143.7, 134.7, 121.1, 119.7, 115.0,
111.9, 55.2, 53.5. HRMS (ESI) m/z calcd for C13H14NO2Se [M+H]+
296.0184; found 296.0186.
Benzyl(4-methoxyphenyl)selane (2am).[74] Compound 2am
(yellow solid, 42.4 mg, 51% yield) was purified via column
chromatography (PE : EA = 30 : 1, Rf = 0.40). 1H NMR 400 MHz,
CDCl3): δ 7.36 (d, J = 8.8 Hz, 2H), 7.25-7.18 (m, 3H), 7.14-7.12
(m, 2H), 6.78 (d, J = 8.8 Hz, 2H). 13C NMR (100 MHz, CDCl3): δ
159.5, 139.0, 136.4, 128.7, 128.2, 126.6, 120.0, 114.5, 55.2, 33.1.
(Benzylselanyl)-2-chloropyridine (2an). Compound 2an (yellow
solid, 61.9 mg, 73% yield, mp = 34-35 oC) was purified via column
chromatography (PE : EA = 30 : 1, Rf = 0.27). 1H NMR (400 MHz,
CDCl3): δ 8.34 (d, J = 2.0 Hz, 1H), 7.55 (dd, J = 8.2, 2.0 Hz, 1H),
7.26-7.20 (m, 3H), 7.15-7.12 (m, 3H), 4.05 (s, 2H). 13C NMR (100
MHz, CDCl3): δ 153.9, 150.8, 144.3, 137.5, 128.8, 128.5, 127.2,
125.2, 124.4, 32.5. HRMS (ESI) m/z calcd for C12H11ClNSe
[M+H]+ 283.9740; found 283.9750.
(3-Bromophenyl)(4-methoxyphenyl)selane
(2af).[72]
Compound 2af (yellow oil, 84.2 mg, 82% yield) was purified via
column chromatography (PE : EA = 40 : 1, Rf(PE:EA 30:1) = 0.45). 1H
NMR (400 MHz, CDCl3): δ 7.53 (d, J = 8.0 Hz, 2H), 7.41 (t, J =
1.8 Hz, 1H), 7.29 (d, J = 8.0 Hz, 1H), 7.20 (d, J = 8.0 Hz, 1H), 7.07
(t, J = 8.0 Hz,1H), 6.89 (d, J = 8.0 Hz, 2H), 3.83 (s, 3H). 13C NMR
(100 MHz, CDCl3): δ 160.1, 137.1, 135.7, 132.6, 130.2, 129.2,
128.7, 123.1, 118.7, 115.3, 55.2.
Ethyl 4-((4-(trifluoromethyl)phenyl)selanyl)benzoate (2ag).[73]
Compound 2ag (yellow oil, 42.5 mg, 38% yield) was purified via
1
column chromatography (PE : EA = 30 : 1, Rf = 0.40). H NMR
(400 MHz, CDCl3): δ 7.98-7.84 (m, 2H), 7.58-7.49 (m, 6H), 4.37
(q, J = 6.8 Hz, 2H), 1.39 (t, J = 6.8 Hz, 3H). 19F NMR (376 MHz,
8
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10.1002/ejoc.202001386
European Journal of Organic Chemistry
FULL PAPER
5-(Benzylselanyl)-2-methoxypyridine (2ao). Compound 2ao
(yellow oil, 36.7 mg, 44% yield) was purified via column
chromatography (PE : EA = 30 : 1, Rf = 0.30). 1H NMR (400 MHz,
CDCl3): δ 8.18 (d, J = 2.0 Hz, 1H), 7.50 (dd, J = 2.0, 8.4 Hz, 1H),
7.23-7.16 (m, 3H), 7.10-7.08 (m, 2H), 6.60 (d, J = 8.4 Hz, 1H) 3.96
(s, 2H), 3.91 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 163.9, 152.9,
145.6, 138.5, 128.8, 128.4, 126.9, 117.1, 111.3, 53.5, 33.1.
HRMS (ESI) m/z calcd for C13H14NOSe [M+H]+280.0235; found
280.0237.
CDCl3): δ 7.60-7.57 (m, 2H), 7.48-7.43 (m, 4H), 7.39-7.33 (m, 3H).
19F NMR (376 MHz, CDCl3): δ -62.78, (s, 3F). 13C NMR (100 MHz,
CDCl3): δ 164.0, 152.3, 145.1, 132.0, 130.2, (d, J = 191.7 Hz, 1C),
130.3 (q, J = 235.8 Hz, 1C), 126.9, 117.8, 112.1, 53.5 (q, J = 5.1
Hz, 1C).
(4-Methoxyphenyl)(phenyl)tellane (3c).[76] Compound 3c
(yellow oil, 44.0 mg, 47% yield) was purified via column
chromatography (PE : EA = 50 : 1, Rf (PE : EA = 30 : 1) = 0.30). 1H NMR
(400 MHz, CDCl3): δ 7.74 (d, J = 7.4 Hz, 2H), 7.58-7.56 (m, 2H),
3-(Benzylselanyl)-1H-indazole (2ap). Compound 2ap (yellow oil, 7.24-7.16 (m, 3H), 6.80 (d, J = 8.8 Hz, 2H), 3.81 (s, 3H). 13C NMR
50. mg, 65% yield) was purified via column chromatography (PE :
EA = 15 : 1, Rf = 0.20). H NMR (400 MHz, CDCl3): δ 11.78 (s,
(100 MHz, CDCl3): δ 160.0, 141.2, 136.4, 129.3, 127.2, 115.9,
115.5, 103.2, 55.2.
1
1H), 7.81 (d, J = 8.4 Hz, 1H), 7.65 (d, J = 8.4 Hz, 1H), 7.46-7.42
(m, 1H), 7.20 (t, J = 7.6 Hz, 1H), 7.15-7.11 (m, 5H), 4.22 (s, 2H).
13C NMR (100 MHz, CDCl3): δ 141.0, 138.5, 133.2, 128.7, 128.3,
127.1, 126.8, 126.3, 121.2, 120.8, 111.0, 32.2. HRMS (ESI) m/z
calcd for C14H13N2Se [M+H]+289.0238; found 289.0240.
2-Chloro-5-(phenyltellanyl)pyridine (3d). Compound 3d (yellow
oil, 74.2 mg, 78% yield) was purified via column chromatography
(PE : EA = 50 : 1, Rf (PE : EA = 30 : 1) = 0.40). H NMR (400 MHz,
1
CDCl3): δ 8.41 (d, J = 2.4 Hz, 1H), 7.65 (dd, J = 6.8, 2.4 Hz, 1H),
7.50-7.47 (m, 2H), 7.33-7.28 (m, 3H), 7.20 (dd, J = 8.2, 0.4 Hz,
1H). 13C NMR (100 MHz, CDCl3): δ 152.2, 150.3, 142.5, 133.6,
129.7, 129.0 128.2, 127.6, 124.9. HRMS (ESI) m/z calcd for
C11H8ClNTeNa [M+Na]+341.9300; found 341.9301.
Benzyl(naphthalen-2-yl)selane (2aq). Compound 2aq (white
solid, 78.5 mg, 88% yield, mp = 67-68 oC) was purified via column
chromatography (PE : EA = 50 : 1, Rf = 0.50). 1H NMR (400 MHz,
CDCl3): δ 7.89 (s, 1H), 7.79-7.67 (m, 1H), 7.71-7.68 (m, 2H) 7.51
2-Methoxy-5-(phenyltellanyl)pyridine (3e).[77] Compound 3e
(yellow oil, 72.3 mg, 77% yield) was purified via column
(dd, J = 8.4, 1.6 Hz, 1H), 7.45 (t, J = 4.0 Hz, 2H), 4.17 (s, 2H). 13
C
1
NMR (100 MHz, CDCl3): δ 138.5, 133.8, 132.3, 130.7, 128.8,
128.4, 128.2, 127.9, 127.7, 127.3, 126.9, 126.3, 126.0, 123.4,
32.2. HRMS (ESI) m/z calcd for C11H15Se [M+H]+299.0333; found
299.0335.
chromatography (PE, Rf = 0.25). H NMR (400 MHz, CDCl3): δ
8.36 (d, J = 2.2 Hz, 1H), 7.72 (dd, J = 8.4, 2.2 Hz, 1H), 7.35-7.33
(m, 2H), 7.25-7.19 (m, 3H), 6.70 (d, J = 8.4 Hz, 1H), 3.93 (s, 3H).
13C NMR (100 MHz, CDCl3): δ 164.0, 152.2, 145.2, 132.0, 131.2,
129.3, 126.9, 117.9, 112.3, 53.7.
Methyl
3-(benzylselanyl)thiophene-2-carboxylate
(2ar).
Compound 2ar (yellow solid, 51.4 mg, 55% yield, mp = 77-78 oC)
was purified via column chromatography (PE : EA = 30 : 1, Rf =
0.25). 1H NMR (400 MHz, CDCl3): δ 7.48 (d, J = 5.2 Hz, 1H), 7.40
(d, J = 7.2 Hz, 2H), 7.32-7.28 (m, 2H), 7.25-7.22 (m, 1H), 7.05 (d,
J = 5.2 Hz, 1H), 4.24 (s, 2H) 3.86 (s, 3H). 13C NMR (100 MHz,
CDCl3): δ 162.8, 138.6, 136.9, 131.6, 129.0, 128.6, 127.9, 127.1,
126.4, 52.0, 30.1. HRMS (ESI) m/z calcd for C13H13O2SSe
[M+H]+312.9796; found 312.9806.
3-(Phenyltellanyl)quinoline (3f). Compound 3f (yellow oil, 47.9
mg, 48% yield) was purified via column chromatography (PE : EA
= 30 : 1, Rf = 0.20). 1H NMR (400 MHz, CDCl3): δ 8.92 (d, J = 2.0
Hz, 1H), 8.25 (d, J = 2.0 Hz, 1H), 8.08 (d, J = 8.8 Hz, 1H), 7.72-
7.68 (m, 2H), 7.56-7.54 (m, 1H), 7.53-7.49 (m, 2H), 7.32-7.28 (m,
3H). 13C NMR (100 MHz, CDCl3): δ 148.9, 142.5, 141.7, 134.3,
131.9, 130.1, 129.1, 128.9, 128.9, 127.9, 127.4, 126.7, 125.8.
HRMS (ESI) m/z calcd for C15H12NTe [M+H]+ 336.0026; found
Ethyl 4-(butylselanyl)benzoate (2as). Compound 2as (yellow oil, 336.0030.
69.3 mg, 81% yield) was purified via column chromatography
(PE : EA = 50 : 1, Rf = 0.22). 1H NMR (400 MHz, CDCl3): δ 7.89
(d, J = 8.0 Hz, 2H), 7.46 (d, J = 8.0 Hz, 2H), 4.36 (q, J = 7.2 Hz,
2H), 2.98 (t, J = 7.4 Hz, 2H), 1.76-1.69 (m, 2H), 1.47-1.42 (m, 2H),
1.38 (t, J = 7.2 Hz, 3H), 0.92 (t, J = 7.4 Hz, 3H). 13C NMR (100
MHz, CDCl3): δ 166.3, 138.3, 130.3, 129.8, 128.1, 60.8, 31.9,
29.7, 26.8, 22.9, 13.5. HRMS (ESI) m/z calcd for C13H18O2SeNa
[M+Na]+ 309.0364; found 309.0364.
Methyl
3-(phenyltellanyl)thiophene-2-carboxylate
(3g).
Compound 3g (yellow oil, 55.0 mg, 53% yield) was purified via
column chromatography (PE : EA = 30 : 1, Rf = 0.23). H NMR
1
(400 MHz, CDCl3): δ 7.74-7.72 (m, 2H), 7.46-7.37 (m, 3H), 7.30
(d, J = 5.2 Hz, 1H), 6.35 (d, J = 5.2 Hz, 1H), 3.92 (s, 3H). 13C NMR
(100 MHz, CDCl3): δ 163.0, 140.5, 136.8, 131.0, 129.6, 129.3,
129.2, 128.3, 122.4, 52.1. HRMS (ESI) m/z calcd for
C12H10O2STeNa [M+Na]+ 370.9356; found 370.9356.
Butyl(4-methoxyphenyl)selane (2at).[65] Compound 2at (yellow
solid, 40.1 mg, 55% yield) was purified via column
chromatography (PE : EA = 50 : 1, Rf (PE:EA = 30:1) = 0.50). 1H NMR
(400 MHz, CDCl3): δ 7.46 (d, J = 8.0 Hz, 2H), 6.81 (d, J = 8.0 Hz,
2H), 3.79 (s, 3H), 2.82 (t, J = 7.4 Hz, 2H), 1.68-1.61 (m, 2H), 1.45-
1.36 (m, 2H), 0.89 (t, J = 7.4 Hz, 3H). 13C NMR (100 MHz, CDCl3):
δ 159.1, 135.4, 120.2, 114.6, 55.2, 32.3, 28.8, 22.8, 13.5.
Ethyl 4-(phenyltellanyl)benzoate (3a).[75] Compound 3a (yellow
oil, 79.6 mg, 75% yield) was purified via column chromatography
(PE : EA = 30 : 1, Rf = 0.25). 1H NMR (400 MHz, CDCl3): δ 7.88
(d, J = 8.5 Hz, 2H), 7.59-7.56 (m, 2H), 7.39-7.32 (m, 5H), 4.35 (q,
J = 7.2 Hz, 2H), 1.37 (t, J = 7.2 Hz, 3H). 13C NMR (100 MHz,
CDCl3): δ 166.2, 139.4, 134.8, 130.4, 130.1, 129.6, 128.8, 128.6,
128.4, 60.9, 14.3.
2-Chloro-5-(pyridin-3-yltellanyl)pyridine (3h). Compound 3h
(yellow solid, 44.9 mg, 47% yield, mp = 111-112 oC) was purified
via column chromatography (PE : EA = 10 : 1, Rf = 0.20). 1H NMR
(400 MHz, CDCl3): δ 8.89 (s, 1H), 8.64 (d, J = 1.8 Hz, 1H), 8.56
(dd, J = 1.2, 4.8 Hz, 1H), 8.01 (dt, J = 7.8, 1.8 Hz, 1H) 7.92 (dd, J
= 2.2, 7.2 Hz, 1H) 7.22-7.19 (m, 2H). 13C NMR (100 MHz, CDCl3):
δ 157.4, 157.3, 151.9, 149.3, 147.4, 145.7, 125.7, 125.0, 111.1,
109.2. HRMS (ESI) m/z calcd for C10H8ClN2Te [M+H]+ 320.9433;
found 320.9435.
N-(4-(heptyltellanyl)phenyl)acetamide (3i). Compound 3i
(yellow oil, 37.9 mg, 35% yield) was purified via column
chromatography (PE : EA = 15 : 1, Rf = 0.20). 1H NMR (400 MHz,
CDCl3): δ 7.66 (d, J = 8.4 Hz, 2H), 7.39 (s, 1H), 7.35 (d, J = 8.4
Hz, 2H), 2.85 (t, J = 7.6 Hz, 2H), 2.16 (s, 3H), 1.79-1.71 (m, 2H),
1.35-1.24 (m, 8H), 0.86 (t, J = 6.6 Hz, 3H). 13C NMR (100 MHz,
CDCl3): δ 168.3, 139.5, 137.6, 120.5, 105.8, 31.8, 31.7, 31.7, 28.5,
Phenyl(4-(trifluoromethyl)phenyl)tellane (3b).[41] Compound
3b (yellow oil, 59.8 mg, 57% yield) was purified via column
chromatography (PE : EA = 20 : 1, Rf = 0.30). 1H NMR (400 MHz,
9
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10.1002/ejoc.202001386
European Journal of Organic Chemistry
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[M+H]+ 364.0915; found 364.0911.
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1
(PE : EA = 50 : 1, Rf (PE : EA = 30 : 1) = 0.50). H NMR (400 MHz,
CDCl3): δ 8.63 (d, J = 2.0 Hz, 1H), 7.97 (dd, J = 8.0, 2.0 Hz, 1H),
7.17 (d, J = 8.0, 0.4 Hz, 1H), 2.88 (t, J = 7.4 Hz, 2H), 1.79-1.72
(m, 2H), 1.36-1.20 (m, 8H), 0.86 (t, J = 6.8 Hz, 3H). 13C NMR (100
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28.5, 22.6,14.0, 9.6. HRMS (ESI) m/z calcd for C12H19ClNTe
[M+H]+342.0263; found 342.0255.
5-(Heptyltellanyl)-2-methoxypyridine (3k). Compound 3k
(yellow oil, 46.2 mg, 46% yield) was purified via column
chromatography (PE : EA = 30 : 1, Rf = 0.30). 1H NMR (400 MHz,
CDCl3): δ 8.48 (d, J = 2.0, Hz, 1H), 7.91 (dd, J = 2.0, 8.4 Hz, 1H),
6.63 (dd, J = 8.4, 0.4 Hz, 1H), 3.91 (s, 3H), 2.78 (t, J = 7.5 Hz,
2H), 1.75-1.70 (m, 2H), 1.34-1.21 (m, 8H), 0.86 (t, J = 6.7 Hz, 3H).
13C NMR (100 MHz, CDCl3): δ 168.5, 136.9, 133.6, 125.3, 120.5,
31.6, 30.1, 29.7, 28.7, 28.5, 24.4, 22.5, 14.0. HRMS (ESI) m/z
calcd for C13H22NOTe [M+H]+ 338.0758; found 338.0761.
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The authors sincerely thank the financial support from National
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Keywords. Aryl Radicals • Dyedauxiliary groups • Chalcogen •
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Key Topic: Dyedauxiliary Groups
Unsymmetrical (hetero)aryl selenides and tellurides have been prepared in satisfactory yields from arylazo sulfones under visible light
driven, photocatalyst- and metal-free conditions.
Institute and/or researcher Twitter usernames: @protti_stefano; @PhotogreenLab
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