Metal-Free Synthesis of Selenodihydronaphthalenes by Selenoxide-Mediated Electrophilic Cyclization of Alkynes

Article abstract of DOI:10.1002/ejoc.202100423

A transition-metal-free, selenium mediated electrophilic cyclization reaction was realized through a one-pot procedure between simple alkynes and triflic anhydride-activated selenoxides to give selenium containing dihydronaphthalene products. This method gave good to very high yields for all products, including selenium-substituted phenanthrene, dihydroquinoline, 2H-chromene, and coumarin, which can be further transformed to other functionalized compounds.

Full text of DOI:10.1002/ejoc.202100423

European Journal of Organic Chemistry
Accepted Article
Accepted Article
Title: Metal-free Synthesis of Selenodihydronaphthalenes by
Selenoxide-mediated Electrophilic Cyclization of Alkynes
Authors: Shaoyu An, Zhong Zhang, and Pingfan Li
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.202100423
Link to VoR: https://doi.org/10.1002/ejoc.202100423
01/2020

10.1002/ejoc.202100423
European Journal of Organic Chemistry
FULL PAPER
Metal-free Synthesis of Selenodihydronaphthalenes by
Selenoxide-mediated Electrophilic Cyclization of Alkynes
Shaoyu An[a], Zhong Zhang[a] and Pingfan Li*[a]
[a]
S. An, Dr. Z. Zhang, Prof. Dr. P. Li
State Key Laboratory of Chemical Resource Engineering, Department of Organic Chemistry, College of Chemistry
Beijing University of Chemical Technology
Beijing 100029, P. R. China
E-mail: lipf@mail.buct.edu.cn
https://chemistry.buct.edu.cn/2015/0331/c1950a22978/page.htm
Supporting information for this article is given via a link at the end of the document.
Abstract: A transition-metal-free, selenium mediated electrophilic
cyclization reaction was realized through one-pot procedure
yl)benzene[8d], respectively, with phenyl selenium halide as
electrophilic reagent (Scheme 1c). However, electrophilic
cyclization of non-heteroatom alkyne substrates using
aromatic ring as nucleophile still remain unexplored.
Inspired by the wide range of reactions of anhydride-activated
sulfoxide[20-21], we were interested in whether the similarly
electrophilic triflic anhydride-activated selenoxide could be
a
between simple alkynes and triflic anhydride-activated selenoxides to
give selenium containing dihydronaphthalene products. This method
gave good to very high yields for all products including selenium-
substituted phenanthrene, dihydroquinoline, 2H-chromene, and
coumarin, which can be further transformed to other functionalized
compounds.
suitable
for
the
synthesis
of
selenium-substituted
dihydronaphthalenes (Scheme 1d). Herein, we describe the
substrate scope of our investigation of such metal-free selenium-
involved electrophilic cyclization, which provides selenium
containing products with better derivatization reactivities than the
corresponding sulfur counterparts.[21]
Introduction
Aryl bicyclic structure are ubiquitous in modern synthetic
chemistry, which not only exist in many biologically and
medicinally important compounds, but can be further
converted to more useful compounds such as chiral ligands
and catalysts.[1] In recent years, easily available methods
towards the construction and derivatization of such cyclic
scaffold are of particular interest and numerous strategies
have been explored, including alkyne insertion cyclization,[2]
free radical-induced intramolecular cyclization,[3] visible-light
Br
H3C CH3
NO2
H3CO
H3CO
Se
Se
Se
OCH3
OCH3
CH3
CO2H
O2N
H3C CH3
Antitumor agent (A)
RAR agonist (B)
TR and GR Inhibitor (C)
b) Aryl diselenide mediated cyclization (Baidya et al.)
R3
R3
N
O
N
O
initiated
cyclization,[4]
Diels−Alder
reaction,[5]
K2S2O8
R1
+
R1
ArSeSeAr
Suzuki−Miyaura coupling[6] and others.[7] Recently,
electrophile-mediated cyclization of internal alkynes has
become one of the most effective method for synthesizing
carbocycles and heterocycles,[1c] which provides cyclic
structures with different substituents, such as halogen,[8]
sulfur,[9] boron,[10] phosphorus[11] and so on.[12]
SeAr
R2
R2
c) Phenyl selenium halide mediated electrophilic cyclization (Larock et al.)
R
N
O
+
or
PhSeX
SePh
SePh
(X = Cl or Br)
Ph
Ph
Ph
(R = NH or O)
Organoselenium compounds are important structural
motifs because of their biological activities and
pharmacological properties.[13] For instance, the diaryl
d) Selenoxide mediated electrophilic cyclization (This work)
O
A
is used as an antitumor agent,[14] the carboxylic
Se
OTf
Se
R1
H3C
Ar
R1
selenide
acid
is a retinoic acid receptor (RAR) agonist,[15] and the
nitro compound can serve as a thioredoxin reductase (TR)
via
OTf
SeAr
CH2Cl2
Tf2O then Et3N
H3C
Ar
B
R2
R2
C
metal free reaction
high yields
broad scope (42 examples)
and glutathione reductase (GR) inhibitor (Scheme 1a).[16]
With these unique features, the incorporation of selenium
groups into arenes[17] and alkenes[18] has gained much
attention in recent years. Besides, several selenium-involved
alkyne reactions, especially the alkyne cyclization reactions,
have also been realized.[9a-d, 19] Baidya’s group designed an
ortho-cyclization of N-aryl alkynamides with diaryl
diselenides to provide 3-selenyl quinolin-2-ones (Scheme
1b).[4c] Larock’s group achieved electrophilic cyclization of N-
Scheme 1. Biologically active organoselenium compounds and selenium
involved cyclization of alkynes.
Results and Discussion
For optimization of the reaction conditions, the 1,4-diphenyl-1-
butyne 1a and the phenyl methyl selenoxide 2a were selected as
the standard substrates (Table 1). Initially, the experiments were
(2-alkynyl)aniline[8c]
and
(3-phenoxyprop-1-yn-1-
1
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10.1002/ejoc.202100423
European Journal of Organic Chemistry
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O
Tf2O, then Et3N
CH2Cl2, -78 °C to rt
started under previous optimization conditions of the sulfoxide-
attended cyclization reaction,[21] which conducted at -78 °C in
methylene chloride with Tf2O as activator and Et3N as basic
nucleophile to leave the methyl group. Gratifyingly, 2a was
effectively activated leading to the desired product 2-
phenylselenyl-1-phenyl-3,4-dihydronaphthalene (3aa) in 92%
isolated yield (entry 2). Subsequently, different time of
electrophilic cyclization was examined to further improve existing
yield and it was found that neither increasing nor decreasing the
reaction time could not have a good effect on yield (entries 1 and
3, respectively). Next, we tried to reduce the loading of base, but
slightly lower yield of 85% was afforded (entry 4), which in the
same time 90% and 87% was yielded when we increase to 5 and
6 equiv., respectively (entries 5 and 6, respectively). Ultimately,
changing solvent to 1,2-dichloromethane was not led to improve
the conversion of 1a into the target product (entry 7) and the
condition of entry 2 was proved to be optimal.
+
Se
H3C
Ar
SeAr
Ph
3a-3j
Ph
1a
2a-2j
R
Se
CH3
Se
Se
3g
3h
87%
87%
3a, R = H, 92%
3b, R = CH3, 91%
, R = Cl, 97%
, R = Br, 87%
, R = CF3, 78%
3c
3d
3e
Se
S
Se
CH3
3f, R = OMe, 74%
3i
3j
47%
91%
Scheme 2. Substrate scope of aryl methyl selenium reagents. Reaction
conditions: A solution of 1a (0.4 mmol) and 2 (0.48 mmol) in 2 mL of solvent
was treated with Tf2O (0.48 mmol) at -78 °C for 0.5 h and stirred at room
temperature for another 0.5 h. Then 1.6 mmol Et3N was added and stirred for 2
h. Yields are of the isolated product after column chromatography.
Table 1. Optimization of reaction conditions[a]
O
Tf2O, then Et3N
-78 °C to rt
+
Se
H3C
Ph
SePh
Next, we continued to test the generality of alkynes by reacting
them with the phenyl methyl selenoxide 2a (Scheme 3). We first
examined the aromatic rings of R2 containing electron-donating or
electron-withdrawing groups. To our delight, all these reactions
proceeded smoothly, furnishing the corresponding cyclization
products 4-16 in good to excellent yields. Notably, halogen (5-7),
methoxy (8), and ester (9) at the para position were well tolerated
in this reaction in 86−96% yields and some strong electron-
withdrawing group like trifluoromethyl (10) and nitro (29) could
also work, although with moderate yields. In addition, the
substrates bearing meta and ortho functional groups could also
provide the expected products 11-16 with good results. We also
verified naphthyl and heteroaryl alkynes posed no problem to this
reaction, and the coupling products 17-19 were obtained in good
efficiency.
Apart from these substrates above, various 4-aryl-1-phenyl-1-
butynes were examined in the reaction (Scheme 3). Different
substituent at the para and ortho position were well tolerated with
good yields, especially in the cases of halo (21, 22, 27) and cyano
(24). Again, 1-naphthyl has no deleterious effect on the target
reaction, leading to the corresponding product 28 in 84% yield.
Because of the issue of regioselectivity during the cyclization,
both meta-substituted products 25 and 25’ were obtained in 54%
and 23% yields, respectively.
It is remarkable that this method can also be applied for the
synthesis of phenyl(10-phenylphenanthren-9-yl)selane 30 by
using 2-(phenylethynyl)-1,1′-biphenyl, albeit with moderate yield.
Also, this methodology is not limited to the preparation of
dihydronaphthalenes but includes heterocyclic system, such as
oxygen and nitrogen heterocycle. 2H-Chromene derivative 31
and dihydroquinoline derivatives 32 can be prepared in 93% and
91%, respectively. Lactone and lactam substrates can also be
used in this reaction, afforded the corresponding products 33 and
34 in 45% and 38% yields, respectively. In addition, bicyclization
product 35 can also be performed in 73% yield.
Ph
3a
Ph
1a
2a
Et3N
(equiv.)
Entry
Solvent
Time (h)
Yield[b] (%)
1
2
3
4
5
6
7
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
4
4
4
3
5
6
4
1
85
92
84
85
90
87
85
2
12
2
2
2
CH2ClCH2Cl
2
[a] Reaction conditions: A solution of 1a (0.4 mmol) and 2a (0.48 mmol) in 2 mL
of solvent was treated with Tf2O (0.48 mmol) at -78 °C and then warmed up to
room temperature, and Et3N was added. [b] Yields are of the isolated product
after column chromatography.
Encouraged by these outcomes, we started to investigate the
substrate scope of this reaction by using various aryl methyl
selenoxides with alkyne 1a (Scheme 2). As the extension of the
previous method, we synthesized a series of selenoxides with
different substituents. In addition to example of phenyl, the aryl
ring bearing methyl on the para, ortho and meta position can
proceed smoothly to give the corresponding products 3b, 3h and
3i with good results. We also examined electron-withdrawing
groups, including halo and trifluoromethyl, and afforded the
products 3c-3e in good yields. The reaction of sulfoxides 2f
bearing electron-donating group could also work, although with a
moderate yield. Furthermore, 1-naphthyl methyl selenoxide can
also be used in this reaction, furnished the expected products 3g
in 87% yield. In order to expand the types of substrates, heteroaryl
methyl selenoxide 2j was then examined and furnished the
expected products 3j in 47% yield under the standard conditions.
To further demonstrate the synthetic utilities of the products, we
performed a large-scale reaction of 1,4-diphenyl-1-butyne 1a,
giving products 3a in 88% yield (Scheme 4). Compared to the
2
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10.1002/ejoc.202100423
European Journal of Organic Chemistry
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R1
R1
O
Tf2O, then Et3N
+
Se
SePh
CH2Cl2, -78 °C to rt
H3C
Ph
R2
R2
2a
1b-1ag
4-35
4
, R = Me, 96%
SePh
R
SePh
5, R = F, 93%
6, R = Cl, 93%
11
12
, R = Me, 94%
, R = Cl, 91%
SePh
SePh
R
7
8
9
, R = Br, 96%
, R = OMe, 92%
, R = COOC2H5, 86%
13, R = CF3, 74%
17
, 97%
14
, R = Me, 98%
10
, R = CF3, 65%
15, R = Cl, 89%
16
R
, R = SMe, 90%
Cl
20, R = Me, 98%
21
, R = F, 98%
22, R = Cl, 96%
23
SePh
SePh
R
SePh
SePh
SePh
Cl
, R = OMe, 96%
S
24, R = CN, 76%
S
25
, 54%
25'
, 23%
18
, 92%
19
, 90%
R
Ts
N
O
SePh
SePh
SePh
SePh
SePh
SePh
NO2
26, R = Me, 93%
27
28
, 84%
29b
30
, 68%
31
, 93%
32
, 91%
, 43%
, R = Cl, 92%
CH3
O
O
SePh
N
O
SePh
SePh PhSe
33b, 45%
34, 38%
35, 73%
Scheme 3. Substrate scope of alkyne. Reaction conditions: Unless otherwise specified, reactions were performed on a 0.4 mmol scale of the alkynes using 0.48
mmol phenyl methyl selenoxide 2a in 2 mL of CH2Cl2 which was treated with Tf2O (0.48 mmol) at -78 °C for 0.5 h and stirred at room temperature for another 0.5 h.
Then 1.6 mmol Et3N was added and stirred for 2 h. Yields are of the isolated product after column chromatography. bPhenyl methyl selenoxide (0.96 mmol), Tf2O
(0.96 mmol) and Et3N (3.2 mmol) were used.
example of sulfur[21], some further transformations were carried
out. For instance, 3a was easily transformed to aromatization
product 36 under mild conditions[11] and same to the method of
selenium oxidation,[4c] 3a and 36 can be further oxidized to the
Ph
corresponding selenoxide 37 and 38 in high yields. With the
1a, 4.0 mmol
treatment of butyl lithium, phenyl selenyl of 36 can be lithiated and
O
Tf2O
then Et3N
Se
react with electrophiles to transfer to the corresponding product
39 and 40 in moderate yields.[1e, 19e] These results all reflect the
scalability and application prospects of the method. Also, the
Suzuki reaction of bromine substitution product 7 can be
implemented,[8g] proving that the substrate can be further modified.
H3C
Ph
a)
Ph
Ph
PPh2
Se
O
SePh
Ph
Ph
Ph
37, 89%
3a, 88%
39, 56%
c)
d)
PhB(OH)2
K3PO4
Pd(PPh3)2Cl2
b)
SePh
SePh
a)
toluene
100 °C
Ph
Se
O
SePh
Ph
Ph OH
40, 73%
Ph
36, 95%
Br
Ph
38, 85%
7
41, 64%
On the basis of the experimental results, we proposed the
mechanism of the reaction outlined in Scheme 5. First, triflic
anhydride-activated selenoxide reacted with the carbon-carbon
Scheme 4. Gram scale synthesis and further transformations. Reaction
conditions: a) m-CPBA (1.05 eq), CH2Cl2, r.t., 2 h; b) DDQ, CH2Cl2, r.t., 12 h; c)
n-BuLi (1.0 eq), THF, -78 °C, 1 h, then PPh2Cl, THF, r.t., 3 h; d) n-BuLi (1.0 eq),
THF, -78 °C, 30 min; then PhCHO, THF, r.t., 1 h. Isolated yield.
3
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10.1002/ejoc.202100423
European Journal of Organic Chemistry
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measurements were carried out on an Agilent LC/MSD TOF mass
spectrometer. Melting points were obtained on a Yanaco MP-500 melting
point apparatus and were uncorrected. Alkynes 1a−1ab and 1ag were
triple bond to generate vinyl cation intermediates I regioselectively
due to the stabilization of phenyl group. Then vinyl cation I can be
captured by the tethered aryl ring and then aromatized to
selenium salts III. Finally, the desired products were afforded after
demethylation with Et3N as nucleophile by SN2 process.
synthesized by Sonogashira coupling and the characterization of 1a[10]
1b[10], 1c[22], 1d[10], 1e[22], 1f[10], 1g[10], 1h[22], 1k[10], 1l[10], 1m[10], 1o[10], 1r[10]
,
,
1s[21], 1t[22], 1u[10], 1v[21], 1w[10], 1y[21], 1z[23] and 1ab[8b] can be found in
published procedures. 1ac,[24] 1ad,[24] 1ae[4b, 25] and 1af[25] were prepared
according to published procedures. All selenoxide were synthesized from
diselenide derivatives[17c, 26] and diselenide derivatives were prepared by
O
Se
H3C
H3C
Ph
the known procedure[17b, 27]
.
R
Tf2O
R
Et3NCH
3 OTf
SePh
OTf
Se
Procedure for the Preparation of the Aryl Alkynes: Take the synthesis
of 1a as an example. To a solution of trimethyl(prop-1-yn-1-yl)silane (2.69
g, 24 mmol) in anhydrous THF (50 mL) in a 100 mL round-bottom flask
was added n-BuLi (2.4 M in Hexane, 22 mmol, 9.2 mL) at -78 °C under a
nitrogen atmosphere. Then the reaction was stirred for 2 hours at the same
temperature followed by adding benzyl chloride (2.53 g, 20 mmol) in the
10 mL THF and moving to room temperature. After a further hour, the
solution was quenched with 30 mL sat. NaCl (aq) and the aqueous layer
was extracted with ethyl acetate. The extracts were combined with the
above organic layer and the merged solution was dried over Na2SO4. After
evaporation of the solvent, the crude residue was directly dissolved in THF
(30 mL) and TBAF (6.7 g, 24 mmol) was then added the solution, which
was stirred overnight. The reaction was neutralized with 12 mL HCl (2 N)
and was extracted with ethyl acetate and the combined organic solution
was dried over Na2SO4. After evaporation of the solvent, the residue was
purified by column chromatography on silica gel (petroleum ether/CH2Cl2,
50/1 (v/v)) to afford 1a’ (70 %). After the preparation of 1a’, to a new flame-
dried flask were added Pd(PPh3)2 (167 mg, 0.15 mmol) and CuI (58 mg,
0.30 mmol), then THF (10 mL) was injected under a nitrogen atmosphere,
which the suspension was stirred for five minutes. After adding
iodobenzene (612 mg, 3.0 mmol) and Et3N (3.75 mL, 27 mmol) and stirring
another five minutes, 4-phenyl-1-butyne (430 mg, 3.3 mmol) was added
and the system was stirred and refluxed for 12 h. After the reaction
completed, the solution was cooled to room temperature, filtered and
eluted with ethyl acetate. The organic phase was collected and
concentrated under reduced pressure. The crude material was purified via
column chromatography on silica gel (petroleum ether/CH2Cl2, 30/1 (v/v))
to yield 1a (87 %).
Ph
1a
3a
Ph
OTf
Step 4
Et3N
SN2 process
Step 1
Electrophilic
addition
OTf
R
CH3
Se
OTf
Ph Ph
R
CH3
Se
Ph
III
Ph
- HOTf
I
OTf
Step 3
Aromatization
OTf
CH3
Step 2
R
Electrophilic
cyclization
Se
H
Ph Ph
OTf
II
Scheme 5. Proposed mechanism.
Conclusion
In summary, we have developed
a
selenium-mediated
electrophilic cyclization of internal alkynes in one pot, which
complements current strategies for synthesizing binary rings. The
metal free condition and functional-group tolerance allowed us to
afford 2-phenylselenyl-3,4-dihydronaphthalene and other
derivatives easily, including selenium-substituted phenanthrene,
dihydroquinoline, 2H-chromene, and coumarin. The obtained
products could be further converted into various valuable aryl-aryl
compounds in simple steps. Further exploration of the current
method for the asymmetric version is underway in our lab.
1-Methyl-3-(4-phenylbut-1-yn-1-yl)benzene (1i): Yellow oil (yield 88%):
Rf = 0.43 (petroleum ether/CH2Cl2, 10/1 (v/v)); 1H NMR (400 MHz, CDCl3)
δ 7.34 − 7.12 (m, 8H), 7.07 (d, J = 6.6 Hz, 1H), 2.92 (t, J = 7.5 Hz, 2H),
2.68 (t, J = 7.6 Hz, 2H), 2.30 (s, 3H); 13C{1H} NMR (101 MHz, CDCl3) δ
140.7, 137.9, 132.1, 128.6, 128.5, 128.5, 128.4, 128.1, 126.3, 123.6, 89.1,
81.4, 35.2, 21.7, 21.2; HRMS (ESI) calcd for C17H17 [M + H]+ m/z
+
221.1325, found 221.1323.
Experimental Section
1-Chloro-3-(4-phenylbut-1-yn-1-yl)benzene (1j): Colorless oil (yield
84%): Rf = 0.50 (petroleum ether/ethyl acetate, 20/1 (v/v)); 1H NMR (400
MHz, CDCl3) δ 7.34 (s, 1H), 7.33 − 7.27 (m, 2H), 7.27 − 7.18 (m, 5H), 7.18
− 7.12 (m, 1H), 2.89 (t, J = 7.5 Hz, 2H), 2.67 (t, J = 7.5 Hz, 2H); 13C{1H}
NMR (101 MHz, CDCl3) δ 140.4, 133.9, 131.4, 129.6, 129.3, 128.5, 128.4,
127.9, 126.3, 125.5, 90.9, 80.1, 35.0, 21.6; HRMS (ESI) calcd for
C16H14Cl+ [M + H]+ m/z 241.0779, found 241.0782.
General Information: Unless otherwise noted, all materials were
purchased from commercial suppliers. Dichloromethane (DCM) and 1,2-
dichloroethane (DCE) were refluxed over CaH2. Tetrahydrofuran (THF)
was refluxed with sodium/benzophenone. All solvents mentioned above
were freshly distilled prior to use. Flash column chromatography was
performed using silica gel (normal phase, 200 - 300 mesh) from Anhui
Liangchen Silicon Material Co., Ltd., with petroleum ether (PE, bp 60 -
90 °C), dichloromethane (DCM), hexane, and ethyl acetate (EA) as eluents.
Reactions were monitored by thin-layer chromatography (TLC) on G254
silica gel plates (0.2 mm) from Anhui Liangchen Silicon Material Co., Ltd.
The plates were visualized under UV light, as well as other TLC stains
(phosphomolybdic acid: 10% in ethanol; potassium permanganate: 1% in
Methyl(2-(4-phenylbut-1-yn-1-yl)phenyl)sulfane (1n): Colorless oil
(yield 41%): Rf = 0.23 (petroleum ether/CH2Cl2, 10/1 (v/v)); 1H NMR (400
MHz, CDCl3) δ 7.34 − 7.30 (m, 1H), 7.30 − 7.26 (m, 4H), 7.26 − 7.17 (m,
2H), 7.10 (d, J = 7.9 Hz, 1H), 7.03 (td, J = 7.5, 1.1 Hz, 1H), 2.96 (t, J = 7.5
Hz, 2H), 2.77 (t, J = 7.6 Hz, 2H), 2.44 (s, 3H); 13C{1H} NMR (101 MHz,
CDCl3) δ 141.1, 140.6, 132.3, 128.5, 128.4, 128.3, 128.1, 126.2, 124.1,
123.8, 121.8, 96.3, 78.7, 35.1, 21.9, 15.0; HRMS (ESI) calcd for C17H17S+
[M + H]+ m/z 253.1045, found 253.1040.
water; iodine: 10 g iodine absorbed on 30 g silica gel). 1H, 13C, 19F and 31
P
NMR spectra were recorded on a Bruker 400 MHz spectrometer, usually
in CDCl3 with TMS as an internal standard, and the chemical shifts (δ)
were reported in parts per million (ppm). Multiplicities are indicated as s
(singlet), d (doublet), t (triplet), q (quartet), dd (double of doublet), dt
(double of triplet), td (triple of doublet), ddd (double of doublet of doublet)
and m (multiplet). Coupling constants (J) are reported in Hertz (Hz). HRMS
2-(4-Phenylbut-1-yn-1-yl)thiophene (1p): Brown oil (yield 91%): Rf =
0.32 (petroleum ether/CH2Cl2, 10/1 (v/v)); 1H NMR (400 MHz, CDCl3) δ
7.34 − 7.27 (m, 2H), 7.27 − 7.18 (m, 3H), 7.14 (d, J = 5.2 Hz, 1H), 7.12 −
4
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10.1002/ejoc.202100423
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7.07 (m, 1H), 6.94 − 6.87 (m, 1H), 2.90 (t, J = 7.5 Hz, 2H), 2.69 (t, J = 7.5
Hz, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ 140.5, 131.0, 128.5, 128.4,
126.7, 126.3, 126.0, 123.9, 93.5, 74.5, 34.9, 21.9; HRMS (ESI) calcd for
C14H13S+ [M + H]+ m/z 213.0732, found 213.0733.
1-Methyl-4-(methylseleninyl)benzene (2b): White solid (yield 71%): Rf =
0.49 (CH2Cl2/CH3OH, 20/1 (v/v)); mp 98−101 °C; 1H NMR (400 MHz,
CDCl3) δ 7.62 (d, J = 8.1 Hz, 2H), 7.36 (d, J = 7.9 Hz, 2H), 2.63 (s, 3H),
2.43 (s, 3H); 13C{1H} NMR (101 MHz, CDCl3) δ 141.7, 138.5, 130.4, 125.4,
37.3, 21.3; HRMS (ESI) calcd for C8H11OSe+ [M + H]+ m/z 202.9970, found
202.9981.
3-(4-Phenylbut-1-yn-1-yl)thiophene (1q): Dark-yellow oil (yield 89%): Rf
= 0.30 (petroleum ether/CH2Cl2, 10/1 (v/v)); 1H NMR (400 MHz, CDCl3) δ
7.33 − 7.21 (m, 5H), 7.21 − 7.17 (m, 1H), 7.03 (dd, J = 5.0, 1.0 Hz, 1H),
2.89 (t, J = 7.6 Hz, 2H), 2.65 (t, J = 7.6 Hz, 2H); 13C{1H} NMR (101 MHz,
CDCl3) δ 140.6, 129.9, 128.5, 128.3, 127.6, 126.3, 125.0, 122.7, 89.0, 76.3,
35.1, 21.6; HRMS (ESI) calcd for C14H13S+ [M + H]+ m/z 213.0732, found
213.0741.
1-Chloro-4-(methylseleninyl)benzene (2c): White solid (yield 81%): Rf =
0.53 (CH2Cl2/CH3OH, 20/1 (v/v)); mp 113−115 °C; 1H NMR (400 MHz,
CDCl3) δ 7.69 (d, J = 8.0 Hz, 2H), 7.54 (d, J = 8.0 Hz, 2H), 2.63 (s, 3H);
13C{1H} NMR (101 MHz, CDCl3) δ 140.1, 137.7, 130.0, 126.9, 37.6; HRMS
(ESI) calcd for C7H8ClOSe+ [M + H]+ m/z 222.9423, found 222.9427.
1-Methyl-2-(4-phenylbut-3-yn-1-yl)benzene (1x): Light-yellow oil (yield
84%): Rf = 0.25 (petroleum ether/CH2Cl2, 10/1 (v/v))); 1H NMR (400 MHz,
CDCl3) δ 7.36 (dd, J = 6.6, 3.0 Hz, 2H), 7.27 − 7.17 (m, 4H), 7.13 (d, J =
4.7 Hz, 3H), 2.91 (t, J = 7.7 Hz, 2H), 2.63 (t, J = 7.7 Hz, 2H), 2.33 (s, 3H);
13C{1H} NMR (101 MHz, CDCl3) δ 138.7, 135.9, 131.5, 130.2, 128.9, 128.1,
127.5, 126.4, 126.0, 123.8, 89.6, 81.1, 32.4, 20.3, 19.2; HRMS (ESI) calcd
for C17H17+ [M + H]+ m/z 221.1325, found 221.1323.
1-Bromo-4-(methylseleninyl)benzene (2d): White solid (yield 75%): Rf =
0.52 (CH2Cl2/CH3OH, 20/1 (v/v)); mp 43−45 °C; 1H NMR (400 MHz, CDCl3)
δ 7.72 − 7.66 (m, 2H), 7.66 − 7.60 (m, 2H), 2.64 (s, 3H); 13C{1H} NMR (101
MHz, CDCl3) δ 140.6, 132.8, 127.0, 125.9, 37.4; HRMS (ESI) calcd for
C7H8BrOSe+ [M + H]+ m/z 266.8918, found 266.8922.
1-(Methylseleninyl)-4-(trifluoromethyl)benzene (2e): White solid (yield
43%): Rf = 0.43 (CH2Cl2/CH3OH, 20/1 (v/v)); mp 77−78 °C; 1H NMR (400
MHz, CDCl3) δ 7.90 (d, J = 8.0 Hz, 2H), 7.82 (d, J = 8.1 Hz, 2H), 2.67 (s,
3H); 13C{1H} NMR (101 MHz, CDCl3) δ 146.2, 133.4 (q, J = 33.3 Hz), 126.5
(d, J = 3.0 Hz), 126.0, 123.4 (d, J = 273.7 Hz), 37.6; 19F NMR (377 MHz,
CDCl3)δ -62.91; HRMS (ESI) calcd for C8H8F3OSe+ [M + H]+ m/z 256.9687,
found 256.9679.
1-Methyl-4-(4-(4-nitrophenyl)but-3-yn-1-yl)benzene (1aa): White solid
(yield 64%): Rf = 0.37 (petroleum ether/ethyl acetate, 20/1 (v/v)); mp
80−81 °C; 1H NMR (400 MHz, CDCl3) δ 8.13 (d, J = 8.8 Hz, 2H), 7.47 (d,
J = 8.7 Hz, 2H), 7.19 − 7.08 (m, 4H), 2.89 (t, J = 7.4 Hz, 2H), 2.71 (t, J =
7.4 Hz, 2H), 2.33 (s, 3H); 13C{1H} NMR (101 MHz, CDCl3) δ 146.6, 137.1,
136.0, 132.2, 130.9, 129.1, 128.3, 123.4, 95.8, 79.9, 34.3, 21.9, 21.0;
HRMS (ESI) calcd for C17H16NO2+ [M + H]+ m/z 266.1176, found 266.1170.
1-(4-Methoxyphenyl)ethan-1-one (2f): White solid (yield 65%): Rf = 0.41
1
(CH2Cl2/CH3OH, 20/1 (v/v)); mp 98−99 °C; H NMR (400 MHz, CDCl3) δ
1,4-Bis(4-phenylbut-1-yn-1-yl)benzene (1ag): To a flame-dried flask
were added Pd(PPh3)2 (58 mg, 0.05 mmol) and CuI (10 mg, 0.05
mmol) ,then THF (5 mL) was injected under a nitrogen atmosphere, which
the suspension was stirred for five minutes. After adding iodobenzene (330
mg, 1.0 mmol) and Et3N (1.3 mL, 9 mmol) and stirring another five minutes,
the alkyne 1a’ (325 mg, 2.5 mmol) was added and the system was stirred
and refluxed for 12 h. After the reaction completed, the solution was cooled
to room temperature, filtered and eluted with ethyl acetate. The organic
phase was collected and concentrated under reduced pressure. The crude
material was purified via column chromatography on silica gel (petroleum
ether/CH2Cl2, 10/1 (v/v)) to yield 1af as a white solid (254 mg, 76%): Rf =
0.34 (CH2Cl2/CH3OH, 20/1 (v/v)); mp 92−94 °C; 1H NMR (400 MHz, CDCl3)
δ 7.34−7.28 (m, 4H), 7.27 (d, J = 2.2 Hz, 6H), 7.26 − 7.20 (m, 4H), 2.91 (t,
J = 7.5 Hz, 4H), 2.69 (t, J = 7.6 Hz, 4H); 13C{1H} NMR (101 MHz, CDCl3) δ
140.6, 131.3, 128.5, 128.4, 126.3, 123.1, 91.0, 81.1, 35.1, 21.7; HRMS
(ESI) calcd for C26H23+ [M + H]+ m/z 335.1794, found 335.1791.
7.67 (d, J = 8.8 Hz, 2H), 7.05 (d, J = 8.8 Hz, 2H), 3.85 (s, 3H), 2.62 (s, 3H);
13C{1H} NMR (101 MHz, CDCl3) δ 161.7, 131.9, 126.9, 126.8, 114.9, 55.2,
37.0; HRMS (ESI) calcd for C8H11O2Se+ [M + H]+ m/z 218.9919, found
218.9927.
1-(Methylseleninyl)naphthalene (2g): Wine red solid (yield 56%): Rf =
0.46 (CH2Cl2/CH3OH, 20/1 (v/v)); mp 94−96 °C; 1H NMR (400 MHz, CDCl3)
δ 8.29 (dd, J = 7.2, 1.2 Hz, 1H), 8.03 − 7.95 (m, 2H), 7.87 − 7.80 (m, 1H),
7.70 (dd, J = 8.2, 7.2 Hz, 1H), 7.65 − 7.56 (m, 2H), 2.71 (s, 3H); 13C{1H}
NMR (101 MHz, CDCl3) δ 138.6, 133.8, 131.3, 130.1, 129.2, 127.5, 126.7,
126.0, 123.9, 122.0, 36.5; HRMS (ESI) calcd for C11H11OSe+ [M + H]+ m/z
238.9970, found 238.9978.
1-Methyl-3-(methylseleninyl)benzene (2h): White solid (yield 73%): Rf =
0.48 (CH2Cl2/CH3OH, 20/1 (v/v)); mp 100−102 °C; 1H NMR (400 MHz,
CDCl3) δ 7.59 (s, 1H), 7.49 (d, J = 7.7 Hz, 1H), 7.42 (t, J = 7.6 Hz, 1H),
7.32 (d, J = 7.5 Hz, 1H), 2.62 (s, 3H), 2.44 (s, 3H); 13C{1H} NMR (101 MHz,
CDCl3) δ 141.6, 140.0, 132.0, 129.3, 125.5, 122.4, 37.2, 21.3; HRMS (ESI)
calcd for C8H11OSe+ [M + H]+ m/z 202.9970, found 202.9982.
General Procedure for the Preparation of the Selenoxide Substrates:
Take the synthesis of 2a as an example. To a new flame-dried three neck
flask was added diphenyl diselenide (3.88 g, 12.4 mmol) and then they
were dissolved with ethanol (30 mL) under a nitrogen atmosphere. Sodium
borohydride (26.4 mmol) dissolved in 20 mL ethanol was added dropwise
and the reaction mixture stirred for 0.5 h at 25 °C, followed by addition of
2.0 mL (0.321 mol) iodomethane. After stirring overnight, the mixture was
treated with 50 mL water and extracted with CH2Cl2. The combined organic
phase was dried over Na2SO4 and concentrated under reduced pressure.
The residue was further purified by flash column chromatography on silica
gel (petroleum ether) and afforded methylphenyl selenide. Then
methylphenyl selenide (168 mg, 1.0 mmol) was dissolved in 10 mL CH2Cl2.
The reaction mixture was cooled to 0 °C, and m-CPBA (190 mg, 1.1 mmol)
was added in one portion. The mixture was stirred at 0 °C for 30 minutes
and at room temperature for additional 30 minutes. The organic phase was
washed with a saturated aqueous solution of potassium carbonate (10 mL)
and the aqueous phase was extracted with CH2Cl2. The organics were
combined and concentrated under reduced pressure. The residue was
purified by column chromatography (EtOAc then CH2Cl2/CH3OH, 20:1
(v/v)) to provide 2a (159 mg, 85%). The characterization of 2a can be
1-Methyl-2-(methylseleninyl)benzene (2i): White solid (yield 69%): Rf =
0.49 (CH2Cl2/CH3OH, 20/1 (v/v)); mp 79−82 °C; 1H NMR (400 MHz, CDCl3)
δ 8.03 (dd, J = 7.7, 1.3 Hz, 1H), 7.47 (t, J = 7.1 Hz, 1H), 7.41 (td, J = 7.4,
1.4 Hz, 1H), 7.24 (d, J = 7.4 Hz, 1H), 2.59 (s, 3H), 2.44 (s, 3H); 13C{1H}
NMR (101 MHz, CDCl3) δ 140.7, 135.3, 131.0, 130.5, 127.6, 124.5, 35.7,
19.2; HRMS (ESI) calcd for C8H11OSe+ [M + H]+ m/z 202.9970, found
202.9981.
2-(Methylseleninyl)thiophene (2j): Light-yellow oil (yield 52%): Rf = 0.57
(CH2Cl2/CH3OH, 20/1 (v/v)); 1H NMR (400 MHz, CDCl3) δ 7.68 (dd, J = 5.0,
1.2 Hz, 1H), 7.52 (dd, J = 3.7, 1.2 Hz, 1H), 7.18 (dd, J = 5.0, 3.6 Hz, 1H),
2.85 (s, 3H); 13C{1H} NMR (101 MHz, CDCl3) δ 140.8, 131.1, 130.2, 127.6,
38.1. HRMS (ESI) calcd for C5H7OSSe+ [M + H]+ m/z 194.9377, found
194.9387.
General Procedure for Electrophilic Cyclization of Alkynes: To a
flame-dried Schlenk tube were added alkyne 1 (0.4 mmol) and sulfoxide 2
(0.48 mmol), and then they were dissolved with dichloromethane (2 mL)
found in our previous work[17c]
.
5
This article is protected by copyright. All rights reserved.

10.1002/ejoc.202100423
European Journal of Organic Chemistry
FULL PAPER
under a nitrogen atmosphere before being cooled to −78 °C (liquid N2/ethyl
acetate bath). Tf2O (81 μL, 0.48 mmol) was added dropwise. After being
stirred for 0.5 h, the mixture was warmed to room temperature and stirred
for an additional 0.5 h, and then Et3N (162 mg, 1.6 mmol) was added. After
being stirred for 2 h, the solution was diluted with CH2Cl2, transferred to a
round-bottom flask, and concentrated under reduced pressure. The
residue was further purified by flash column chromatography on silica gel
and afforded pure product.
125.8 (q, J = 4.0 Hz), 124.1 (d, J = 272.7 Hz), 31.4, 29.8; 19F NMR (377
MHz, CDCl3) δ -62.58; HRMS (ESI) calcd for C23H18F3Se+ [M + H]+ m/z
431.0520, found 431.0521.
(4-Methoxyphenyl)(1-phenyl-3,4-dihydronaphthalen-2-yl)selane (3f):
Synthesized from 1a (0.4 mmol) and 2f (0.48 mmol). Purification by flash
column chromatography [petroleum ether/CH2Cl2, 10/1 (v/v)], to give the
product as a light-yellow solid (116 mg, 74%): Rf = 0.56 (petroleum
ether/ethyl acetate, 20/1 (v/v)); mp 92−93 °C; 1H NMR (400 MHz, CDCl3)
δ 7.51 − 7.42 (m, 4H), 7.38 (tdd, J = 7.4, 3.4, 1.6 Hz, 1H), 7.28 (ddd, J =
8.0, 3.7, 1.5 Hz, 2H), 7.12 − 7.05 (m, 2H), 7.03 (dtd, J = 7.7, 6.0, 5.1, 2.6
Hz, 1H), 6.86 − 6.77 (m, 2H), 6.63 (dd, J = 7.6, 3.9 Hz, 1H), 3.82 − 3.74
(m, 3H), 2.85 − 2.74 (m, 2H), 2.42 (ddd, J = 9.2, 7.7, 3.9 Hz, 2H); 13C{1H}
NMR (101 MHz, CDCl3) δ 159.7, 140.0, 137.2, 137.0, 136.2, 134.6, 133.3,
129.9, 128.5, 127.5, 127.1, 126.4, 126.3, 125.3, 119.7, 114.7, 55.2, 29.8,
29.5; HRMS (ESI) calcd for C23H21OSe+ [M + H]+ m/z 393.0752, found
393.0754.
Phenyl(1-phenyl-3,4-dihydronaphthalen-2-yl)selane (3a): Synthesized
from 1a (0.4 mmol) and 2a (0.48 mmol). Purification by flash column
chromatography [petroleum ether/CH2Cl2, 25/1 (v/v)], to give the product
as a white solid (133 mg, 92%): Rf = 0.43 (petroleum ether/CH2Cl2, 10/1
(v/v)); mp 87−89 °C; 1H NMR (400 MHz, CDCl3) δ 7.56−7.48 (m, 2H),
7.48−7.41 (m, 2H), 7.41−7.35 (m, 1H), 7.32−7.21 (m, 5H), 7.14−7.08 (m,
2H), 7.04 (ddd, J = 8.8, 5.6, 3.4 Hz, 1H), 6.65 (d, J = 7.6 Hz, 1H), 2.91−2.77
(m, 2H), 2.58−2.46 (m, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ 140.1, 139.4,
136.1, 134.9, 134.3, 132.1, 130.3, 130.0, 129.1, 128.4, 127.6, 127.5, 127.2,
126.8, 126.4, 125.8, 30.6, 29.7; HRMS (ESI) calcd for C22H19Se+ [M + H]+
m/z 363.0646, found 363.0641.
Naphthalen-1-yl(1-phenyl-3,4-dihydronaphthalen-2-yl)selane
(3g):
Synthesized from 1a (0.4 mmol) and 2g (0.48 mmol). Purification by flash
column chromatography [petroleum ether/CH2Cl2, 30/1 (v/v)], to give the
product as a white solid (144 mg, 87%): Rf = 0.55 (petroleum ether/CH2Cl2,
10/1 (v/v)); mp 119−121 °C; 1H NMR (400 MHz, CDCl3) δ 8.31 (dd, J = 6.8,
2.2 Hz, 1H), 7.95 − 7.83 (m, 3H), 7.55 (ddd, J = 7.6, 5.9, 1.7 Hz, 4H), 7.50
− 7.38 (m, 4H), 7.17 − 7.04 (m, 3H), 6.72 (dd, J = 5.6, 2.7 Hz, 1H), 2.68 (t,
J = 7.8 Hz, 2H), 2.36 − 2.28 (m, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ
140.1, 138.1, 136.2, 135.1, 134.9, 134.8, 134.0, 133.0, 129.8, 129.4, 128.9,
128.6, 128.5, 128.1, 127.7, 127.1, 126.8, 126.6, 126.4, 126.3, 125.7, 125.4,
29.9, 29.4; HRMS (ESI) calcd for C26H21Se+ [M + H]+ m/z 413.0803, found
413.0796.
(1-Phenyl-3,4-dihydronaphthalen-2-yl)(p-tolyl)selane
(3b):
Synthesized from 1a (0.4 mmol) and 2b (0.48 mmol). Purification by flash
column chromatography [petroleum ether/CH2Cl2, 50/1 (v/v)], to give the
product as a light-yellow solid (137 mg, 91%): Rf = 0.33 (petroleum
ether/CH2Cl2, 10/1 (v/v)); mp 97−98 °C; 1H NMR (400 MHz, CDCl3) δ 7.49
− 7.36 (m, 5H), 7.32 − 7.27 (m, 2H), 7.14 − 7.08 (m, 4H), 7.08 − 7.01 (m,
1H), 6.65 (d, J = 7.2 Hz, 1H), 2.83 (t, J = 7.9 Hz, 2H), 2.53 − 2.45 (m, 2H),
2.35 (s, 3H); 13C{1H} NMR (101 MHz, CDCl3) δ 140.1, 138.4, 137.8, 136.2,
134.9, 134.8, 132.7, 130.0, 129.9, 128.4, 127.5, 127.1, 126.6, 126.4, 126.2,
125.6, 30.2, 29.6, 21.2; HRMS (ESI) calcd for C23H21Se+ [M + H]+ m/z
377.0803, found 377.0785.
(1-Phenyl-3,4-dihydronaphthalen-2-yl)(m-tolyl)selane
(3h):
Synthesized from 1a (0.4 mmol) and 2h (0.48 mmol). Purification by flash
column chromatography [petroleum ether/CH2Cl2, 30/1 (v/v)], to give the
product as a yellow solid (132 mg, 87%): Rf = 0.45 (petroleum ether/CH2Cl2,
10/1 (v/v)); mp 76−78 °C; 1H NMR (400 MHz, CDCl3) δ 7.47 − 7.41 (m,
2H), 7.41 − 7.36 (m, 1H), 7.33 (q, J = 7.6, 7.0 Hz, 2H), 7.30 − 7.24 (m, 2H),
7.15 (t, J = 7.6 Hz, 1H), 7.13 − 7.07 (m, 3H), 7.04 (tt, J = 5.2, 2.8 Hz, 1H),
6.65 (d, J = 7.5 Hz, 1H), 2.84 (t, J = 7.8 Hz, 2H), 2.52 (td, J = 8.3, 7.6, 2.2
Hz, 2H), 2.32 (s, 3H); 13C{1H} NMR (101 MHz, CDCl3) δ 140.1, 139.1,
138.8, 136.1, 135.0, 134.9, 132.2, 131.4, 129.9, 128.8, 128.4, 128.4, 127.5,
127.1, 126.7, 126.4, 125.7, 30.6, 29.7, 21.3; HRMS (ESI) calcd for
C23H21Se+ [M + H]+ m/z 377.0803, found 377.0806.
(4-Chlorophenyl)(1-phenyl-3,4-dihydronaphthalen-2-yl)selane (3c):
Synthesized from 1a (0.4 mmol) and 2c (0.48 mmol). Purification by flash
column chromatography [petroleum ether/CH2Cl2, 40/1 (v/v)], to give the
product as a yellow solid (154 mg, 97%): Rf = 0.41 (petroleum ether/CH2Cl2,
10/1 (v/v)); mp 74−75 °C; 1H NMR (400 MHz, CDCl3) δ 7.44 (d, J = 8.2 Hz,
4H), 7.42 − 7.37 (m, 1H), 7.27 (s, 1H), 7.24 (s, 3H), 7.14 (d, J = 4.1 Hz,
2H), 7.06 (dt, J = 8.4, 4.3 Hz, 1H), 6.66 (d, J = 7.7 Hz, 1H), 2.86 (t, J = 7.8
Hz, 2H), 2.60 − 2.45 (m, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ 140.02,
139.95, 135.9, 135.5, 134.8, 133.9, 131.4, 129.9, 129.3, 128.6, 128.5,
127.6, 127.2, 127.0, 126.5, 125.9, 30.7, 29.7; HRMS (ESI) calcd for
C22H18ClSe+ [M + H]+ m/z 397.0257, found 397.0261.
(1-Phenyl-3,4-dihydronaphthalen-2-yl)(o-tolyl)selane (3i): Synthesized
from 1a (0.4 mmol) and 2i (0.48 mmol). Purification by flash column
chromatography [petroleum ether/CH2Cl2, 30/1 (v/v)], to give the product
as a yellow solid (138 mg, 91%): Rf = 0.39 (petroleum ether/CH2Cl2, 10/1
(v/v)); mp 86−88 °C; 1H NMR (400 MHz, CDCl3) δ 7.60 (d, J = 7.5 Hz, 1H),
7.52 − 7.45 (m, 2H), 7.45 − 7.39 (m, 1H), 7.34 − 7.29 (m, 2H), 7.25 − 7.22
(m, 2H), 7.16 − 7.10 (m, 3H), 7.07 (ddd, J = 8.9, 5.4, 3.6 Hz, 1H), 6.68 (d,
J = 7.5 Hz, 1H), 2.89 − 2.83 (m, 2H), 2.49 − 2.43 (m, 2H), 2.41 (s, 3H);
13C{1H} NMR (101 MHz, CDCl3) δ 141.4, 140.2, 139.3, 136.2, 135.4, 134.9,
132.0, 130.8, 130.1, 129.7, 128.4, 128.2, 127.5, 127.1, 126.7, 126.4, 126.4,
125.6, 30.3, 29.6, 22.8; HRMS (ESI) calcd for C23H21Se+ [M + H]+ m/z
377.0803, found 377.0797.
(4-Bromophenyl)(1-phenyl-3,4-dihydronaphthalen-2-yl)selane (3d):
Synthesized from 1a (0.4 mmol) and 2d (0.48 mmol). Purification by flash
column chromatography [petroleum ether/CH2Cl2, 30/1 (v/v)], to give the
product as a yellow solid (153 mg, 87%): Rf = 0.43 (petroleum ether/CH2Cl2,
10/1 (v/v)); mp 95−97 °C; 1H NMR (400 MHz, CDCl3) δ 7.49 − 7.43 (m,
2H), 7.43 − 7.35 (m, 5H), 7.27 (d, J = 1.6 Hz, 1H), 7.25 (d, J = 1.1 Hz, 1H),
7.16 − 7.11 (m, 2H), 7.10 − 7.02 (m, 1H), 6.66 (d, J = 7.6 Hz, 1H), 2.90 −
2.83 (m, 2H), 2.57 − 2.49 (m, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ 140.2,
139.9, 135.9, 135.7, 134.8, 132.2, 131.3, 129.8, 129.3, 128.5, 127.7, 127.2,
127.0, 126.5, 125.9, 122.0, 30.7, 29.7; HRMS (ESI) calcd for C22H18BrSe+
[M + H]+ m/z 440.9752, found 440.9757.
(1-Phenyl-3,4-dihydronaphthalen-2-yl)(4-(trifluoromethyl)-phenyl)-
selane (3e): Synthesized from 1a (0.4 mmol) and 2e (0.48 mmol).
Purification by flash column chromatography [petroleum ether/CH2Cl2,
15/1 (v/v)], to give the product as a light-yellow solid (135 mg, 78%): Rf =
0.56 (petroleum ether/ethyl acetate, 20/1 (v/v)); mp 71−72 °C; 1H NMR
(400 MHz, CDCl3) δ 7.59 (d, J = 8.1 Hz, 2H), 7.51 (d, J = 8.2 Hz, 2H), 7.49
− 7.37 (m, 3H), 7.27 (d, J = 1.7 Hz, 1H), 7.26 − 7.23 (m, 1H), 7.17 (d, J =
4.1 Hz, 2H), 7.08 (dp, J = 7.6, 3.5 Hz, 1H), 6.69 (d, J = 7.6 Hz, 1H), 3.04 −
2.80 (m, 2H), 2.76 − 2.52 (m, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ 142.2,
139.9, 136.3 (d, J = 1.0 Hz), 135.7, 135.0, 132.99, 132.95, 130.0, 129.7,
129.2 (d, J = 32.3 Hz), 128.4, 127.7, 127.3 (d, J = 2.0 Hz), 126.5, 126.3,
2-((1-Phenyl-3,4-dihydronaphthalen-2-yl)selanyl)thiophene
(3j):
Synthesized from 1a (0.4 mmol) and 2j (0.48 mmol). Purification by flash
column chromatography [petroleum ether/CH2Cl2, 30/1 (v/v)], to give the
product as a light-yellow solid (69 mg, 47%): Rf = 0.49 (petroleum
ether/CH2Cl2, 10/1 (v/v)); mp 68−70 °C; 1H NMR (400 MHz, CDCl3) δ 7.54
− 7.47 (m, 2H), 7.47 − 7.40 (m, 2H), 7.36 − 7.31 (m, 2H), 7.25 (dd, J = 3.5,
1.1 Hz, 1H), 7.15 − 7.09 (m, 2H), 7.09 − 7.05 (m, 1H), 7.03 (dd, J = 5.3,
3.5 Hz, 1H), 6.65 (d, J = 7.5 Hz, 1H), 2.89 − 2.81 (m, 2H), 2.51 − 2.43 (m,
2H); 13C{1H} NMR (101 MHz, CDCl3) δ 139.4, 137.6, 136.6, 136.0, 134.5,
133.5, 132.0, 129.9, 128.6, 128.1, 127.7, 127.1, 126.6, 126.4, 125.2, 123.1,
6
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10.1002/ejoc.202100423
European Journal of Organic Chemistry
FULL PAPER
29.4, 28.6; HRMS (ESI) calcd for C20H17SSe+ [M + H]+ m/z 369.0211,
found 369.0216.
as a light-yellow solid (150 mg, 86%): Rf = 0.36 (petroleum ether/CH2Cl2,
10/1 (v/v)); mp 91−92 °C; 1H NMR (400 MHz, CDCl3) δ 8.14 (d, J = 8.3 Hz,
2H), 7.51 (dd, J = 7.3, 2.1 Hz, 2H), 7.36 (d, J = 8.3 Hz, 2H), 7.31 − 7.27
(m, 3H), 7.13 (d, J = 4.2 Hz, 2H), 7.08 − 6.97 (m, 1H), 6.58 (d, J = 7.6 Hz,
1H), 4.41 (q, J = 7.1 Hz, 2H), 2.94 − 2.78 (m, 2H), 2.65 − 2.46 (m, 2H),
1.42 (t, J = 7.1 Hz, 3H); 13C{1H} NMR (101 MHz, CDCl3) δ 166.5, 144.9,
138.7, 135.6, 134.8, 134.4, 132.5, 130.1, 129.9, 129.8, 129.7, 129.2, 127.8,
127.3, 127.0, 126.5, 125.6, 61.0, 30.7, 29.6, 14.4; HRMS (ESI) calcd for
C25H23O2Se+ [M + H]+ m/z 435.0858, found 435.0861.
Phenyl(1-(p-tolyl)-3,4-dihydronaphthalen-2-yl)selane (4): Synthesized
from 1b (0.4 mmol) and 2a (0.48 mmol). Purification by flash column
chromatography [petroleum ether/CH2Cl2, 25/1 (v/v)], to give the product
as a white solid (144 mg, 96%): Rf = 0.36 (petroleum ether/CH2Cl2, 10/1
(v/v)); mp 67−68 °C; 1H NMR (400 MHz, CDCl3) δ 7.56 − 7.47 (m, 2H),
7.33 − 7.20 (m, 5H), 7.16 (d, J = 7.9 Hz, 2H), 7.10 (d, J = 4.3 Hz, 2H), 7.07
− 7.00 (m, 1H), 6.68 (d, J = 7.6 Hz, 1H), 2.88 − 2.78 (m, 2H), 2.56 − 2.47
(m, 2H), 2.41 (s, 3H); 13C{1H} NMR (101 MHz, CDCl3) δ 139.3, 137.2,
137.1, 136.2, 134.9, 134.3, 131.9, 130.4, 129.8, 129.2, 129.0, 127.5, 127.1,
126.7, 126.4, 125.8, 30.6, 29.7, 21.4; HRMS (ESI) calcd for C23H21Se+ [M
+ H]+ m/z 377.0803, found 377.0785.
Phenyl(1-(4-(trifluoromethyl)phenyl)-3,4-dihydronaphthalen-2-yl)-
selane (10): Synthesized from 1h (0.4 mmol) and 2a (0.48 mmol).
Purification by flash column chromatography [petroleum ether/CH2Cl2,
30/1 (v/v)], to give the product as a white solid (112 mg, 65%): Rf = 0.24
(petroleum ether/CH2Cl2, 10/1 (v/v)); mp 86−88 °C; 1H NMR (400 MHz,
CDCl3) δ 7.70 (d, J = 8.0 Hz, 2H), 7.54 − 7.47 (m, 2H), 7.40 (d, J = 7.9 Hz,
2H), 7.33 − 7.25 (m, 3H), 7.13 (d, J = 4.1 Hz, 2H), 7.05 (dp, J = 7.5, 3.4
Hz, 1H), 6.56 (d, J = 7.6 Hz, 1H), 2.89 − 2.80 (m, 2H), 2.58 − 2.49 (m, 2H);
13C{1H} NMR (101 MHz, CDCl3) δ 143.8, 138.3, 135.5, 134.8, 134.4, 132.9,
130.4, 129.73, 129.65 (d, J = 32.3 Hz), 129.2, 127.8, 127.4, 127.1, 126.5,
125.5, 125.4 (q, J = 4.0 Hz), 124.2 (d, J = 272.7 Hz), 30.7, 29.5; 19F NMR
(377 MHz, CDCl3) δ -62.41; HRMS (ESI) calcd for C23H18F3Se+ [M + H]+
m/z 431.0520, found 431.0517.
(1-(4-Fluorophenyl)-3,4-dihydronaphthalen-2-yl)(phenyl)selane (5):
Synthesized from 1c (0.4 mmol) and 2a (0.48 mmol). Purification by flash
column chromatography [petroleum ether/CH2Cl2, 20/1 (v/v)], to give the
product as
a colorless oil (142 mg, 93%): Rf = 0.44 (petroleum
ether/CH2Cl2, 10/1 (v/v)); 1H NMR (400 MHz, CDCl3) δ 7.51 (dd, J = 7.3,
2.1 Hz, 2H), 7.33 − 7.18 (m, 5H), 7.19 − 7.09 (m, 4H), 7.05 (dt, J = 8.8, 4.4
Hz, 1H), 6.62 (d, J = 7.6 Hz, 1H), 2.89 − 2.78 (m, 2H), 2.56 − 2.45 (m, 2H);
13C{1H} NMR (101 MHz, CDCl3) δ 162.2 (d, J = 247.5 Hz), 138.2, 136.0,
135.9 (d, J = 3.0 Hz), 134.9, 134.4, 132.7, 131.6 (d, J = 8.1 Hz), 130.0,
129.1, 127.7, 127.2, 126.9, 126.4, 125.5, 115.4 (d, J = 21.2 Hz), 30.6, 29.6;
19F NMR (377 MHz, CDCl3) δ -114.45; HRMS (ESI) calcd for C22H18FSe+
[M + H]+ m/z 381.0552, found 381.0544.
Phenyl(1-(m-tolyl)-3,4-dihydronaphthalen-2-yl)selane
(11):
Synthesized from 1i (0.4 mmol) and 2a (0.48 mmol). Purification by flash
column chromatography [petroleum ether/CH2Cl2, 20/1 (v/v)], to give the
product as a white solid (141 mg, 94%): Rf = 0.39 (petroleum ether/CH2Cl2,
10/1 (v/v)); mp 57−58 °C; 1H NMR (400 MHz, CDCl3) δ 7.56 − 7.48 (m,
2H), 7.33 (t, J = 7.8 Hz, 1H), 7.27 (dd, J = 5.1, 1.8 Hz, 3H), 7.20 (d, J = 7.6
Hz, 1H), 7.11 (d, J = 4.2 Hz, 2H), 7.05 (ddd, J = 12.6, 7.7, 2.7 Hz, 3H),
6.66 (d, J = 7.6 Hz, 1H), 2.88 − 2.79 (m, 2H), 2.55 − 2.47 (m, 2H), 2.40 (s,
3H); 13C{1H} NMR (101 MHz, CDCl3) δ 140.0, 139.4, 138.0, 136.2, 134.9,
134.4, 131.8, 130.5, 130.4, 129.0, 128.3, 128.3, 127.5, 127.1, 127.0, 126.7,
126.4, 125.8, 30.5, 29.7, 21.5; HRMS (ESI) calcd for C23H21Se+ [M + H]+
m/z 377.0803, found 377.0805.
(1-(4-Chlorophenyl)-3,4-dihydronaphthalen-2-yl)(phenyl)selane (6):
Synthesized from 1d (0.4 mmol) and 2a (0.48 mmol). Purification by flash
column chromatography [petroleum ether/CH2Cl2, 20/1 (v/v)], to give the
product as a white solid (147 mg, 93%): Rf = 0.38 (petroleum ether/CH2Cl2,
10/1 (v/v)); mp 124−125 °C; 1H NMR (400 MHz, CDCl3) δ 7.65 − 7.46 (m,
2H), 7.41 (d, J = 8.2 Hz, 2H), 7.24 (dd, J = 28.1, 6.9 Hz, 5H), 7.12 (d, J =
3.9 Hz, 2H), 7.05 (dd, J = 7.6, 4.2 Hz, 1H), 6.62 (d, J = 7.5 Hz, 1H), 2.83
(t, J = 7.7 Hz, 2H), 2.67 − 2.38 (m, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ
138.4, 138.2, 135.8, 134.9, 134.4, 133.5, 132.7, 131.4, 129.9, 129.1, 128.7,
127.8, 127.3, 126.9, 126.5, 125.5, 30.6, 29.6; HRMS (ESI) calcd for
(1-(3-Chlorophenyl)-3,4-dihydronaphthalen-2-yl)(phenyl)selane (12):
Synthesized from 1j (0.4 mmol) and 2a (0.48 mmol). Purification by flash
column chromatography [petroleum ether/CH2Cl2, 25/1 (v/v)], to give the
C
22H18ClSe+ [M + H]+ m/z 397.0257, found 397.0263.
product as
a colorless oil (143 mg, 91%): Rf = 0.33 (petroleum
(1-(4-Bromophenyl)-3,4-dihydronaphthalen-2-yl)(phenyl)selane (7):
Synthesized from 1e (0.4 mmol) and 2a (0.48 mmol). Purification by flash
column chromatography [petroleum ether/CH2Cl2, 30/1 (v/v)], to give the
product as a white solid (169 mg, 96%): Rf = 0.35 (petroleum ether/CH2Cl2,
10/1 (v/v)); mp 133−135 °C; 1H NMR (400 MHz, CDCl3) δ 7.57 (d, J = 8.3
Hz, 2H), 7.50 (dd, J = 7.3, 2.1 Hz, 2H), 7.33 − 7.25 (m, 3H), 7.15 (d, J =
8.3 Hz, 2H), 7.12 (d, J = 4.1 Hz, 2H), 7.05 (dt, J = 8.7, 4.3 Hz, 1H), 6.62
(d, J = 7.6 Hz, 1H), 2.87 − 2.79 (m, 2H), 2.55 − 2.47 (m, 2H); 13C{1H} NMR
(101 MHz, CDCl3) δ 138.9, 138.2, 135.7, 134.9, 134.4, 132.6, 131.7, 131.7,
129.9, 129.2, 127.8, 127.3, 127.0, 126.5, 125.5, 121.7, 30.6, 29.5; HRMS
(ESI) calcd for C22H18BrSe+ [M + H]+ m/z 440.9752, found 440.9753.
ether/CH2Cl2, 10/1 (v/v)); 1H NMR (400 MHz, CDCl3) δ 7.54 − 7.47 (m, 2H),
7.40 − 7.33 (m, 2H), 7.28 (qd, J = 4.8, 1.8 Hz, 4H), 7.16 (ddd, J = 5.8, 3.1,
1.6 Hz, 1H), 7.14 − 7.10 (m, 2H), 7.09 − 7.02 (m, 1H), 6.62 (d, J = 7.5 Hz,
1H), 2.87 − 2.77 (m, 2H), 2.55 − 2.45 (m, 2H); 13C{1H} NMR (101 MHz,
CDCl3) δ 141.8, 138.0, 135.6, 134.8, 134.5, 134.3, 132.9, 130.0, 129.9,
129.7, 129.2, 128.3, 127.8, 127.7, 127.3, 127.0, 126.5, 125.5, 30.6, 29.5;
HRMS (ESI) calcd for C22H18ClSe+ [M + H]+ m/z 397.0257, found 397.0256.
Phenyl(1-(3-(trifluoromethyl)phenyl)-3,4-dihydronaphthalen-2-
yl)selane (13): Synthesized from 1k (0.4 mmol) and 2a (0.48 mmol).
Purification by flash column chromatography [petroleum ether/CH2Cl2,
30/1 (v/v)], to give the product as a colorless oil (127 mg, 74%): Rf = 0.19
(petroleum ether/CH2Cl2, 10/1 (v/v)); 1H NMR (400 MHz, CDCl3) δ 7.64 (d,
J = 7.7 Hz, 1H), 7.61 − 7.53 (m, 2H), 7.53 − 7.44 (m, 3H), 7.28 (d, J = 6.7
Hz, 3H), 7.13 (d, J = 4.1 Hz, 2H), 7.06 (dq, J = 8.7, 3.8 Hz, 1H), 6.56 (d, J
= 7.6 Hz, 1H), 2.90 − 2.80 (m, 2H), 2.59 − 2.48 (m, 2H); 13C{1H} NMR (101
MHz, CDCl3) δ 140.8, 138.0, 135.6, 134.9, 134.5, 133.5, 133.3, 130.8 (q,
J = 32.3 Hz), 129.7, 129.2, 128.9, 127.9, 127.3, 127.1, 126.9 (q, J = 4.0
Hz), 126.5, 124.1 (d, J = 272.7 Hz), 125.4, 124.4 (q, J = 4.0 Hz), 30.7, 29.5;
19F NMR (377 MHz, CDCl3) δ -62.42; HRMS (ESI) calcd for C23H18F3Se+
[M + H]+ m/z 431.0520, found 431.0511.
(1-(4-Methoxyphenyl)-3,4-dihydronaphthalen-2-yl)(phenyl)selane (8):
Synthesized from 1f (0.4 mmol) and 2a (0.48 mmol). Purification by flash
column chromatography [petroleum ether/CH2Cl2, 5/1 (v/v)], to give the
product as a white solid (144 mg, 92%): Rf = 0.62 (petroleum ether/ethyl
acetate, 20/1 (v/v)); mp 141−142 °C; 1H NMR (400 MHz, CDCl3) δ 7.60 −
7.46 (m, 2H), 7.27 (d, J = 3.9 Hz, 3H), 7.19 (d, J = 8.3 Hz, 2H), 7.10 (d, J
= 4.1 Hz, 2H), 7.04 (dt, J = 8.5, 4.4 Hz, 1H), 6.98 (d, J = 8.4 Hz, 2H), 6.69
(d, J = 7.5 Hz, 1H), 3.85 (s, 3H), 2.82 (t, J = 7.7 Hz, 2H), 2.50 (m, 2H);
13C{1H} NMR (101 MHz, CDCl3) δ 158.9, 138.8, 136.3, 134.9, 134.4, 132.3,
132.2, 131.2, 130.3, 129.0, 127.6, 127.1, 126.7, 126.4, 125.7, 113.8, 55.2,
30.5, 29.7; HRMS (ESI) calcd for C23H21OSe+ [M + H]+ m/z 393.0752,
found 393.0757.
Phenyl(1-(o-tolyl)-3,4-dihydronaphthalen-2-yl)selane
(14):
Synthesized from 1l (0.4 mmol) and 2a (0.48 mmol). Purification by flash
column chromatography [petroleum ether/CH2Cl2, 20/1 (v/v)], to give the
product as a light yellow oil (147 mg, 98%): Rf = 0.44 (petroleum
ether/CH2Cl2, 10/1 (v/v)); 1H NMR (400 MHz, CDCl3) δ 7.57 − 7.47 (m, 2H),
Ethyl 4-(2-(phenylselanyl)-3,4-dihydronaphthalen-1-yl)benzoate (9):
Synthesized from 1g (0.4 mmol) and 2a (0.48 mmol). Purification by flash
column chromatography [hexane/CH2Cl2, 30/1 (v/v)], to give the product
7
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10.1002/ejoc.202100423
European Journal of Organic Chemistry
FULL PAPER
7.35 − 7.22 (m, 6H), 7.19 − 7.07 (m, 3H), 7.02 (td, J = 7.6, 2.0 Hz, 1H),
6.53 (d, J = 7.6 Hz, 1H), 2.98 − 2.79 (m, 2H), 2.54 − 2.46 (m, 2H), 2.20 (s,
3H); 13C{1H} NMR (101 MHz, CDCl3) δ 139.3, 138.1, 136.5, 135.3, 134.6,
132.3, 130.2, 129.8, 129.1, 127.9, 127.7, 127.2, 126.7, 126.6, 126.0, 124.8,
30.0, 29.6, 19.4; HRMS (ESI) calcd for C23H21Se+ [M + H]+ m/z 377.0803,
found 377.0804.
125.40, 125.35, 124.9, 30.5, 29.5; HRMS (ESI) calcd for C20H17SSe+ [M +
H]+ m/z 369.0211, found 369.0214.
(7-Methyl-1-phenyl-3,4-dihydronaphthalen-2-yl)(phenyl)selane (20):
Synthesized from 1r (0.4 mmol) and 2a (0.48 mmol). Purification by flash
column chromatography [petroleum ether/CH2Cl2, 30/1 (v/v)], to give the
product as a white solid (147 mg, 98%): Rf = 0.32 (petroleum ether/CH2Cl2,
10/1 (v/v)); mp 123−124 °C; 1H NMR (400 MHz, CDCl3) δ 7.51 (dd, J = 7.0,
2.5 Hz, 2H), 7.45 (t, J = 7.1 Hz, 2H), 7.39 (t, J = 7.3 Hz, 1H), 7.27 (dd, J =
4.3, 2.4 Hz, 5H), 7.02 (d, J = 7.5 Hz, 1H), 6.93 (d, J = 7.5 Hz, 1H), 6.47 (s,
1H), 2.80 (t, J = 7.8 Hz, 2H), 2.55 − 2.46 (m, 2H), 2.16 (s, 3H); 13C{1H}
NMR (101 MHz, CDCl3) δ 140.2, 139.5, 135.9, 135.9, 134.3, 132.1, 131.9,
130.4, 129.9, 129.0, 128.4, 127.52, 127.48, 127.4, 127.1, 126.4, 30.8, 29.3,
21.2; HRMS (ESI) calcd for C23H21Se+ [M + H]+ m/z 377.0803, found
377.0805.
(1-(2-Chlorophenyl)-3,4-dihydronaphthalen-2-yl)(phenyl)selane (15):
Synthesized from 1m (0.4 mmol) and 2a (0.48 mmol). Purification by flash
column chromatography [petroleum ether/CH2Cl2, 5/1 (v/v)], to give the
product as
a colorless oil (141 mg, 89%): Rf = 0.42 (petroleum
ether/CH2Cl2, 20/1 (v/v)); 1H NMR (400 MHz, CDCl3) δ 7.59 − 7.53 (m, 2H),
7.53 − 7.47 (m, 1H), 7.39 − 7.31 (m, 2H), 7.27 (dd, J = 5.2, 2.1 Hz, 4H),
7.17 − 7.09 (m, 2H), 7.05 (ddd, J = 8.7, 5.9, 3.1 Hz, 1H), 6.54 (d, J = 7.6
Hz, 1H), 2.95 − 2.79 (m, 2H), 2.63 − 2.47 (m, 2H); 13C{1H} NMR (101 MHz,
CDCl3) δ 138.7, 137.3, 134.8, 134.6, 134.3, 133.9, 133.5, 131.9, 129.9,
129.7, 129.1, 129.1, 127.6, 127.3, 127.0, 126.9, 126.5, 124.8, 30.5, 29.5;
HRMS (ESI) calcd for C22H18ClSe+ [M + H]+ m/z 397.0257, found 397.0244.
(7-Fluoro-1-phenyl-3,4-dihydronaphthalen-2-yl)(phenyl)selane (21):
Synthesized from 1s (0.4 mmol) and 2a (0.48 mmol). Purification by flash
column chromatography [petroleum ether/CH2Cl2, 30/1 (v/v)], to give the
Methyl(2-(2-(phenylselanyl)-3,4-dihydronaphthalen-1-yl)phenyl)-
sulfane (16): Synthesized from 1n (0.4 mmol) and 2a (0.48 mmol).
Purification by flash column chromatography [petroleum ether/CH2Cl2,
10/1 (v/v)], to give the product as a yellow oil (146 mg, 90%): Rf = 0.08
product as a colorless oil (148 mg, 98%): Rf = 0.39 (petroleum
ether/CH2Cl2, 10/1 (v/v)); 1H NMR (400 MHz, CDCl3) δ 7.52 (dd, J = 7.4,
2.0 Hz, 2H), 7.49 − 7.37 (m, 3H), 7.31 − 7.25 (m, 5H), 7.05 (dd, J = 8.2,
5.8 Hz, 1H), 6.78 (td, J = 8.3, 2.7 Hz, 1H), 6.35 (dd, J = 10.5, 2.6 Hz, 1H),
2.78 (t, J = 7.9 Hz, 2H), 2.52 − 2.45 (m, 2H); 13C{1H} NMR (101 MHz,
CDCl3) δ 161.6 (d, J = 243.4 Hz), 139.4, 138.0 (d, J = 2.0 Hz), 137.8 (d, J
= 8.1 Hz), 134.7, 134.1, 130.2 (d, J = 3.0 Hz), 129.8, 129.7, 129.1, 128.6,
128.1 (d, J = 8.1 Hz), 127.9, 127.8, 112.9 (d, J = 22.2 Hz), 112.5 (d, J =
23.2 Hz), 30.5, 28.8; 19F NMR (377 MHz, CDCl3) δ -117.06; HRMS (ESI)
calcd for C22H17FKSe+ [M + K]+ m/z 419.0111, found 419.0112.
1
(petroleum ether/CH2Cl2, 5/1 (v/v)); H NMR (400 MHz, CDCl3) δ 7.61 –
7.54 (m, 2H), 7.40 (ddd, J = 7.9, 7.2, 1.6 Hz, 1H), 7.32 – 7.20 (m, 5H), 7.16
(dd, J = 7.5, 1.5 Hz, 1H), 7.14 – 7.08 (m, 2H), 7.07 – 7.00 (m, 1H), 6.57 (d,
J = 7.5 Hz, 1H), 2.96 – 2.78 (m, 2H), 2.62 – 2.45 (m, 2H), 2.41 (s, 3H);
13C{1H} NMR (101 MHz, CDCl3) δ 138.3, 138.1, 137.6, 134.8, 134.3, 134.0,
130.4, 130.2, 129.0, 128.4, 127.5, 127.3, 126.9, 126.5, 124.8, 124.6, 30.5,
29.5, 15.3; HRMS (ESI) calcd for C23H21SSe+ [M + H]+ m/z 409.0524,
found 409.0529.
(7-Chloro-1-phenyl-3,4-dihydronaphthalen-2-yl)(phenyl)selane (22):
Synthesized from 1t (0.4 mmol) and 2a (0.48 mmol). Purification by flash
column chromatography [petroleum ether/CH2Cl2, 30/1 (v/v)], to give the
product as a white solid (152 mg, 96%): Rf = 0.52 (petroleum ether/CH2Cl2,
10/1 (v/v)); mp 93−95 °C; 1H NMR (400 MHz, CDCl3) δ 7.52 (dd, J = 7.6,
1.8 Hz, 2H), 7.47 (t, J = 7.1 Hz, 2H), 7.41 (t, J = 7.3 Hz, 1H), 7.32 − 7.23
(m, 5H), 7.09 − 7.00 (m, 2H), 6.61 (d, J = 1.8 Hz, 1H), 2.82 − 2.74 (m, 2H),
2.52 − 2.43 (m, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ 139.2, 137.7, 134.8,
134.3, 133.1, 132.1, 129.8, 129.7, 129.1, 128.7, 128.3, 127.9, 127.9, 126.3,
125.4, 30.2, 29.0; HRMS (ESI) calcd for C22H18ClSe+ [M + H]+ m/z
397.0257, found 397.0254.
(3,4-Dihydro-[1,1'-binaphthalen]-2-yl)(phenyl)selane (17): Synthesized
from 1o (0.4 mmol) and 2a (0.48 mmol). Purification by flash column
chromatography [petroleum ether/CH2Cl2, 5/1 (v/v)], to give the product as
a white solid (160 mg, 97%): Rf = 0.42 (petroleum ether/CH2Cl2, 20/1 (v/v));
mp 94−95 °C; 1H NMR (400 MHz, CDCl3) δ 7.95 (d, J = 8.2 Hz, 2H), 7.82
(d, J = 8.3 Hz, 1H), 7.64 − 7.57 (m, 1H), 7.53 (dq, J = 6.9, 3.0, 2.4 Hz, 3H),
7.47 (d, J = 6.9 Hz, 2H), 7.35 − 7.25 (m, 3H), 7.21 (d, J = 7.2 Hz, 1H), 7.18
− 7.09 (m, 1H), 6.97 (t, J = 7.4 Hz, 1H), 6.49 (d, J = 7.7 Hz, 1H), 3.09 −
2.94 (m, 2H), 2.67 (t, J = 7.7 Hz, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ
137.6, 137.2, 136.0, 134.5, 134.4, 134.2, 133.8, 131.8, 130.0, 129.0, 128.4,
128.1, 127.8, 127.7, 127.2, 126.8, 126.6, 126.3, 125.9, 125.6, 125.6, 30.5,
29.7; HRMS (ESI) calcd for C26H21Se+ [M + H]+ m/z 413.0803, found
413.0807.
(7-Methoxy-1-phenyl-3,4-dihydronaphthalen-2-yl)(phenyl)selane (23):
Synthesized from 1u (0.4 mmol) and 2a (0.48 mmol). Purification by flash
column chromatography [petroleum ether/CH2Cl2, 5/1 (v/v)], to give the
product as a white solid (151 mg, 96%): Rf = 0.56 (petroleum ether/ethyl
acetate, 20/1 (v/v)); mp 76−77 °C; 1H NMR (400 MHz, CDCl3) δ 7.54 −
7.48 (m, 2H), 7.43 (t, J = 7.2 Hz, 2H), 7.40 − 7.34 (m, 1H), 7.30 − 7.21 (m,
5H), 7.03 (d, J = 8.2 Hz, 1H), 6.65 (dd, J = 8.1, 2.6 Hz, 1H), 6.24 (d, J =
2.6 Hz, 1H), 3.62 (s, 3H), 2.88 − 2.69 (m, 2H), 2.61 − 2.39 (m, 2H); 13C{1H}
NMR (101 MHz, CDCl3) δ 158.2, 139.9, 139.1, 137.1, 134.4, 133.0, 130.2,
129.9, 129.0, 128.4, 127.8, 127.61, 127.58, 127.1, 112.5, 111.1, 55.2, 30.9,
28.8; HRMS (ESI) calcd for C23H21OSe+ [M + H]+ m/z 393.0752, found
393.0752.
2-(2-(Phenylselanyl)-3,4-dihydronaphthalen-1-yl)thiophene
(18):
Synthesized from 1p (0.4 mmol) and 2a (0.48 mmol). Purification by flash
column chromatography [petroleum ether/CH2Cl2, 30/1 (v/v)], to give the
product as a white solid (135 mg, 92%): Rf = 0.32 (petroleum ether/CH2Cl2,
10/1 (v/v)); mp 58−60 °C; 1H NMR (400 MHz, CDCl3) δ 7.62 − 7.50 (m,
2H), 7.42 (d, J = 5.1 Hz, 1H), 7.34 − 7.24 (m, 3H), 7.15 − 7.05 (m, 4H),
7.04 − 7.00 (m, 1H), 6.90 − 6.84 (m, 1H), 2.79 (t, J = 7.8 Hz, 2H), 2.57 −
2.40 (m, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ 140.4, 137.5, 136.1, 135.0,
134.4, 131.0, 129.8, 129.1, 128.6, 128.0, 127.1, 126.9, 126.5, 126.1, 125.4,
30.5, 29.3; HRMS (ESI) calcd for C20H17SSe+ [M + H]+ m/z 369.0211,
found 369.0217.
8-Phenyl-7-(phenylselanyl)-5,6-dihydronaphthalene-2-carbonitrile
(24): Synthesized from 1v (0.4 mmol) and 2a (0.48 mmol). Purification by
flash column chromatography [petroleum ether/CH2Cl2, 10/1 (v/v)], to give
the product as a white solid (117 mg, 76%): Rf = 0.28 (petroleum
ether/CH2Cl2, 10/1 (v/v)); mp 142−143 °C; 1H NMR (400 MHz, CDCl3) δ
7.56 − 7.47 (m, 4H), 7.47 − 7.42 (m, 1H), 7.37 (dd, J = 7.7, 1.6 Hz, 1H),
7.35 − 7.27 (m, 3H), 7.27 − 7.23 (m, 2H), 7.19 (d, J = 7.7 Hz, 1H), 6.89 (d,
J = 1.4 Hz, 1H), 2.90 − 2.84 (m, 2H), 2.53 − 2.46 (m, 2H); 13C{1H} NMR
(101 MHz, CDCl3) δ 140.0, 138.6, 137.1, 136.4, 135.8, 135.2, 130.0, 129.7,
129.2, 129.1, 129.0, 128.5, 128.21, 127.9, 119.1, 110.3, 29.6; HRMS (ESI)
calcd for C23H18NSe+ [M + H]+ m/z 388.0599, found 388.0596.
3-(2-(Phenylselanyl)-3,4-dihydronaphthalen-1-yl)thiophene
(19):
Synthesized from 1q (0.4 mmol) and 2a (0.48 mmol). Purification by flash
column chromatography [petroleum ether/CH2Cl2, 30/1 (v/v)], to give the
product as a white solid (133 mg, 90%): Rf = 0.34 (petroleum ether/CH2Cl2,
10/1 (v/v)); mp 67−68 °C; 1H NMR (400 MHz, CDCl3) δ 7.56 − 7.49 (m,
2H), 7.39 (dd, J = 4.9, 2.9 Hz, 1H), 7.28 (p, J = 3.1 Hz, 3H), 7.26 − 7.22
(m, 1H), 7.14 − 7.00 (m, 4H), 6.75 (d, J = 7.4 Hz, 1H), 2.86 − 2.75 (m, 2H),
2.52 − 2.43 (m, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ 139.8, 135.8, 134.8,
134.6, 133.8, 133.6, 130.0, 129.1, 129.0, 127.7, 127.1, 126.8, 126.4,
8
This article is protected by copyright. All rights reserved.

10.1002/ejoc.202100423
European Journal of Organic Chemistry
FULL PAPER
(6-Chloro-1-phenyl-3,4-dihydronaphthalen-2-yl)(phenyl)selane (25):
Synthesized from 1w (0.4 mmol) and 2a (0.48 mmol). Purification by flash
column chromatography [hexane/CH2Cl2, 50/1 (v/v)], to give the product
as a white solid (86 mg, 54%): Rf = 0.41 (petroleum ether/CH2Cl2, 10/1
(v/v)); mp 83−85 °C; 1H NMR (400 MHz, CDCl3) δ 7.55 − 7.47 (m, 2H),
7.47 − 7.41 (m, 2H), 7.41 − 7.35 (m, 1H), 7.31 − 7.21 (m, 5H), 7.09 (d, J =
2.0 Hz, 1H), 6.98 (dd, J = 8.3, 2.2 Hz, 1H), 6.56 (d, J = 8.3 Hz, 1H), 2.83 −
2.74 (m, 2H), 2.48 (dd, J = 8.7, 7.1 Hz, 2H); 13C{1H} NMR (101 MHz,
CDCl3) δ 139.6, 138.1, 136.6, 134.6, 132.7, 132.0, 129.9, 129.8, 129.1,
128.5, 127.8, 127.7, 127.1, 126.9, 126.3, 30.2, 29.4; HRMS (ESI) calcd for
C22H18ClSe+ [M + H]+ m/z 397.0257, found 397.0258.
7.5 Hz, 1H), 6.32 (s, 1H), 2.81 (t, J = 7.8 Hz, 2H), 2.57 − 2.49 (m, 2H), 2.17
(s, 3H). 13C{1H} NMR (101 MHz, CDCl3) δ 147.3, 137.9, 136.1, 135.0,
134.3, 133.4, 131.8, 131.1, 129.5, 129.3, 127.9, 127.4, 126.0, 123.8, 31.0,
29.0, 21.1; HRMS (ESI) calcd for C23H20NO2Se+ [M + H]+ m/z 422.0654,
found 422.0664.
Phenyl(10-phenylphenanthren-9-yl)selane (30): Synthesized from 1ab
(0.4 mmol) and 2a (0.48 mmol). Purification by flash column
chromatography [petroleum ether/CH2Cl2, 20/1 (v/v)], to give the product
as a yellow oil (112 mg, 68%): Rf = 0.45 (petroleum ether/CH2Cl2, 10/1
(v/v)); 1H NMR (400 MHz, CDCl3) δ 8.76 (t, J = 8.8 Hz, 2H), 8.68 (dd, J =
8.3, 1.3 Hz, 1H), 7.66 (tdd, J = 8.3, 5.5, 2.3 Hz, 2H), 7.55 (ddd, J = 8.3, 7.0,
1.2 Hz, 1H), 7.50 − 7.44 (m, 2H), 7.42 (dd, J = 5.0, 2.0 Hz, 3H), 7.26 (q, J
= 2.8 Hz, 1H), 7.23 (q, J = 4.0, 3.0 Hz, 3H), 7.03 (s, 5H); 13C{1H} NMR (101
MHz, CDCl3) δ 146.8, 142.0, 134.2, 132.9, 132.4, 132.2, 131.1, 130.7,
130.6, 129.7, 129.2, 128.91, 128.90, 127.9, 127.6, 127.4, 127.3, 127.0,
126.7, 125.5, 122.7, 122.6; HRMS (ESI) calcd for C26H19Se+ [M + H]+ m/z
411.0646, found 411.0654.
(8-Chloro-1-phenyl-3,4-dihydronaphthalen-2-yl)(phenyl)selane (25’):
Synthesized from 1w (0.4 mmol) and 2a (0.48 mmol). Purification by flash
column chromatography [hexane/CH2Cl2, 50/1 (v/v)], to give the product
as a light-yellow solid (37 mg, 23%): Rf = 0.37 (petroleum ether/CH2Cl2,
10/1 (v/v)); mp 113−115 °C; 1H NMR (400 MHz, CDCl3) δ 7.58 − 7.51 (m,
2H), 7.42 − 7.27 (m, 8H), 7.13 (dd, J = 7.1, 2.2 Hz, 1H), 7.09 − 7.01 (m,
2H), 2.72 (dd, J = 8.5, 6.0 Hz, 2H), 2.44 − 2.36 (m, 2H); 13C{1H} NMR (101
MHz, CDCl3) δ 141.4, 140.2, 137.4, 135.8, 135.1, 133.8, 131.7, 130.0,
129.9, 129.8, 129.1, 128.0, 127.8, 127.4, 127.1, 125.5, 31.2, 30.1; HRMS
(ESI) calcd for C22H18ClSe+ [M + H]+ m/z 397.0257, found 397.0262.
4-Phenyl-3-(phenylselanyl)-2H-chromene (31): Synthesized from 1ac
(0.4 mmol) and 2a (0.48 mmol). Purification by flash column
chromatography [petroleum ether/CH2Cl2, 40/1 (v/v)], to give the product
as a light-yellow solid (135 mg, 93%): Rf = 0.47 (petroleum ether/CH2Cl2,
10/1 (v/v)); mp 71−72 °C; 1H NMR (400 MHz, CDCl3) δ 7.52 (dd, J = 6.5,
2.9 Hz, 2H), 7.49 − 7.38 (m, 3H), 7.32 − 7.26 (m, 5H), 7.14 (td, J = 8.0, 1.5
Hz, 1H), 6.86 (d, J = 8.0 Hz, 1H), 6.84 − 6.79 (m, 1H), 6.74 − 6.68 (m, 1H),
4.74 (s, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ 153.6, 138.3, 137.5, 133.5,
129.7, 129.4, 129.1, 128.6, 128.4, 128.1, 127.8, 126.2, 125.0, 122.5, 121.5,
115.9, 69.5; HRMS (ESI) calcd for C21H17OSe+ [M + H]+ m/z 365.0439,
found 365.0429.
(5-Methyl-1-phenyl-3,4-dihydronaphthalen-2-yl)(phenyl)selane (26):
Synthesized from 1x (0.4 mmol) and 2a (0.48 mmol). Purification by flash
column chromatography [petroleum ether/CH2Cl2, 25/1 (v/v)], to give the
product as a white solid (140 mg, 93%): Rf = 0.31 (petroleum ether/CH2Cl2,
10/1 (v/v)); mp 115−116 °C; 1H NMR (400 MHz, CDCl3) δ 7.56 − 7.48 (m,
2H), 7.43 (t, J = 7.3 Hz, 2H), 7.40 − 7.34 (m, 1H), 7.32 − 7.22 (m, 5H), 7.00
(d, J = 7.4 Hz, 1H), 6.94 (t, J = 7.6 Hz, 1H), 6.52 (d, J = 7.6 Hz, 1H), 2.80
(t, J = 7.9 Hz, 2H), 2.52 (t, J = 7.9 Hz, 2H), 2.28 (s, 3H); 13C{1H} NMR (101
MHz, CDCl3) δ 140.5, 139.7, 136.0, 134.5, 134.3, 133.2, 131.4, 130.3,
129.9, 129.0, 128.9, 128.4, 127.5, 127.4, 125.7, 124.1, 30.2, 25.6, 19.6;
HRMS (ESI) calcd for C23H21Se+ [M + H]+ m/z 377.0803, found 377.0797.
4-Phenyl-3-(phenylselanyl)-1-tosyl-1,2-dihydroquinoline
(32):
Synthesized from 1ad (0.4 mmol) and 2a (0.48 mmol). Purification by flash
column chromatography [petroleum ether/ethyl acetate, 50/1 (v/v)], to give
the product as a yellow solid (188 mg, 91%): Rf = 0.37 (petroleum
ether/CH2Cl2, 10/1 (v/v)); mp 161−163 °C; 1H NMR (400 MHz, CDCl3) δ
7.74 (dd, J = 8.0, 1.0 Hz, 1H), 7.64 − 7.57 (m, 2H), 7.45 − 7.33 (m, 5H),
7.31 (dd, J = 5.1, 1.9 Hz, 3H), 7.29 − 7.23 (m, 1H), 7.19 (d, J = 8.0 Hz, 2H),
7.07 (td, J = 7.7, 1.2 Hz, 1H), 6.61 − 6.53 (m, 3H), 4.43 (s, 2H), 2.44 (s,
3H); 13C{1H} NMR (101 MHz, CDCl3) δ 143.6, 137.6, 136.0, 135.92, 135.86,
135.7, 133.7, 132.0, 129.5, 129.3, 129.1, 128.9, 128.3, 127.8, 127.5, 127.0,
126.7, 126.2, 125.8, 125.5, 50.1, 21.4; HRMS (ESI) calcd for
C28H24NO2SSe+ [M + H]+ m/z 518.0687, found 518.0687.
(5-Chloro-1-phenyl-3,4-dihydronaphthalen-2-yl)(phenyl)selane (27):
Synthesized from 1y (0.4 mmol) and 2a (0.48 mmol). Purification by flash
column chromatography [petroleum ether/CH2Cl2, 25/1 (v/v)], to give the
product as a white solid (146 mg, 92%): Rf = 0.35 (petroleum ether/CH2Cl2,
10/1 (v/v)); mp 143−145 °C; 1H NMR (400 MHz, CDCl3) δ 7.52 (dd, J = 7.5,
1.7 Hz, 2H), 7.45 (t, J = 7.1 Hz, 2H), 7.40 (dd, J = 8.4, 6.1 Hz, 1H), 7.34 −
7.22 (m, 5H), 7.16 (d, J = 7.9 Hz, 1H), 6.95 (t, J = 7.9 Hz, 1H), 6.54 (d, J =
7.7 Hz, 1H), 3.00 − 2.93 (m, 2H), 2.55 − 2.45 (m, 2H); 13C{1H} NMR (101
MHz, CDCl3) δ 139.8, 138.0, 137.9, 134.8, 133.7, 132.8, 132.4, 129.9,
129.6, 129.1, 128.6, 127.9, 127.7, 127.5, 126.9, 124.3, 29.6, 26.0; HRMS
(ESI) calcd for C22H18ClSe+ [M + H]+ m/z 397.0257, found 397.0263.
4-Phenyl-3-(phenylselanyl)-2H-chromen-2-one (33): Synthesized from
1ae (0.4 mmol) and 2a (0.96 mmol) in 2 mL CH2Cl2 and Tf2O (0.96 mmol)
and Et3N (3.2 mmol) were used. Purification by flash column
chromatography [petroleum ether/ethyl acetate, 10/1 (v/v)], to give the
product as a white solid (68 mg, 45%): Rf = 0.15 (petroleum ether/ethyl
acetate, 20/1 (v/v)); mp 146−148 °C; 1H NMR (400 MHz, CDCl3) δ 7.51
(ddd, J = 8.6, 7.2, 1.7 Hz, 1H), 7.47 − 7.42 (m, 3H), 7.37 (dd, J = 8.3, 1.2
Hz, 1H), 7.34 − 7.29 (m, 2H), 7.22 − 7.10 (m, 6H), 7.06 (dd, J = 8.0, 1.6
Hz, 1H); 13C{1H} NMR (101 MHz, CDCl3) δ 159.5, 158.9, 153.4, 136.2,
132.8, 132.0, 130.3, 129.0, 128.8, 128.5, 128.2, 127.9, 127.4, 124.2, 120.7,
120.5, 116.8; HRMS (ESI) calcd for C21H15O2Se+ [M + H]+ m/z 379.0232,
found 379.0240.
Phenyl(1-phenyl-3,4-dihydrophenanthren-2-yl)selane
(28):
Synthesized from 1z (0.4 mmol) and 2a (0.48 mmol). Purification by flash
column chromatography [petroleum ether/CH2Cl2, 15/1 (v/v)], to give the
product as a light-yellow solid (138 mg, 84%): Rf = 0.32 (petroleum
ether/CH2Cl2, 10/1 (v/v)); mp 140−141 °C; 1H NMR (400 MHz, CDCl3) δ
8.02 (d, J = 8.5 Hz, 1H), 7.75 (d, J = 8.0 Hz, 1H), 7.57 (dd, J = 6.4, 3.2 Hz,
2H), 7.53 (d, J = 8.7 Hz, 1H), 7.47 (t, J = 8.2 Hz, 3H), 7.41 (td, J = 7.3, 2.8
Hz, 2H), 7.30 (dt, J = 5.0, 2.6 Hz, 5H), 6.88 (d, J = 8.6 Hz, 1H), 3.30 − 3.21
(m, 2H), 2.71 − 2.60 (m, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ 140.4,
139.6, 134.4, 133.1, 132.6, 131.8, 131.0, 130.3, 130.1, 130.0, 129.1, 128.5,
127.7, 127.6, 126.12, 126.08, 125.2, 124.6, 123.5, 30.3, 24.9; HRMS (ESI)
calcd for C26H21Se+ [M + H]+ m/z 413.0803, found 413.0797.
1-Methyl-4-phenyl-3-(phenylselanyl)quinolin-2(1H)-one
(34):
Synthesized from 1af (0.4 mmol) and 2a (0.48 mmol). Purification by flash
column chromatography [petroleum ether/ethyl acetate, 10/1 (v/v)], to give
the product as a yellow oil (60 mg, 38%): Rf = 0.13 (petroleum ether/ethyl
acetate, 5/1 (v/v)); 1H NMR (400 MHz, CDCl3) δ 7.55 (ddd, J = 8.6, 7.1, 1.6
Hz, 1H), 7.43 − 7.35 (m, 4H), 7.27 (dt, J = 7.2, 2.4 Hz, 2H), 7.18 − 7.04 (m,
7H), 3.81 (s, 3H); 13C{1H} NMR (101 MHz, CDCl3) δ 160.5, 154.9, 139.8,
138.0, 132.1, 131.7, 130.8, 128.7, 128.6, 128.2, 128.0, 126.6, 126.2, 122.0,
121.4, 114.1, 30.8; HRMS (ESI) calcd for C22H18NOSe+ [M + H]+ m/z
392.0548, found 392.0542.
(7-Methyl-1-(4-nitrophenyl)-3,4-dihydronaphthalen-2-
yl)(phenyl)selane (29): Synthesized from 1aa (0.4 mmol) and 2a (0.96
mmol) in 2 mL CH2Cl2 and Tf2O (0.96 mmol) and Et3N (3.2 mmol) were
used. Purification by flash column chromatography [petroleum
ether/CH2Cl2, 5/1 (v/v)], to give the product as a light-yellow solid (72 mg,
1
43%): Rf = 0.32 (petroleum ether/CH2Cl2, 5/1 (v/v)); mp 148−149 °C; H
NMR (400 MHz, CDCl3) δ 8.35 − 8.27 (m, 2H), 7.51 − 7.47 (m, 2H), 7.47
− 7.43 (m, 2H), 7.32 − 7.25 (m, 3H), 7.04 (d, J = 7.6 Hz, 1H), 6.97 (d, J =
9
This article is protected by copyright. All rights reserved.

10.1002/ejoc.202100423
European Journal of Organic Chemistry
FULL PAPER
1,4-Bis(2-(phenylselanyl)-3,4-dihydronaphthalen-1-yl)benzene (35):
Synthesized from 1ag (0.2 mmol) and 2a (0.48 mmol). Purification by flash
column chromatography [petroleum ether/CH2Cl2, 5/1 (v/v)], to give the
product as a white solid (94 mg, 73%): Rf = 0.46 (petroleum ether/CH2Cl2,
5/1 (v/v)); mp 221−222 °C; 1H NMR (400 MHz, CDCl3) δ 7.61 − 7.52 (m,
4H), 7.37 − 7.32 (m, 4H), 7.32 − 7.25 (m, 6H), 7.16 − 7.06 (m, 6H), 6.79
(d, J = 6.9 Hz, 2H), 2.86 (t, J = 7.7 Hz, 4H), 2.54 (td, J = 8.0, 7.3, 2.0 Hz,
4H). 13C{1H} NMR (101 MHz, CDCl3) δ 139.1, 138.9, 136.1, 134.9, 134.6,
132.3, 130.3, 130.0, 129.1, 127.6, 127.1, 126.7, 126.5, 125.8, 30.6, 29.7;
HRMS (ESI) calcd for C38H31Se2+ [M + H]+ m/z 647.0751, found 647.0756.
5H), 6.95 (d, J = 7.5 Hz, 1H); 13C{1H} NMR (101 MHz, CDCl3) δ 142.9,
140.1, 139.4, 135.8, 134.5, 132.1, 131.2, 130.9, 130.3, 129.5, 129.2, 129.1,
128.8, 128.4, 128.3, 127.5, 127.0, 126.7, 126.4, 120.5; HRMS (ESI) calcd
for C22H17OSe+ [M + H]+ m/z 377.0439, found 377.0433.
Diphenyl(1-phenylnaphthalen-2-yl)phosphane (39): To a flame-dried
Schlenk tube was added 36 (0.2 mmol, 72 mg). The flask was evacuated
and purged with nitrogen for three times. 1 mL THF was added under
nitrogen atmosphere and the solution was cooled to -78 °C. n-BuLi (0.24
M in THF, 1 mL, 0.24 mmol) was added dropwise. The solution was stirred
at -78 °C for 1 h and then Ph2PCl (0.24 mmol, 53 mg) was added. The
resulting solution was stirred at room temperature for 12 h. The reaction
was quenched with water and extracted with ethyl acetate. Combined
organic layers were dried over Na2SO4, filtered, and concentrated under
reduced pressure. The residue was purified by flash silica gel column
chromatography [petroleum ether/ethyl acetate, 50/1 (v/v)], to give product
39 as a white solid (44 mg, 56%): Rf = 0.41 (petroleum ether/ethyl acetate,
20/1 (v/v)); mp 183−185 °C; 1H NMR (400 MHz, CDCl3) δ 7.84 (d, J = 8.1
Hz, 1H), 7.76 (d, J = 8.5 Hz, 1H), 7.51 − 7.44 (m, 2H), 7.36 (q, J = 8.0, 6.9
Hz, 4H), 7.31 − 7.25 (m, 6H), 7.21 (ddd, J = 8.6, 6.4, 4.6 Hz, 5H), 7.15 (d,
J = 7.5 Hz, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ 146.8 (d, J = 31.3 Hz),
139.4 (d, J = 8.1 Hz), 138.0 (d, J = 13.1 Hz), 133.7 (d, J = 19.2 Hz), 137.6
(d, J = 27.3 Hz), 132.8 (d, J = 6.1 Hz), 130.8 (d, J = 2.0 Hz), 129.7, 128.32,
128.27, 127.8, 127.7, 127.6, 127.4, 127.0 (d, J = 2.0 Hz), 126.5, 126.2;
31P{1H} NMR (162 MHz, CDCl3) δ -13.70; HRMS (ESI) calcd for C28H22P+
[M + H]+ m/z 389.1454, found 389.1461.
Procedure of large-scale synthesis: To a flame-dried Schlenk tube were
added alkyne 1a (4.0 mmol) and sulfoxide 2a (4.8 mmol), and then they
were dissolved with dichloromethane (20 mL) under
a nitrogen
atmosphere before being cooled to −78 °C (liquid N2/ethyl acetate bath).
Tf2O (2.0 mL, 4.8 mmol) was added dropwise. After being stirred for 0.5 h,
the mixture was warmed to room temperature and stirred for an additional
0.5 h, and then Et3N (2.0 g, 20 mmol) was added dropwise at 0 °C. After
being stirred for 2 h, the solution was extracted with CH2Cl2. The combined
organic phase was dried over Na2SO4 and concentrated under reduced
pressure. The residue was further purified by flash column
chromatography on silica gel [petroleum ether/CH2Cl2, 30/1 (v/v)] and
afforded pure product (1.27 g, 88 %).
Procedure and characterization for transformations of products:
Phenyl(1-phenylnaphthalen-2-yl)selane (36): 3a (0.5 mmol, 181 mg)
was dissolved in CH2Cl2 (5 mL) and 2,3-dichloro-5,6-dicyano-1,4-
benzoquinone (341 mg, 1.5 mmol) was added at room temperature. The
brown mixture was stirred at room temperature for 12 h, and then
concentrated under reduced pressure. The residue was purified by flash
silica gel column chromatography [petroleum ether/CH2Cl2, 30/1 (v/v)] to
yield the corresponding product 36 as a white solid (171 mg, 95%): Rf =
Phenyl(1-phenylnaphthalen-2-yl)methanol (40): To
a flame-dried
Schlenk tube was added 36 (0.2 mmol, 72 mg). The flask was evacuated
and purged with nitrogen for three times. 1 mL THF was added under
nitrogen atmosphere and the solution was cooled to -78 °C. n-BuLi (0.24
M in THF, 1 mL, 0.24 mmol) was added dropwise. The solution was stirred
at -78 °C for 1 h and then benzaldehyde (0.24 mmol, 25 mg) was added.
The resulting solution was stirred at room temperature for 2 h. The reaction
was quenched with water and extracted with ethyl acetate. Combined
organic layers were dried over Na2SO4, filtered, and concentrated under
reduced pressure. The residue was purified by flash silica gel column
chromatography [petroleum ether/ethyl acetate, 50/1 (v/v)], to give product
40 as a white solid (45 mg, 73%): Rf = 0.41 (petroleum ether/ethyl acetate,
20/1 (v/v)); mp 88−89 °C; 1H NMR (400 MHz, CDCl3) δ 7.86 (dd, J = 11.8,
8.4 Hz, 2H), 7.67 (d, J = 8.7 Hz, 1H), 7.56 − 7.50 (m, 1H), 7.49 − 7.38 (m,
5H), 7.37 − 7.32 (m, 1H), 7.29 − 7.17 (m, 6H), 7.17 − 7.13 (m, 1H), 5.85
(s, 1H); 13C{1H} NMR (101 MHz, CDCl3) δ 143.7, 138.4, 138.2, 137.9,
132.8, 132.7, 130.8, 130.0, 128.5, 128.3, 128.2, 128.2, 127.8, 127.5, 127.1,
126.9, 126.5, 126.1, 125.9, 124.5, 72.8; HRMS (ESI) calcd for C23H18NaO+
[M + Na]+ m/z 333.1250, found 311.1252.
1
0.43 (petroleum ether/CH2Cl2, 10/1 (v/v)); mp 107−108 °C; H NMR (400
MHz, CDCl3) δ 7.78 (dd, J = 7.3, 1.8 Hz, 1H), 7.64 (d, J = 8.7 Hz, 1H), 7.50
(dtd, J = 8.7, 6.6, 4.9 Hz, 5H), 7.41 (td, J = 7.3, 6.8, 1.3 Hz, 2H), 7.35 (ddd,
J = 8.1, 4.1, 1.6 Hz, 3H), 7.32 − 7.24 (m, 4H). 13C{1H} NMR (101 MHz,
CDCl3) δ 139.7, 139.6, 135.0, 133.1, 132.1, 131.0, 130.5, 130.2, 129.4,
128.5, 128.1, 127.91, 127.86, 127.8, 126.4, 126.1, 125.5; HRMS (ESI)
calcd for C22H17Se+ [M + H]+ m/z 361.0490, found 361.0497.
4-Phenyl-3-(phenylseleninyl)-1,2-dihydronaphthalene (37): To
a
flame-dried 25 mL round-bottom flask was added 3a (0.5 mmol, 181 mg)
and dissolved in CH2Cl2 (5 mL) at 0 °C. A solution of m-CPBA (1.05 mmol,
107 mg, 85%) in CH2Cl2 (5 mL) was added dropwise to the cooled solution.
The mixture was stirred for 0.5 h at 0 °C and then stirred at room
temperature for an additional 2 h. Then the solvent was removed under
reduced pressure and purified by flash column chromatography
[CH2Cl2/CH3OH, 30/1 (v/v)], to give 37 as a colorless oil (168 mg, 89%): Rf
(1-([1,1'-Biphenyl]-4-yl)-3,4-dihydronaphthalen-2-yl)(phenyl)selane
(41): To a flame-dried Schlenk tube was added 7 (0.3 mmol, 132 mg),
phenylboronic acid (0.45 mmol, 55 mg), [(C6H5)3P]2PdCl2 (6 mol %, 13 mg)
and K3PO4 (0.6 mmol, 127mg). The flask was evacuated and purged with
nitrogen for three times. 1.5 mL toluene was added under nitrogen
atmosphere and the solution was stirred at 100 °C for 20 h. The reaction
was quenched with water and extracted with ethyl acetate. Combined
organic layers were dried over Na2SO4, filtered, and concentrated under
reduced pressure. The residue was purified by flash silica gel column
chromatography [petroleum ether CH2Cl2, 10/1 (v/v)], to give product 41
as a white solid (75 mg, 64%): Rf = 0.23 (petroleum ether/CH2Cl2, 5/1
(v/v)); mp 159−161 °C; 1H NMR (400 MHz, CDCl3) δ 7.73 − 7.63 (m, 4H),
7.53 (dd, J = 6.4, 3.0 Hz, 2H), 7.45 (t, J = 7.7 Hz, 2H), 7.34 (dd, J = 7.4,
4.8 Hz, 3H), 7.27 (dd, J = 5.0, 1.7 Hz, 3H), 7.12 (d, J = 4.3 Hz, 2H), 7.07
(ddt, J = 8.7, 5.7, 3.6 Hz, 1H), 6.73 (d, J = 7.6 Hz, 1H), 2.85 (t, J = 7.8 Hz,
2H), 2.54 (dd, J = 9.0, 6.7 Hz, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ 140.8,
140.2, 139.0, 136.1, 134.9, 134.4, 132.2, 130.4, 130.2, 129.1, 128.7, 127.6,
127.3, 127.2, 127.1, 126.8, 126.4, 125.8, 30.6, 29.7; HRMS (ESI) calcd for
C28H23Se+ [M + H]+ m/z 439.0959, found 439.0951.
1
= 0.50 (CH2Cl2/CH3OH, 20/1 (v/v)); H NMR (400 MHz, CDCl3) δ 7.68 −
7.59 (m, 2H), 7.55 − 7.22 (m, 8H), 7.20 (td, J = 7.3, 1.0 Hz, 1H), 7.15 (d, J
= 6.5 Hz, 1H), 7.08 (td, J = 7.6, 1.3 Hz, 1H), 6.76 (d, J = 7.7 Hz, 1H), 3.08
− 2.94 (m, 2H), 2.88 − 2.74 (m, 1H), 2.31 − 2.17 (m, 1H); 13C{1H} NMR
(101 MHz, CDCl3) δ 144.8, 142.3, 140.6, 136.4, 136.2, 134.3, 130.8, 129.3,
129.2, 128.7, 127.7, 127.3, 126.6, 126.3, 28.7, 19.1; HRMS (ESI) calcd for
C22H19OSe+ [M + H]+ m/z 379.0596, found 379.0606.
1-Phenyl-2-(phenylseleninyl)naphthalene (38): To a flame-dried 25 mL
round-bottom flask was added 36 (0.5 mmol, 180 mg) and dissolved in
CH2Cl2 (5 mL) at 0 °C. A solution of m-CPBA (1.05 mmol, 107 mg, 85%)
in CH2Cl2 (5 mL) was added dropwise to the cooled solution. The mixture
was stirred for 0.5 h at 0 °C and then stirred at room temperature for an
additional 2 h. Then the solvent was removed under reduced pressure and
purified by flash column chromatography [CH2Cl2/CH3OH, 30/1 (v/v)], to
give 38 as a light-pink solid (160 mg, 85%): Rf = 0.48 (CH2Cl2/CH3OH, 20/1
(v/v)); mp 148−150 °C; 1H NMR (400 MHz, CDCl3) δ 8.26 (d, J = 8.7 Hz,
1H), 8.08 (d, J = 8.7 Hz, 1H), 7.95 − 7.88 (m, 1H), 7.65 − 7.58 (m, 1H),
7.58 − 7.50 (m, 4H), 7.42 (tdd, J = 7.3, 2.9, 0.9 Hz, 2H), 7.38 − 7.26 (m,
10
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10.1002/ejoc.202100423
European Journal of Organic Chemistry
FULL PAPER
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Acknowledgements
This work was supported by National Natural Science Foundation
of China (21402005), Natural Science Foundation of Beijing
Municipality (2202040), and the Fundamental Research Funds for
the Central Universities (XK-1802-6 and 12060093063).
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Keywords: Electrophilic cyclization of alkynes
• Activated
selenoxide • Alkyne • Metal-free synthesis • Benzobicyclic
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11
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Entry for the Table of Contents
OTf
Se
O
via
OTf
Se
R1
R1
H3C
Ar
H3C
Ar
metal free reaction
high yields (up to 97%)
broad scope (42 examples)
SeAr
CH2Cl2
Tf2O then Et3N
R2
R2
A metal-free, one-pot selenium mediated electrophilic cyclization reaction of alkynes and triflic anhydride-activated selenoxides was
realized, giving selenium containing dihydronaphthalene products, including selenium-substituted phenanthrene, dihydroquinoline,
2H-chromene, and coumarin.
12
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