KI catalyzed azidoselenenylation of alkenes with sodium azide and diselenides via an oxidative cleavage of Se–Se bond

Article abstract of DOI:10.1080/10426507.2016.1192625

Using potassium iodide as a catalyst and m-chloroperbenzoic acid as an oxidant, an efficient catalytic procedure has been developed for the azidoselenenylation of alkenes with sodium azide and diselenides, and a series of corresponding β-azidoselenides, m

Full text of DOI:10.1080/10426507.2016.1192625

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: http://www.tandfonline.com/loi/gpss20
KI Catalyzed Azidoselenenylation of Alkenes with
Sodium Azide and Diselenides via an Oxidative
Cleavage of Se-Se Bond
Yikun Zhang, Sixue Wu, Hongwei Shi & Jie Yan
To cite this article: Yikun Zhang, Sixue Wu, Hongwei Shi & Jie Yan (2016): KI Catalyzed
Azidoselenenylation of Alkenes with Sodium Azide and Diselenides via an Oxidative
Cleavage of Se-Se Bond, Phosphorus, Sulfur, and Silicon and the Related Elements, DOI:
10.1080/10426507.2016.1192625
To link to this article: http://dx.doi.org/10.1080/10426507.2016.1192625
Accepted author version posted online: 26
May 2016.
Published online: 26 May 2016.
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Date: 01 June 2016, At: 07:07

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KI Catalyzed Azidoselenenylation of Alkenes with Sodium Azide and Diselenides via an
Oxidative Cleavage of Se-Se Bond
Yikun Zhang, Sixue Wu, Hongwei Shi, and Jie Yan*
College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310015,
P. R .China
*corresponding authors E-mail: jieyan87@zjut.edu.cn
Abstract
Using potassium iodide as a catalyst and m-chloroperbenzoic acid as an oxidant, an efficient
catalytic procedure has been developed for the azidoselenenylation of alkenes with sodium azide
and diselenides, and a series of corresponding β-azidoselenides, most of which are new
compounds, have been prepared in moderate to good yields under mild reaction conditions. This
in situ generation of the electrophilic selenenylating reagents with addition to alkenes is a
stereospecific anti addition, which occurs with a Markovnikov orientation.
N
3
2
KI (cat.), mCPBA
R
Se
+
1
NaN
Se
2
3
R
Se
2
R
1
R
MeCN/H O, 24h, r.t.
2
R
1
2
3
Keywords
Azidoselenenylation, diselenide, alkene, sodium azide, potassium iodide, catalysis
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Introduction
Organoselenium chemistry has developed as an important synthetic tool in the hands of synthetic
chemists since the discovery of the selenoxide elimination in the early 1970s.1-5 Because of their
synthetic applications6 and biological activities such as antitumor, antibacterial activities and
other properties,7-14 selenium compounds have been increasing in importance in recent years. β-
Azidoselenides is a significant class of organoselenium compounds which have a greater
synthetic importance since they combine the well known reactivity of the azido group with that
of the selenium containing group.15-18 The first example of the azidoselenenylation of alkenes
was reported by Hassner and Amarasekara.19 The reaction was effected with PhSeCl and sodium
azide in DMSO, resulting in the stereospecific (anti) but not regiospecific products. Using a
particular but expensive silver salt, silver triflate (AgOTf), the generated highly electrophilic
phenylselenenyl triflate can promote the azidoselenenylation of alkenes efficiently, and the
corresponding β-azidoselenides have been obtained with stereospecific and regiospecific
selectivity.20 In the similar manner, the asymmetric azidoselenenylation of alkenes can be carried
out, affording a series of β-azidoselenides with high facial selectivity.21 The radical
azidoselenenylation of alkenes was discovered by Tingoli and co-workers when treatment of
diphenyl diselenide with hypervalent iodine reagent PhI(OAc)2 in the presence of sodium azide,
gave the anti-Markovnikov products.22 More recently, an iodine catalyzed seleno-
functionalization of olefins under microwave irradiation has been reported.23 However, the
product β-azidoselenide was obtained only in 21% yield. Although β-azidoselenides can be
prepared by above methods, the use of toxic, moisture-sensitive and expensive selenenylating
reagents limit this application, so the members of β-azidoselenides are still limited. Therefore,
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the development of simple and convenient methods, especially catalytic protocols for preparation
of β-azidoselenides is still desired.
It is known that hypervalent iodine reagents can promote the oxidative cleavage of Se-Se bond of
diphenyl diselenide to generate the reactive electrophilic selenium species.24-28 In our recent
research, we have found that some inorganic iodides such as KI combined with oxidants can be
used to replace hypervalent iodine reagents, resulting in the similar results.29-30 On this basis, we
have investigated the novel procedure for the azidoselenenylation of alkenes. Herein, we wish to
report an efficient azidoselenenylation of alkenes with sodium azide and diphenyl diselenide
using KI as catalyst and m-chloroperbenzoic acid as oxidant. To the best of our knowledge, this
method has not been reported before.
Results and Discussion
Initially, we examined the reaction of styrene 1a with diphenyl diselenide 2a and sodium azide
(NaN3) in the presence of oxidant m-chloroperbenzoic acid (mCPBA) and catalyst KI at room
temperature. It was observed that stirring the mixture of 1.0 equiv of 2a, 1.5 equiv of NaN3, 1.2
equiv of 1a and mCPBA with 0.1 equiv of KI in MeCN for 24 h, the expected addition product
(2-azido-2-phenylethyl)(phenyl)selane 3a was obtained in 24 % yield (Table 1, entry 1). As a
control experiment, 3a was isolated only in 3% yield in the absence of KI (entry 2). Then, the
catalytic azidoselenenylation of 1.2 equiv of 1a with 1.0 equiv of 2a using KI as catalyst and
mCPBA as oxidant at room temperature for 24 h was optimized. The reaction was first evaluated
in several solvents. As a result, a poor yield was obtained in CH2Cl2, and in DMF or THF no
product was detected (Table 1, entries 3-5). With the observation of the low solubility of NaN3 in
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MeCN, to improve the reaction, several mixed solvents of MeCN were treated in the reaction. It
was obvious that when the volume ratio of MeCN to H2O was 10:1, the yield of the
azidoselenenylation increased greatly to 57% (entry 6). Other mixed solvents can also promote
the azidoselenenylation, resulting in the desired product in yields ranging from 42-50% (entries
7-9). After then more H2O was added and when the ratio of MeCN to H2O reached 5:6, this
mixed solvent had the best effect (entries 6, 10-17). In the mixed solvent MeCN/H2O (5:6), other
iodine-containing compounds such as NH4I, PhI and C3H7I had the catalytic effect, but the given
yields were not more than 80% (entries 15, 18-20). When the amount of KI was increased from
0.1 equiv to 0.2 equiv, the yields of 3a dropped down, so 0.1 equiv was the best choice (entries
15 and 21). Finally, the amounts of mCPBA and NaN3 were also evaluated, and as a result, 1.2
equiv and 1.5 equiv were found to be the suitable amounts for mCPBA and NaN3, respectively
(entries 22-25).
Based on the extensive screening process, we arrived at the optimal reaction conditions. The
catalytic azidoselenenylation of 1.2 equiv of alkenes 1 with 1.0 equiv of diselenides 2, 1.5 equiv
of NaN3, 1.2 equiv of mCPBA and 0.1 equiv of KI in MeCN/H2O (5/6) at room temperature for
24 h was investigated (Scheme 1), and as a consequence a series of corresponding β-
azidoselenides 3 were obtained. The results were summarized in Table 2.
The azidoselenenylation proceeded efficiently, affording the corresponding β-azidoselenides 3a-
3f in moderate to good yields when 2a was treated with aromatic alkenes (Table 2, entries 1-6).
Dibenzyl diselenide 2b, similar to 2a, an aliphatic diselenide also reacted with alkenes, resulting
in the corresponding products 3h-3j in moderate to good yields (entries 8-10). This
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azidoselenenylation is a regiospecific reaction as all the obtained β-azidoselenides are the
Markovnikov orientation products. In order to investigate the stereospecificity of the
azidoselenenylation, cyclohexene 1g was selected to react with 2a, and the obtained product 3f
showed a trans single stereoisomer with 48% yield (entry 7).
A proposed catalytic mechanism for the azidoselenenylation of alkenes is shown in Scheme 2.
KI is first oxidized by mCPBA into hypoiodous acid A, which reacts smoothly with diselenide 2
to form the active intermediate B, followed by a rapid cleavage of Se-Se bond.29-31 The in situ
generated active electrophilic selenium species then reacts with alkene to form cyclic
intermediate C. Finally, intermediate C is attacked by anion of azide to provide the desired
product β-azidoselenide 3, which is a single isomer via an SN1 mechanism for the aromatic
alkenes. When aliphatic alkene 1g is treated in the reaction, the trans single stereoisomer via an
SN2 mechanism is obtained. In the cycle, another active intermediate ArSeI32-33 can further
transfer a second equivalent of electrophilic selenium to alkene.
Conclusions
We have developed an efficient catalytic processor for synthesis of β-azidoselenide compounds
by the azidoselenenylation of alkenes with diselenides, sodium azide and mCPBA in the
presence of catalytic amount of KI at room temperature. This method has some advantages such
as mild reaction conditions, simple procedure, and affording a series of β-azidoselenide, most are
new compounds with high regioselectivity and good yields. Furthermore, the use of KI in the
catalytic reaction will extend the application scope of inorganic iodides in organic synthesis.
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Experimental
General IR spectra were recorded on a Thermo-Nicolet 6700 instrument, 1H NMR and 13C NMR
spectra were measured on a Bruker-AVANCE Ⅲ (500 MHz) spectrometer, Mass spectra were
determined on Waters-GCT Premier, Thermo-DECAX-60000 LCQ Deca XP and Thermo-ITQ
1100 mass spectrometers. Alkenes, diselenides, mCPBA, KI, NaN3 and solvents were
1
13
commercially available. The Supplemental Materials contains sample H and C NMR spectra
of the products 3a – 3j (Figures S 1 – S 12)
General procedure for the KI catalyzed azidoselenenylation of alkenes. In a mixed solvent of
MeCN and H2O (5:6, V/V) (2.0 mL), alkenes 1 (0.24 mmol), diselenide 2 (0.10 mmol), NaN3
(0.3mmol), KI (0.02 mmol) and mCPBA (0.24 mmol) were added successively. The suspension
mixture was vigorously stirred at room temperature for 24 h. Upon completion, the reaction was
quenched by addition of sat. aq. Na2S2O3 (2 mL), sat. aq. Na2CO3 (8 mL) and H2O (5 mL),
respectively. The mixture was extracted with CH2Cl2 (3×5 mL) and the combined organic phase
was dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The
residue was then purified on a silica gel plate (10:1 petroleum ether-ethyl acetate) to furnish
products 3.
(2-azido-2-phenylethyl)(phenyl)selane 3a
Pale yellow oil.23
IR (neat): 2101 cm-1. 1H NMR (500 MHz, CDCl3) δ (ppm): 7.56 – 7.49 (m, 2H), 7.43 – 7.32 (m,
3H), 7.32 – 7.26 (m, 5H), 4.65 (dd, J = 8.3, 6.2 Hz, 1H), 3.27 (dd, J = 12.7, 6.3 Hz, 1H), 3.22
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(dd, J = 12.7, 6.2 Hz, 1H). 13C NMR (125 MHz, CDCl3) δ (ppm): 138.8, 133.3, 129.4, 129.3,
128.9, 128.7, 127.5, 126.9, 66.0, 34.0. MS (ESI): m/z (%) 320 (M+18).
(2-azido-2-(4-tolyl)ethyl)(phenyl)selane 3b
Pale yellow oil.
IR (neat): 2095 cm-1. 1H NMR (500 MHz, CDCl3) δ (ppm): 7.55 – 7.51 (m, 2H), 7.31 – 7.26 (m,
3H), 7.20 (s, 4H), 4.65 – 4.60 (m, 1H), 3.27 (dd, J = 12.5, 8.3 Hz, 1H), 3.21 (dd, J = 12.7, 6.3
Hz, 1H), 2.38 (s, 3H). 13C NMR (125 MHz, CDCl3) δ (ppm): 138.6, 135.7, 133.2, 129.6, 129.5,
129.2, 127.4, 126.8, 65.8, 33.9, 21.2. MS (ESI): m/z (%) 334 (M+18). HRMS: m/z calcd for
C15H19N4Se [M+18]: 335.0775; found: 335.0743.
(2-azido-2-(4-tert-butylphenyl)ethyl)(phenyl)selane 3c
Pale yellow oil.
IR (neat): 2103 cm-1. 1H NMR (500 MHz, CDCl3) δ (ppm): 7.54 – 7.51 (m, 2H), 7.42 – 7.40 (m,
2H), 7.30 – 7.27 (m, 3H), 7.26 – 7.23 (m, 2H), 4.65 (dd, J = 8.4, 6.1 Hz, 1H), 3.28 (dd, J = 12.7,
8.4 Hz, 1H), 3.23 (dd, J = 12.7, 6.0 Hz, 1H), 1.35 (s, 9H). 13C NMR (125 MHz, CDCl3) δ (ppm):
151.6, 135.7, 133.2, 129.6, 129.2, 127.4, 126.5, 125.8, 65.8, 34.6, 34.0, 31.3. MS (ESI): m/z (%)
376 (M+18). HRMS: m/z calcd for C18H25N4Se [M+18]: 377.1244; found: 377.1241.
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(2-(4-Acetoxyphenyl)-2-azidoethyl)(phenyl)selane 3d
Pale yellow oil.
IR (neat): 2101 cm-1. 1H NMR (500 MHz, CDCl3) δ (ppm): 7.53 – 7.50 (m, 2H), 7.33 – 7.27 (m,
5H), 7.13 – 7.10 (m, 2H), 4.65 (dd, J = 8.3, 6.0 Hz, 1H), 3.24 (dd, J = 12.8, 8.3 Hz, 1H), 3.19
(dd, J = 12.8, 6.0 Hz, 1H), 2.32 (s, 3H). 13C NMR (125 MHz, CDCl3) δ (ppm): 169.2, 150.8,
136.4, 133.3, 129.3, 127.9, 127.5, 122.0, 65.5, 34.1, 21.1. MS (ESI): m/z (%) 378 (M+18).
HRMS: m/z calcd for C16H19N4SeO2 [M+18]: 379.0673; found: 379.0661.
(2-azido-2-(4-fluorophenyl)ethyl)(phenyl)selane 3e
Pale yellow oil.
IR (neat): 2103 cm-1. 1H NMR (500 MHz, CDCl3) δ (ppm): 7.52 – 7.49 (m, 2H), 7.33 – 7.24 (m,
5H), 7.10 – 7.04 (m, 2H), 4.64 (dd, J = 7.6, 6.9 Hz, 1H), 3.26 (dd, J = 12.7, 7.9 Hz, 1H), 3.18
(dd, J = 12.7, 6.5 Hz, 1H). 13C NMR (125 MHz, CDCl3) δ (ppm): 163.7, 161.7, 134.53, 134.50,
133.3, 129.3, 129.2, 128.8, 128.74, 128.7, 128.6, 127.6, 116.2, 116.0, 115.9, 115.7, 65.3, 34.0.
MS (ESI): m/z (%) 319 (M-1). HRMS: m/z calcd for C14H12N3FSe: 321.0180; found: 321.0173.
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(2-azido-2-(4-chlorophenyl)ethyl)(phenyl)selane 3f
Pale yellow oil.
IR (neat): 2102 cm-1. 1H NMR (500 MHz, CDCl3) δ (ppm): 7.53 – 7.48 (m, 2H), 7.37 – 7.32 (m,
2H), 7.31 – 7.26 (m, 3H), 7.25 – 7.20 (m, 2H), 4.63 (dd, J = 7.7, 6.7 Hz, 1H), 3.24 (dd, J = 12.7,
7.9 Hz, 1H), 3.17 (dd, J = 12.7, 6.5 Hz, 1H). 13C NMR (125 MHz, CDCl3) δ (ppm): 137.2, 134.5,
133.4, 129.3, 129.14, 129.06, 128.3, 127.6, 65.3, 33.9. MS (ESI): m/z (%) 354 (M+18). HRMS:
m/z calcd for C14H16N4ClSe [M+18]: 355.0229; found: 355.0201.
(2-azidocyclohexyl)(phenyl)selane 3g
Pale yellow oil.15
IR (neat): 2095 cm-1. 1H NMR (500 MHz, CDCl3) δ (ppm): 7.66 – 7.61 (m, 2H), 7.37 – 7.26 (m,
3H), 3.30 (td, J = 9.9, 4.0 Hz, 1H), 3.06 (td, J = 10.3, 4.0 Hz, 1H), 2.19 – 2.08 (m, 2H), 1.84 –
1.59 (m, 2H), 1.52 – 1.35 (m, 2H), 1.32 – 1.22 (m, 2H). 13C NMR (125 MHz, CDCl3) δ (ppm):
135.9, 129.0, 128.0, 127.7, 64.5, 47.0, 32.9, 31.7, 25.8, 23.9. MS (ESI): m/z (%) 298 (M+18).
HRMS: m/z calcd for C12H19N4Se [M+18]: 299.0775; found: 299.0771.
(2-azido-2-phenylethyl)(benzyl)selane 3h
Pale yellow oil.
IR (neat): 2100 cm-1. 1H NMR (500 MHz, CDCl3) δ (ppm): 7.45 – 7.32 (m, 5H), 7.31 – 7.22 (m,
5H), 4.48 (dd, J = 8.1, 6.4 Hz, 1H), 3.76 (s, 2H), 2.91 – 2.84 (m, 1H), 2.78 (dd, J = 13.0, 6.2 Hz,
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1H). 13C NMR (125 MHz, CDCl3) δ (ppm): 138.8, 133.3, 129.4, 129.3, 128.9, 128.7, 127.5,
126.9, 66.0, 34.0, 21.3. MS (ESI): m/z (%) 334 (M+18). HRMS: m/z calcd for C15H19N4Se
[M+18]: 335.0775; found: 335.0742.
(2-azido-2-(4-tolyl)ethyl)(benzyl)selane 3i
Pale yellow oil.
IR (neat): 2101 cm-1. 1H NMR (500 MHz, CDCl3) δ (ppm): 7.37 – 7.24 (m, 5H), 7.23 – 7.20 (m,
2H), 7.18 – 7.15 (m, 2H), 4.47 (dd, J = 7.8, 6.6 Hz, 1H), 3.78 (s, 2H), 2.88 (dd, J = 12.9, 8.2 Hz,
1H), 2.78 (dd, J = 12.9, 6.3 Hz, 1H), 2.40 (d, J = 6.8 Hz, 1H). 13C NMR (125 MHz, CDCl3) δ
(ppm): 138.9, 138.4, 135.9, 129.4, 128.9, 128.5, 126.9, 126.7, 66.6, 29.4, 28.0, 21.1. MS (ESI):
m/z (%) 348 (M+18). HRMS: m/z calcd for C16H21N4Se [M+18]: 349.0931; found: 349.0913.
(2-azido-2-(4-chlorophenyl)ethyl)(benzyl)selane 3j
Pale yellow oil.
IR (neat): 2103 cm-1. 1H NMR (500 MHz, CDCl3) δ (ppm): 7.37 – 7.32 (m, 3H), 7.32 – 7.25 (m,
4H), 7.20 – 7.15 (m, 2H), 4.42 (dd, J = 7.7, 6.6 Hz, 1H), 3.78 (s, 2H), 2.83 (dd, J = 12.9, 7.9 Hz,
1H), 2.73 (dd, J = 12.9, 6.4 Hz, 1H). 13C NMR (125 MHz, CDCl3) δ (ppm): 138.8, 137.5, 134.4,
129.3, 129.0, 128.7, 128.3, 128.2, 127.0, 66.1, 29.4, 28.2. MS (ESI): m/z (%) 368 (M+18).
HRMS: m/z calcd for C15H18N4ClSe [M+18]: 369.0385; found: 369.0379.
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Table 1. Optimization of azidoselenenylation of styrene using KI as catalyst
N
3
-
I , mCPBA
Se
Se
NaN
3
+
Se
Solvent, 24h, r.t.
Ph
3a
1a
2a
Entr
y
mCPBA
I- (equiv.)
NaN3
Solvent
Yield
(%)a
(equiv.)
(equiv.)
1.5
1
2
3
4
5
6
7
1.2
1.2
1.2
1.2
1.2
1.2
1.2
KI (0.1)
-
MeCN
MeCN
CH2Cl2
DMF
24
3
1.5
KI (0.1)
KI (0.1)
KI (0.1)
KI (0.1)
KI (0.1)
1.5
12
-
1.5
1.5
THF
-
1.5
MeCN/H2O (10/1)
57
42
1.5
MeCN/AcOH
(10/1)
8
1.2
KI (0.1)
1.5
13
MeCN/MeOH
50
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(10/1)
9
1.2
KI (0.1)
1.5
MeCN/CF3CH2OH
(10/1)
49
10
11
12
13
14
15
16
17
18
19
20
21
22
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.5
KI (0.1)
KI (0.1)
KI (0.1)
KI (0.1)
KI (0.1)
KI (0.1)
KI (0.1)
KI (0.1)
NH4I (0.1)
PhI (0.1)
C3H7I(0.1)
KI (0.2)
KI (0.1)
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
MeCN/H2O (5/1)
MeCN/H2O (5/2)
MeCN/H2O (5/3)
MeCN/H2O (5/4)
MeCN/H2O (1/1)
MeCN/H2O (5/6)
MeCN/H2O (5/7)
MeCN/H2O (5/8)
MeCN/H2O (5/6)
MeCN/H2O (5/6)
MeCN/H2O (5/6)
MeCN/H2O (5/6)
MeCN/H2O (5/6)
56
59
62
74
77
80
75
70
70
31
41
75
68
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23
24
25
1.2
1.2
1.2
KI (0.1)
KI (0.1)
KI (0.1)
2.0
2.5
3.0
MeCN/H2O (5/6)
MeCN/H2O (5/6)
MeCN/H2O (5/6)
45
69
51
a Isolated yield.
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Table 2 The result of KI catalyzed azidoselenenylation of alkenes
Entry
1
Alkene
Diselenide
Product
Yield(%
a
)
PhSeSePh 2a
N
3
1a
Se
80
3a
2
3
1b
N
3
Se
52
61
2a
2a
3b
N
3
1c
SePh3c
N3
Se
4
5
57
2a
O
O
3d
1d
1e
1f
N
3
Se
2a
2a
65
56
F
3e
3f
6
N3
Se
Cl
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7
1g
N3
Se
2a
3g
3h
48
51
8
9
1a
N3
Se
PhCH2SeSeC
H2Ph 2b
71
47
1b
1f
2b
2b
N
3
Se
3i
10
N
3
Se
3j
Cl
a Isolated yields.
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N
3
2
KI (cat.), mCPBA
R
Se
+
1
NaN
Se
2
3
R
Se
2
R
1
R
MeCN/H O, 24h, r.t.
R
2
1
2
3
Scheme 1 KI catalyzed azidoselenenylation of alkenes
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Se
R2
R2
Se
I
2
Se
R2
R1
R2
Se
( I+ )
HOI
A
B
R2
Se
mCBA
1
N3
R1
C
Se
I
R2
I-
R1
N3
R1
1
mCPBA
SeR2
3
Scheme 2 Proposed mechanism for the catalyzed azidoselenenylation of alkenes
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