Novel and convenient acetoxyselenenylation of alkenes catalyzed by potassium iodide

Article abstract of DOI:10.1016/j.jorganchem.2014.10.025

With KI as catalyst and m-chloroperbenzoic acid as the oxidant in acetic acid, a novel and efficient catalytic procedure has been developed for acetoxyselenenylation of alkenes, which providing a series of 2-acetoxy-1-selenenylation compounds with high regioselectivity and good yields in mild conditions. In this protocol, KI is first oxidized by m-chloroperbenzoic acid into acetylhypoiodite, which rapidly reacts with diselenide to form the active electrophilic selenenylating reagent, following an electrophilic addition of alkenes and 2-acetoxy-1-selenenylation compounds are obtained. The suitable equivalent ratio of alkene to diselenide is 1.2.

Full text of DOI:10.1016/j.jorganchem.2014.10.025

Journal of Organometallic Chemistry 776 (2015) 117e122
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Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Novel and convenient acetoxyselenenylation of alkenes catalyzed by
potassium iodide
,
*
Hongwei Shi a, Chen Yu a, Min Zhu b, Jie Yan a
a College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, Zhejiang, PR China
b College of Biological and Environmental Sciences, Zhejiang Shuren University, Hangzhou 310015, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
With KI as catalyst and m-chloroperbenzoic acid as the oxidant in acetic acid, a novel and efficient
catalytic procedure has been developed for acetoxyselenenylation of alkenes, which providing a series of
2-acetoxy-1-selenenylation compounds with high regioselectivity and good yields in mild conditions. In
this protocol, KI is first oxidized by m-chloroperbenzoic acid into acetylhypoiodite, which rapidly reacts
with diselenide to form the active electrophilic selenenylating reagent, following an electrophilic addi-
tion of alkenes and 2-acetoxy-1-selenenylation compounds are obtained. The suitable equivalent ratio of
alkene to diselenide is 1.2.
Received 20 July 2014
Received in revised form
9 October 2014
Accepted 21 October 2014
Available online 30 October 2014
Keywords:
Acetoxyselenenylation
Diselenide
© 2014 Elsevier B.V. All rights reserved.
Alkene
Potassium iodide
Catalysis
Introduction
electrophilic selenium species to alkenes proceeded smoothly [9].
Several further modifications of this reaction have recently been
The oxyselenenylation reaction is a very useful procedure for the
anti-l, 2-addition of an organylseleno group and an oxygen sub-
stituent (HO, RO, RCO2) to an olefin [1]. The prepared products can
also be transformed to the double-bond transpositioned allylic al-
cohols and ethers by oxidative deselenenylation sequence [2]. In
the electrophilic addition, the most common selenenylating re-
agents PhSeX (X ¼ Cl, Br) are usually commercially available, they
are also prepared from oxidative cleavage of diphenyl diselenide by
halogens [3]. However, the presence of toxic and moisture-sensitive
nature of PhSeX, and the nucleophilic halide anions are sometimes
responsible for some undesirable processes such as addition of the
halide ion and the decrease in stereoselectivity, some new alter-
native methods have been developed such as cupric catalytic
oxidation [4], electrolytic oxidation [2c,5] and photoelectron
transfer [6]. Other production of the electrophilic phenylselenium
cation can be effected by the reaction of diphenyl diselenide with
ammonium peroxydisulfate [7] and m-nitrobenzenesulfonyl
peroxide [8]. Using hypervalent iodine reagent PhI(OAc)2, Tingoli
and co-workers reported the successful oxidative cleave the SeeSe
bond, and the electrophilic addition of the in situ generated reactive
reported [10]. However, the catalytic oxyselenenylation using
hypervalent iodine reagents as catalysts is developed rarely.
We have been interesting in oxidation and functionalization
of organic compounds using hypervalent iodine reagents, espe-
cially the catalytic utilization of hypervalent iodine reagents in
organic synthesis. In our new research, we have found that some
inorganic iodides or molecular iodine can be used to replace
hypervalent iodine reagents and the similar results have been
obtained [11]. Recently, we have investigated the acetox-
yselenenylation of alkenes with a catalytic amount hypervalent
iodine reagent. In a parallel study, we found that when the
hypervalent iodine reagent was replaced by KI, the acetox-
yselenenylation of alkenes was carried out fluently with high
regioselectivity and yields in mild conditions. Herein, we wish to
report the novel and convenient acetoxyselenenylation of al-
kenes using KI as catalyst and m-chloroperbenzoic acid as the
terminal oxidant, and to our knowledge this method has not
been reported before.
Discussion and results
Initially, NH4I was used as representative of inorganic iodides to
attempt the novel catalytic acetoxyselenenylation of alkenes. When
* Corresponding author. Fax: þ86 571 88320238.
E-mail address: jieyan87@zjut.edu.cn (J. Yan).
http://dx.doi.org/10.1016/j.jorganchem.2014.10.025
0022-328X/© 2014 Elsevier B.V. All rights reserved.

118
H. Shi et al. / Journal of Organometallic Chemistry 776 (2015) 117e122
0.2 equiv. of NH4I was added to the mixture of 1.0 equiv. of diphenyl
diselenide (2a), 1.2 equiv. of m-chloroperbenzoic acid (mCPBA) and
1.5 equiv. of styrene (1a) in acetic acid (AcOH), it was found that the
novel acetoxyselenenylation occurred smoothly at room tempera-
ture and after 6 h it afforded the predominated Markovnikov
addition product, 1-phenyl-2-(phenylselanyl)ethyl acetate (3a) in
70% yield (Table 1, entry 1). If NH4I was absent, a parallel experi-
ment gave only 5% yield of 3a (entry 2). Therefore, it was obvious
that NH4I played a key action in the reaction.
completed in only 2 h (entries 17, 22e25). Finally, the amount of
styrene was also checked, and 1.2 equiv. of it was optimal for the
reaction (entries 26e28).
With the optimal conditions in hand, in order to assess the
scope of this method, several alkenes 1 (1.2 equiv.) were treated
with mCPBA (1.0 equiv.) and diselenide 2 (1.0 equiv.) in the
presence of KI (0.2 equiv.) in AcOH for 2 h, a series of 2-acetoxy-1-
selenenylation compounds, most new compounds were prepared
(Table 2).
In light of the successful formation of 3a in the presence of NH4I,
the reaction conditions were optimized and the results are sum-
marized in Table 1. Firstly, several mixture solvents of acetic acid
were used in the reaction, however, the yields were low (Table 1,
entries 3e6). When CH2Cl2, CH3CN and H2O were used as sole
solvent respectively, and 3.0 equiv. of AcOH was added in the re-
action, the rather poor yields were determined (entries 7e9). When
NaOAc took the place of AcOH as nucleophilic reagent in CH3CN, no
the desired product was observed (entry 10). With AcOH as the
suitable solvent, two iodides NaI and KI were compared with NH4I,
and KI was the most effective one among them (entries 1, 11 and
12). Other oxidants, such as Oxone® and NaBO3$4H2O were active
in the reaction, normally resulted in good yields (entries 13 and 14).
The yields of 3a dropped down when the amount of mCPBA was
more or less then 1.0 equiv. due to the excess oxidant could lead to
As shown in Table 2, the reaction was compatible with most of
the studied alkenes except 2-methyl-3-buten-2-ol (1k), which
provided the corresponding 2-acetoxy-1-selenenylation com-
pounds in good to excellent yields (entries 1e11). It was also found
that the groups on the benzene ring, no matter they were electron-
donating or electron-withdrawing groups, did not influence on the
yield (entries 2e7). Cyclohexene (1i) and bicyclo[2.2.1]hept-2-ene
(1j), when they were treated under the same conditions, the
addition proceeded in a trans fashion and single stereoisomers
were isolated with excellent yields (entries 9 and 10). Compared
with 2a, dibenzyl diselenide (2b), an aliphatic diselenide also
reacted easily with alkenes, but the yields slightly dropped down
(entries 12e14).
Based on the remarkably catalytic effect of KI in the acetox-
yselenenylation of alkenes, a plausible reaction pathway is sug-
gested in Scheme 1 [2c,5]. Thus, KI is first oxidized by mCPBA to
the corresponding acetylhypoiodite A, which reacts smoothly
with diselenide 2 to form the active intermediate B [13], following
a rapid cleavage of SeeSe bond, the electrophilic selenium species
elimination reaction to produce the vinylic acetate a-acetoxystyr-
ene (entries 12, 15e19) [2,12]. The amount of KI was investigated
and 0.2 equiv. was the best choice (entries 17, 20 and 21). As the
results showed that the reaction proceeded rapidly and it was
Table 1
Optimization of the acetoxyselenenylation of alkenes using KI as catalyst.
OAc
I-, Oxidant
Solvent, r.t.
Se
Se
+
Se
3a
1a
2a
Entry
Styrene (equiv.)
Oxidant (equiv.)
Iꢀ (equiv.)
Solvent
Time (h)
Yield (%)a
1
2
3
4
5
6
7
8
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
1.5
mCPBA (1.2)
mCPBA (1.2)
mCPBA (1.2)
mCPBA (1.2)
mCPBA (1.2)
mCPBA (1.2)
mCPBA (1.2)
mCPBA (1.2)
mCPBA (1.2)
mCPBA (1.2)
mCPBA (1.2)
mCPBA (1.2)
Oxone (1.2)
NaBO3.4H2O
(1.2)
NH4I (0.2)
e
AcOH
AcOH
6
6
6
6
6
6
6
6
6
6
6
6
6
6
70
5
NH4I (0.2)
NH4I (0.2)
NH4I (0.2)
NH4I (0.2)
NH4I (0.2)
NH4I (0.2)
NH4I (0.2)
NH4I (0.2)
NaI (0.2)
KI (0.2)
AcOH-CH2Cl2 (1:1)
AcOH-CH3CN (1:1)
AcOH-H2O (1:1)
AcOH-EtOAc (1:1)
CH2Cl2
CH3CN
H2O
CH3CN
AcOH
54
47
20
52
15b
11b
0b
9
10
11
12
13
14
0c
87
90
89
80
AcOH
AcOH
AcOH
KI (0.2)
KI (0.2)
15
16
17
18
19
20
21
22
23
24
25
26
27
28
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.3
1.2
1.0
mCPBA (2.0)
mCPBA (1.5)
mCPBA (1.0)
mCPBA (0.8)
mCPBA (0.6)
mCPBA (1.0)
mCPBA (1.0)
mCPBA (1.0)
mCPBA (1.0)
mCPBA (1.0)
mCPBA (1.0)
mCPBA (1.0)
mCPBA (1.0)
mCPBA (1.0)
KI (0.2)
KI (0.2)
KI (0.2)
KI (0.2)
KI (0.2)
KI (0.3)
KI (0.15)
KI (0.2)
KI (0.2)
KI (0.2)
KI (0.2)
KI (0.2)
KI (0.2)
KI (0.2)
AcOH
AcOH
AcOH
AcOH
AcOH
AcOH
AcOH
AcOH
AcOH
AcOH
AcOH
AcOH
AcOH
AcOH
6
6
6
6
6
6
6
2
1.5
1
0.5
2
2
2
38
78
94
88
71
94
89
95
92
86
71
95
95
84
a
Isolated yields.
3.0 equiv. HOAc was added.
3.0 equiv. NaOAc was added in CH3CN.
b
c

H. Shi et al. / Journal of Organometallic Chemistry 776 (2015) 117e122
119
reacts with alkene to produce the unstable cyclic intermediate C.
The in situ generated active ArSeI [14] can further transfer a sec-
ond equivalent of electrophilic selenium to alkenes to form the
cyclic intermediate C. After a solvolysis of C in AcOH, the desired
product 2-acetoxy-1-selenenylation compound 3 as a single iso-
mer is obtained via an SN1 mechanism for the aromatic alkenes.
When aliphatic alkenes such as 1i and 1j are used as alkene
substrates, the reaction provides the trans single stereoisomers via
an SN2 mechanism, which supports the first formation of the cy-
clic selenium intermediate C, then acetate anion attacks the cyclic
intermediate affording the corresponding anti-l, 2-addition
products 3.
Table 2
Preparation of 2-acetoxy-1-selenenylation compounds 3.
OAc
KI, m-CPBA
R2
Se
+
R1
R2
Se
Se
AcOH, 2h, r.t.
R2
R1
1
2
3
Entry
1
Alkene 1
Diselenide 2
Product 3
Yield (%)a
95
OAc
Se
Se
Se
1a
3a
2a
2a
2
3
93
92
OAc
Se
1b
3b
2a
2a
OAc
O
Se
O
O
1c
O
3c
4
88
OAc
Se
1d
3d
5
6
7
2a
2a
2a
91
84
91
OAc
Se
F
1e
F
3e
OAc
OAc
Se
Cl
1f
Cl
3f
Se
Br
1g
Br
3g
8
2a
2a
2a
2a
67
90
86
47
72
OAc
Se
N
1h
N
3h
3i
9
OAc
Se
1i
10
11
12
OAc
Se
1j
3j
OH
OH
Se
1k
OAc
3k
1a
1b
1f
OAc
Se
Se
Se
2b
2b
3l
13
14
87
70
OAc
Se
3m
2b
OAc
Se
Cl
3n
a
Isolated yields.

120
H. Shi et al. / Journal of Organometallic Chemistry 776 (2015) 117e122
IR (KBr) n .
: 3061, 3033, 1742, 1371, 1236, 1020, 738, 698 cmꢀ1
MS (ESI): m/z (%) 320 (Mþ, 1.8), 261 (100).
2-(phenylselanyl)-1-p-tolylethyl acetate (3b)
Yield: 93%; colorless viscous oil.
1H NMR (500 MHz, CDCl3)
d (ppm): 7.64e7.42 (m, 2H), 7.28 (dd,
J ¼ 4.9, 1.7 Hz, 3H), 7.24 (d, J ¼ 8.1 Hz, 2H), 7.17 (d, J ¼ 8.0 Hz, 2H),
5.93 (dd, J ¼ 7.9, 5.9 Hz, 1H), 3.40 (dd, J ¼ 12.8, 8.0 Hz, 1H), 3.24 (dd,
J ¼ 12.8, 5.9 Hz, 1H), 2.36 (s, 3H), 2.02 (s, 3H).
13C NMR (125 MHz, CDCl3)
d (ppm): 170.1, 138.3, 136.5, 133.1,
129.9, 129.3, 129.1, 127.2, 126.7, 75.2, 33.3, 21.2, 21.1.
IR (KBr) : 3055, 3027, 1742, 1370, 1236, 1020, 816, 738,
692 cmꢀ1
n
.
MS (EI): m/z (%) 334 (Mþ, 6.5), 194 (100).
HRMS: m/z [M]þ calcd for C17H18O2Se: 334.0472; found:
334.0451.
Scheme 1. Proposed mechanism for the acetoxyselenenylation of alkenes using KI as
catalyst.
4-(1-acetoxy-2-(phenylselanyl)ethyl)phenyl acetate (3c)
Yield: 92%; pale yellow viscous oil.
Conclusions
1H NMR (500 MHz, CDCl3)
d (ppm): 7.54e7.48 (m, 2H),
7.37e7.33 (m, 2H), 7.27e7.23 (m, 3H), 7.09e7.04 (m, 2H), 5.96e5.92
(m, 1H), 3.41e3.34 (m, 1H), 3.21 (dd, J ¼ 12.9, 5.7 Hz, 1H), 2.31 (s,
3H), 2.02 (s, 3H).
We have developed a novel and efficient catalytic processor for
synthesis of 2-acetoxy-1-selenenylation compounds by the elec-
trophilic addition of alkenes with diselenides and mCPBA in the
presence of catalytic amount of KI in AcOH at room temperature.
This method has some advantages such as mild reaction conditions
and simple procedure, which provided a series of 2-acetoxy-1-
selenenylation 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 syn-
thesis. Other convenient anti-l, 2-addition of an organylseleno
group and an oxygen substituent to unsaturated functions will be
reported in due course.
13C NMR (125 MHz, CDCl3)
d
(ppm): 169.9, 169.3, 150.6, 137.0,
133.2, 129.7, 129.2, 127.9, 127.3, 121.7, 74.6, 33.3, 21.1, 21.0.
IR (KBr)
: 3056, 1761, 1369, 1198, 1018, 840, 737, 691 cmꢀ1
MS (EI): m/z (%) 378 (Mþ, 2.8), 123 (100).
HRMS: m/z [M]þ calcd for C18H18O4Se: 378.0370; found:
378.0362.
n
.
1-(4-tert-butylphenyl)-2-(phenylselanyl)ethyl acetate (3d)
Yield: 88%; colorless viscous oil.
1H NMR (500 MHz, CDCl3)
d (ppm): 7.52e7.50 (m, 2H),
7.37e7.36 (m, 2H), 7.29e7.26 (m, 5H), 5.96 (dd, J ¼ 8.0, 5.7 Hz, 1H),
3.40 (dd, J ¼ 12.8, 8.1 Hz, 1H), 3.25 (dd, J ¼ 12.8, 5.6 Hz, 1H), 2.03 (s,
3H), 1.33 (s, 9H).
Experimental
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 and AcOH (AR, 99.5%) were commercially available.
13C NMR (125 MHz, CDCl3)
d
(ppm): 170.0, 151.4, 136.4, 133.1,
130.0, 129.1, 127.2, 126.4, 125.4, 75.1, 34.6, 33.4, 31.3, 21.0.
IR (KBr) : 3057, 2963, 1745, 1370.0, 1235, 1021, 828, 737,
691 cmꢀ1
n
.
MS (EI): m/z (%) 376 (Mþ, 14.1), 219 (100).
HRMS: m/z [M]þ calcd for C20H24O2Se: 376.0942; found:
376.0916.
A typical procedure for acetoxyselenenylation of alkenes using KI as
catalyst
1-(4-fluorophenyl)-2-(phenylselanyl)ethyl acetate (3e)
Yield: 91%; colorless viscous oil.
1H NMR (500 MHz, CDCl3)
d (ppm): 7.59e7.45 (m, 2H),
In AcOH (1 mL), alkene 1 (0.24 mmol), diselenide 2 (0.1 mmol),
KI (0.02 mmol) and m-CPBA (0.1 mmol) were added successively.
The suspension mixture was vigorously stirred at r. t. for 2 h. Upon
completion, the reaction was quenched by addition of sat. aq.
Na2S2O3 (2 mL), basified with sat. aq. Na2CO3 (8 mL) and H2O
(5 mL). 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 (4:1 petroleum ether-ethyl acetate) to
furnish 2-acetoxy-1-selenenylation compound 3.
7.36e7.29 (m, 2H), 7.27e7.26 (m, 3H), 7.08e6.97 (m, 2H), 5.92 (dd,
J ¼ 7.5, 6.2 Hz, 1H), 3.38 (dd, J ¼ 12.9, 7.7 Hz, 1H), 3.21 (dd, J ¼ 12.8,
6.1 Hz, 1H), 2.02 (s, 3H).
13C NMR (125 MHz, CDCl3)
d (ppm): 170.0, 164.5, 162.1, 135.2 (d,
J ¼ 3.2 Hz), 133.2 (d, J ¼ 5.3 Hz), 129.6, 129.2, 128.6 (d, J ¼ 8.2 Hz),
127.4, 115.5 (d, J ¼ 21.6 Hz), 74.7, 33.3, 21.0.
IR (KBr) n .
: 3057, 1743, 1371, 1225, 1021, 836, 738, 691 cmꢀ1
MS (EI): m/z (%) 338 (Mþ, 19.7), 198 (100).
HRMS: m/z [M]þ calcd for C16H15FO2Se: 338.0221; found:
338.0219.
1-phenyl-2-(phenylselanyl)ethyl acetate (3a) [9d]
Yield: 95%; colorless viscous oil.
1-(4-chlorophenyl)-2-(phenylselanyl)ethyl acetate (3f)
1H NMR (500 MHz, CDCl3)
d
(ppm): 7.52 (dd, J ¼ 6.5, 2.9 Hz, 2H),
Yield: 84%; pale yellow viscous oil.
7.39e7.30 (m, 5H), 7.30e7.24 (m, 3H), 5.96 (dd, J ¼ 8.0, 5.7 Hz, 1H),
3.40 (dd, J ¼ 12.9, 8.0 Hz, 1H), 3.25 (dd, J ¼ 12.9, 5.7 Hz, 1H), 2.04 (s,
3H).
1H NMR (500 MHz, CDCl3)
d (ppm): 7.54e7.44 (m, 2H),
7.33e7.29 (m, 2H), 7.29e7.20 (m, 5H), 5.93e5.85 (m, 1H), 3.42e3.30
(m, 1H), 3.26e3.14 (m, 1H), 2.02 (s, 3H).
13C NMR (125 MHz, CDCl3)
d
(ppm): 170.0, 139.4, 133.1, 129.8,
13C NMR (125 MHz, CDCl3)
d
(ppm): 169.9, 137.8, 134.2, 133.2,
129.1, 128.5, 128.4, 127.2, 126.6, 75.2, 33.4, 21.0.
129.5, 129.2, 128.7, 128.1, 127.4, 74.6, 33.1, 21.0.

H. Shi et al. / Journal of Organometallic Chemistry 776 (2015) 117e122
121
IR (KBr)
MS (EI): m/z (%) 354 (Mþ, 11.2), 214 (100).
HRMS: m/z [M]þ calcd for C16H15ClO2Se: 353.9926; found:
353.9902.
n
: 3057, 1741, 1371, 1235, 1051, 1016, 824, 738, 692 cmꢀ1
.
HRMS: m/z [M]þ calcd for C13H18O3Se: 302.0421; found:
302.0399.
2-(benzylselanyl)-1-phenylethyl acetate (3l)
Yield: 72%; pale yellow viscous oil.
1H NMR (500 MHz, CDCl3)
d (ppm): 7.50e7.09 (m,10H), 5.83 (dd,
1-(4-bromophenyl)-2-(phenylselanyl)ethyl acetate (3g)
Yield: 91%; pale yellow viscous oil.
J ¼ 7.6, 6.3 Hz, 1H), 3.67 (d, J ¼ 2.4 Hz, 2H), 2.92 (dd, J ¼ 13.0, 7.7 Hz,
1H NMR (500 MHz, CDCl3)
d (ppm): 7.50e7.45 (m, 4H),
1H), 2.78 (dd, J ¼ 13.0, 6.2 Hz, 1H), 2.09 (s, 3H).
13C NMR (125 MHz, CDCl3)
d (ppm): 169.9, 139.7, 138.9, 129.0,
7.28e7.26 (m, 3H), 7.21e7.19 (m, 2H), 5.93e5.82 (m, 1H), 3.43e3.29
(m, 1H), 3.28e3.13 (m, 1H), 2.02 (s, 3H).
128.5, 128.3, 126.9, 126.7, 75.5, 29.0, 27.8, 21.1.
IR (KBr)
: 3061, 3029, 1739, 1371, 1237, 1018, 758, 698 cmꢀ1
MS (ESI): m/z (%) 334 (Mþ, 3.1), 336 (100).
HRMS: m/z [M]þ calcd for C17H18O2Se: 334.0472; found:
334.0439.
13C NMR (125 MHz, CDCl3)
d
(ppm): 169.9, 138.3, 133.2, 131.6,
129.5, 129.2, 128.4, 127.4, 122.4, 74.7, 33.1, 21.0.
IR (KBr)
: 3056, 1741, 1481, 1072, 1007, 823, 736, 690 cmꢀ1
MS (EI): m/z (%) 398 (Mþ, 58.5), 338 (100).
HRMS: m/z [M]þ calcd for C16H15BrO2Se: 397.9421; found:
397.9413.
n
.
n
.
2-(benzylselanyl)-1-p-tolylethyl acetate (3m)
Yield: 87%; pale yellow viscous oil.
2-(phenylselanyl)-1-(pyridin-2-yl)ethyl acetate (3h)
1H NMR (500 MHz, CDCl3)
d (ppm): 7.33e7.17 (m, 9H), 5.83 (dd,
Yield: 67%; colorless viscous oil.
J ¼ 7.5, 6.5 Hz, 1H), 3.72 (d, J ¼ 3.2 Hz, 2H), 2.95 (dd, J ¼ 12.9, 7.7 Hz,
1H NMR (500 MHz, CDCl3)
d (ppm): 8.59e8.53 (m, 1H), 7.67 (td,
1H), 2.80 (dd, J ¼ 12.9, 6.3 Hz, 1H), 2.36 (s, 3H), 2.10 (s, 3H).
J ¼ 7.7, 1.8 Hz, 1H), 7.58e7.45 (m, 2H), 7.33 (d, J ¼ 7.8 Hz, 1H),
7.29e7.21 (m, 4H), 6.14e5.96 (m, 1H), 3.52 (d, J ¼ 6.0 Hz, 1H), 3.49
(d, J ¼ 7.0 Hz, 1H), 2.05 (s, 3H).
13C NMR (125 MHz, CDCl3)
d (ppm): 169.9, 139.0, 138.1, 136.7,
129.2, 129.0, 128.5, 126.8 (d, J ¼ 19.7 Hz), 75.4, 29.0, 27.8, 21.2.
IR (KBr)
: 3059, 3027, 1741, 1370, 1237, 1018, 817, 759, 698 cmꢀ1
MS (ESI): m/z (%) 348 (Mþ, 3.5), 369 (100).
HRMS: m/z [M]þ calcd for C18H20O2Se: 348.0629; found:
348.0602.
n
.
13C NMR (125 MHz, CDCl3)
d (ppm): 170.2, 157.8, 149.5, 136.6,
133.0, 129.8, 129.1, 127.1, 123.2, 122.1, 75.7, 31.4, 21.0.
IR (KBr)
: 3056, 1739, 1371, 1234, 1022, 739, 692 cmꢀ1
MS (EI): m/z (%) 321 (Mþ, 4.8), 183 (100).
HRMS: m/z [M]þ calcd for C15H15NO2Se: 321.0268; found:
321.0233.
n
.
2-(benzylselanyl)-1-(4-chlorophenyl)ethyl acetate (3n)
Yield: 70%; colorless viscous oil.
1H NMR (500 MHz, CDCl3)
d (ppm): 7.35e7.12 (m, 9H),
2-(phenylselanyl)cyclohexyl acetate (3i) [9d]
5.82e5.66 (m, 1H), 3.77e3.62 (m, 2H), 2.89 (dd, J ¼ 13.0, 7.6 Hz, 1H),
Yield: 90%; colorless viscous oil.
1H NMR (500 MHz, CDCl3)
d (ppm): 7.68e7.49 (m, 2H), 7.28 (m,
2.74 (dd, J ¼ 13.0, 6.4 Hz, 1H), 2.08 (s, 3H).
13C NMR (125 MHz, CDCl3)
d (ppm): 169.8, 138.7, 138.2, 134.2,
3H), 4.95e4.78 (m, 1H), 3.33e3.10 (m, 1H), 2.22e2.05 (m, 2H), 1.96
(s, 3H), 1.79e1.61 (m, 2H), 1.54e1.29 (m, 4H).
129.0, 128.7, 128.6, 128.1, 126.9, 74.7, 28.7, 27.9, 21.1.
IR (KBr) : 3061, 3028, 1739, 1371, 1236, 1015, 825, 759,
698 cmꢀ1
13C NMR (125 MHz, CDCl3)
d
(ppm): 170.3, 135.0, 128.9, 128.7,
127.6, 75.4, 46.1, 32.3, 31.8, 25.8, 23.6, 21.1.
IR (KBr) : 3056, 2936, 2858, 1738, 1373, 1238, 1036, 741,
693 cmꢀ1
n
.
MS (ESI): m/z (%) 369 (Mþ þ 1, 15.0), 289 (100).
n
HRMS: m/z [M]þ calcd for C17H17ClO2Se: 368.0082; found:
.
MS (EI): m/z (%) 298 (Mþ, 4.5), 81 (100).
368.0058.
3-(phenylselanyl)bicyclo[2.2.1]heptan-2-yl acetate (3j)
Acknowledgment
Yield: 86%; colorless viscous oil.
1H NMR (500 MHz, CDCl3)
d (ppm): 7.61e7.45 (m, 2H), 7.29e7.25
(m, 3H), 5.08e4.88 (m, 1H), 3.09 (t, J ¼ 3.3 Hz, 1H), 2.62e2.60 (m,
1H), 2.30 (d, J ¼ 3.9 Hz, 1H), 2.01 (s, 3H), 1.93e1.70 (m, 2H),
1.70e1.59 (m, 2H), 1.45e1.38 (m, 2H).
Financial support from the National Natural Science Foundation
of China (Project 21072176) is greatly appreciated.
References
13C NMR (125 MHz, CDCl3)
d
(ppm): 170.4, 133.6, 130.1, 129.0,
127.2, 82.2, 49.5, 43.5, 41.3, 35.7, 29.9, 20.9, 20.2.
IR (KBr)
: 3056, 2963, 1738, 1374, 1235, 1036, 738, 692 cmꢀ1
MS (EI): m/z (%) 310 (Mþ, 18.0), 91 (100).
HRMS: m/z [M]þ calcd for C15H18O2Se: 310.0472; found:
310.0466.
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n
.
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d
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692 cmꢀ1
MS (EI): m/z (%) 302 (Mþ, 2.5), 184 (100).
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