New Catalytic Method for the Synthesis of β-Hydroxy Selenides

Article abstract of DOI:10.1002/hlca.201600115

In the presence of NH₄I as catalyst and m-chloroperbenzoic acid as oxidant, the Se–Se bond cleavage of diselenides undergoes smoothly. The in?situ generated reactive electrophilic Se species reacts with alkenes quickly, and a series of β-hydroxy selenides are prepared in good yields. This new catalytic method for synthesis of β-hydroxy selenides is a stereospecific anti addition, which occurs with a Markovnikov orientation.

Full text of DOI:10.1002/hlca.201600115

Helv. Chim. Acta 2016, 99, 1 – 5
1
201600115
FULL PAPER
New Catalytic Method for the Synthesis of b-Hydroxy Selenides
by Yikun Zhang, Sixue Wu, and Jie Yan*
College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, P. R. China
(phone: +86(571)88320163; fax: +86(571)88320238; e-mail: jieyan87@zjut.edu.cn)
In the presence of NH4I as catalyst and m-chloroperbenzoic acid as oxidant, the Se–Se bond cleavage of diselenides
undergoes smoothly. The in situ generated reactive electrophilic Se species reacts with alkenes quickly, and a series of
b-hydroxy selenides are prepared in good yields. This new catalytic method for synthesis of b-hydroxy selenides is a
stereospecific anti addition, which occurs with a Markovnikov orientation.
Keywords: b-Hydroxy selenides, Hydroxyselenenylation, Diselenide, Alkenes, Catalysis.
corresponding zinc selenolate [34]. However, these gener-
ated in situ selenolate anions are relatively unstable, they
Introduction
In recent years, organoselenium compounds have been should be prepared under controlled anhydrous condi-
gaining importance due to their synthetic applications [1], tions, and above methods also have some disadvantages,
biological activities, and other properties [2 – 9]. Among such as long reaction times, the use of low temperatures,
them, b-hydroxy selenides is a kind of valuable intermedi-
ates in the synthesis of allylic alcohols [10], olefins [11],
bromohydrins [12], vinyl selenides [13][14], and some
low to poor yields of products and multistep procedures,
etc. Therefore, it is of significant interest to find mild and
simple, especially catalytic methods for the synthesis of b-
important natural compounds [15 – 17]. Several methods hydroxy selenides.
are available for the preparation of b-hydroxy selenides.
Recently, we have found that some inorganic haloid
The electrophilic addition of the commercially available salts can catalyze the Se–Se bond cleavage of diselenides
selenenylating reagent PhSeCl to alkenes is a useful pro-
cedure [18][19]. However, the presence of toxic and mois-
ture-sensitive nature of PhSeCl, and the nucleophilic ClÀ
in the present of suitable oxidants. With the in situ gener-
ated electrophilic Se species, some new electrophilic reac-
tions have been reported [35 – 37]. Based on the success,
anion is sometimes responsible for some undesirable pro- we have investigated the new synthetic method for prepa-
cesses, such as addition of the halide ion and the decrease
in stereoselectivity. For this purpose, some novel alterna-
tive reagents, which do not contain nucleophilic counteri-
ration of b-hydroxy selenides. Herein, we wish to report a
convenient hydroxyselenenylation of alkenes with dise-
lenides, m-chloroperbenzoic acid (mCPBA), and H2O
ons, such as PhSeOSO2Ar, N-phenylselenophtalimide, using NH4I as catalyst. To the best of our knowledge, this
and N-phenylselenosuccinimide, have been developed new catalytic method for synthesis of b-hydroxy selenides
[20 – 22]. Since diphenyl diselenide is less expensive and
less toxic, a simpler way for formation of the electrophilic
phenylselenium cation is oxidation of diphenyl diselenide
with oxidants, like DDQ, iodobenzene diacetate, or elec-
has not been previously reported.
Results and Discussion
trolytic system [23 – 25]. Using selenolate anions, the SN2 Initially, we investigated the hydroxyselenenylation of
ring opening of epoxides is another common method for styrene 1a with diphenyl diselenide 2a and oxidant mCPBA
access to b-hydroxy selenides. The selenolate anions can in the presence of a catalytic amount of KI at room tempera-
be generated by the treatment of diphenyl diselenide with
Na, Zn, NaBH4, zinc/aluminum (III) chloride,
tributylphosphine in an alkaline medium and sodium
hydroxymethanesulfinate [26 – 31]. They are also trans-
ture. It was found that only stirring the mixture of 1.0 equiv.
of 2a, 1.2 equiv. of 1a, and mCPBA with 0.1 equiv. of KI in a
mixed solvent of H2O (1.5 ml) and MeCN (1.5 ml) for 3 h,
the expected addition product 1-phenyl-2-(phenylselanyl)
formed from benzeneselenol under supramolecular cataly- ethanol 3a was obtained in 49% yield (Table 1, Entry 1).
sis in the presence of b-cyclodextrin [32] and promoted As a control experiment, 3a was not observed in the
by [Bmim]BF4 [33]. Treatment of commercially available absence of KI (Entry 2). Therefore, it was obvious that KI
PhSeX with Zn powder in refluxing THF can lead to the
played a key role in the reaction. Then, the catalytic
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DOI: 10.1002/hlca.201600115
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Helv. Chim. Acta 2016, 99, 1 – 5
hydroxyselenenylation of 1a with 1.0 equiv. of 2a at room
temperature for 3 h was optimized (Table 1).
Having established the optimum conditions, the
hydroxyselenenylation of 1.2 equiv. of alkenes 1 with 1.0
As shown in Table 1, several mixed solvents of H2O equiv. of diselenides 2, 1.0 equiv. of mCPBA, and 0.1
with CH2Cl2, DMF, THF, DMSO, and AcOEt (1:1 v/v) equiv. of NH4I in H2O/AcOEt (2:1 v/v) was carried out
were first evaluated. As a result, in H2O/AcOEt the reac- at room temperature for 3 h, and a series of correspond-
tion provided 3a in moderate yield of 50%, while other
mixed solvents or neat H2O usually resulted in poor or
low yields (Entries 3 – 8). The reaction in H2O/MeCN
ing b-hydroxy selenides 3 were obtained. The results are
summarized in Table 2.
As shown in Table 2, the reaction was compatible
(1:1 v/v) or in H2O/AcOEt (1:1 v/v) led closely to the with the studied alkenes, providing the corresponding b-
same result. However, with H2O/AcOEt (2:1 v/v), a bet- hydroxy selenides 3 in moderate to good yields when 2a
ter yield was observed (Entries 9 – 14). In the mixed sol- was used (Table 2, Entries 1 – 9). Dibenzyl diselenide 2b,
vent H2O/AcOEt (2:1 v/v), the suitable amount of 1a an aliphatic diselenide similar to 2a, also reacted with
was determined: 1.2 equiv. of it was the best choice
(Entries 12, 15 – 16). The appropriate amount of
mCPBA was 1.0 equiv., and when it increased or
decreased, the yields were not above 86% (Entries 12,
17 – 21). Compared with KI, NH4I had a better catalytic
effect to the reaction; other iodine-containing catalysts,
such as NaI and PhI, gave moderate to poor yields, and
alkenes, resulting in the corresponding products 3j – 3n in
similar yields (Entries 10 – 15). This hydroxyselenenyla-
tion is a regiospecific reaction; all the obtained b-hydroxy
selenides are Markovnikov orientation products. In order
to investigate the stereospecificity of this reaction, cyclo-
hexene 1h was selected to react with 2a and 2b, and the
obtained products 3h and 3n showed the trans stereoiso-
PrI had no catalytic effect at all (Entries 22 – 25). mer mixtures (Entries 8 and 15).
Finally, the optimum amount of NH4I was determined,
0.1 equiv. of it had the best effect to the reaction
(Entries 22, 26, and 27).
According to the above results, a proposed catalytic
cycle for the NH4I-mediated hydroxyselenenylation of
alkenes is shown in the Scheme. Thus, NH4I is first
Table 1. Optimization of the hydroxyselenenylation of styrene using NH4I as catalyst
Entry
Styrene (equiv.)
mCPBA (equiv.)
IÀ (equiv.)
H2O [ml]
Solvent [ml]
Yield [%]a)
1
2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
2.0
3.0
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.5
2.0
1.0
0.8
0.6
1.0
1.0
1.0
1.0
1.0
1.0
KI (0.1)
–
1.5
1.5
1.5
1.5
1.5
1.5
1.5
3.0
1.0
2.0
1.0
2.0
1.8
1.2
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
MeCN (1.5)
MeCN (1.5)
CH2Cl2 (1.5)
DMF (1.5)
49
0
3
KI (0.1)
KI (0.1)
KI (0.1)
KI (0.1)
KI (0.1)
KI (0.1)
KI (0.1)
KI (0.1)
KI (0.1)
KI (0.1)
KI (0.1)
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)
NaI (0.1)
PhI (0.1)
PrI (0.1)
NH4I (0.2)
NH4I (0.3)
12
21
44
19
50
38
58
42
62
73
56
68
71
73
39
10
86
81
79
92
65
12
0
4
5
THF (1.5)
6
DMSO (1.5)
AcOEt (1.5)
–
7
8
9
MeCN (2.0)
MeCN (1.0)
AcOEt (2.0)
AcOEt (1.0)
AcOEt (1.2)
AcOEt (1.8)
AcOEt (1.0)
AcOEt (1.0)
AcOEt (1.0)
AcOEt (1.0)
AcOEt (1.0)
AcOEt (1.0)
AcOEt (1.0)
AcOEt (1.0)
AcOEt (1.0)
AcOEt (1.0)
AcOEt (1.0)
AcOEt (1.0)
AcOEt (1.0)
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
85
83
a) Yield of isolated product.
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Helv. Chim. Acta 2016, 99, 1 – 5
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Table 2. Preparation of b-hydroxy selenides 3
Entry
Alkene (1)
R1
Diselenide (2)
R2
Product (3)
Yield [%]a)
1
2
1a
1b
1c
1d
1e
1f
1g
1h
1a
1b
1c
1f
Ph
2a
2a
2a
2a
2a
2a
2a
2a
2b
2b
2b
2b
2b
2b
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Bn
Bn
Bn
Bn
Bn
Bn
3a
3b
3c
3d
3e
3f
3g
3h
3i
92
71
68
69
62
59
61
58
89
71
72
55
50
58
4-Me–C6H4
4-AcO–C6H4
4-tBu–C6H4
4-F–C6H4
4-Cl–C6H4
4-Br–C6H4
3
4
5
6
7
8
9
Ph
10
11
12
13
14
4-Me–C6H4
4-AcO–C6H4
4-Cl–C6H4
4-Br–C6H4
3j
3k
3l
1g
1h
3m
3n
a) Yield of isolated products.
oxidized by mCPBA to the corresponding hypoiodous
a Bruker Avance III (500 MHz) spectrometer. Mass spec-
acid A, which reacts smoothly with diselenide 2 to form tra: Thermo ITQ 1100 mass spectrometer.
the active intermediate B, following a rapid cleavage of
Se–Se bond [38]. The in situ generated active electrophilic Typical Procedure for the Catalytic Hydroxyselenenylation
selenium species then reacts with alkene to form the
of Alkenes Using a Catalytic Amount of NH4I. To a
unstable cyclic intermediate C. Finally, intermediate C is mixed solvent of AcOEt (1.0 ml) and H2O (2.0 ml),
attacked by H2O to provide the desired products, b- alkene 1 (0.24 mmol), diselenide 2 (0.1 mmol), NH4I
hydroxy selenides 3 as a single isomer via an SN1 mecha-
(0.02 mmol), and mCPBA (0.2 mmol) were added
nism for the aromatic alkenes. When aliphatic alkene 1h successively. The resulting suspension was vigorously
is treated in the reaction, the trans stereoisomer mixture stirred at r.t. for 3 h. Then, H2O (5 ml), sat. aq. Na2S2O3
via a SN2 mechanism is obtained. In the cycle, another (2 ml), and sat. aq. Na2CO3 (2 ml) were poured into the
active intermediate ArSeI [39] can further transfer a sec-
ond equivalent of electrophilic Se to alkene.
In summary, we have developed a novel and efficient
mixture. The mixture was extracted with CH2Cl2
(3 9 5 ml) and the combined org. layer was washed with
brine, dried over anh. Na2SO4, filtered, and concentrated
catalytic procedure for the synthesis of b-hydroxy sele- under reduced pressure. The residue was purified by prep.
nides. This method has some advantages, such as rela- TLC (SiO2) with AcOEt/hexane (1:4) to give the pure
tively short reaction times, mild reaction conditions, a product 3.
simple workup, moderate to good yields of products, and 1-Phenyl-2-(phenylselanyl)ethanol (3a) [18]. Pale yellow
remarkable regioselectivity. Furthermore, the scope of
catalytic use of inorganic haloids in organic synthesis
could be extended.
oil. Yield: 92%. IR (film): 3060 – 3010, 3059, 3030, 1578,
1477, 1437, 1054, 1023, 737, 700. H-NMR: 7.59 – 7.53 (m,
1
2 H); 7.40 – 7.25 (m, 8 H); 4.77 (dd, J = 9.4, 3.7, 1 H);
3.32 (dd, J = 12.8, 3.7, 1 H); 3.16 (dd, J = 12.8, 9.4, 1 H).
13C-NMR: 142.5; 133.1; 129.24; 129.20; 128.5; 127.9; 127.4;
125.8; 72.3; 38.4. ESI-MS: 295 (42, [M + NH4]+).
1-(4-Methylphenyl)-2-(phenylselanyl)ethanol (3b) [29]. Pale
yellow oil. Yield: 71%. IR (film): 3600 – 3100, 3054, 3021,
1579, 1477, 1437, 1058, 1022, 818, 737, 691. 1H-NMR:
7.59 – 7.54 (m, 2 H); 7.32 – 7.23 (m, 5 H); 7.19 – 7.14 (m,
2 H); 4.75 (dd, J = 9.3, 3.8, 1 H); 3.30 (dd, J = 12.8, 3.8, 1
H); 3.17 (dd, J = 12.7, 9.3, 1 H); 2.36 (s, 3 H). 13C-NMR:
Experimental Part
General
Ammonium iodide, mCPBA, alkenes, and diselenides
were commercially available. IR Spectra: Thermo Nicolet
1
6700 instrument. H- and 13C-NMR spectra: in CDCl3 on
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Helv. Chim. Acta 2016, 99, 1 – 5
Scheme. Proposed mechanism for the catalyzed hydroxyselenenylation of alkenes.
139.6; 137.7; 133.0; 129.3; 129.23; 129.21; 127.3; 125.7; 72.1;
128.8; 128.6; 127.5; 127.2; 71.5; 38.4. ESI-MS: 330 (14,
38.4; 21.1. ESI-MS: 309 (50, [M + NH4]+).
4-[1-Hydroxy-2-(phenylselanyl)ethyl]phenyl Acetate (3c). 1-(4-Bromophenyl)-2-(phenylselanyl)ethanol (3g). Pale
[M + NH4]+).
Pale yellow oil. Yield: 68%. IR (film): 3600 – 3100, 3056,
yellow oil. Yield: 61%. IR (film): 3600 – 3100, 3056,
1757, 1579, 1506, 1370, 1198, 1165, 1018, 913, 847, 738, 1578, 1478, 1070, 1010, 823, 737, 690. 1H-NMR:
1
692. H-NMR: 7.57 – 7.52 (m, 2 H); 7.37 – 7.33 (m, 2 H); 7.57 – 7.53 (m, 2 H); 7.49 – 7.43 (m, 2 H); 7.33 – 7.27
7.36 – 7.31 (m, 3 H); 7.12 – 7.01 (m, 2 H); 4.75 (dd, (m, 3 H); 7.24 – 7.20 (m, 2 H); 4.71 (dd, J = 9.2, 3.8, 1
J = 9.4, 3.7, 1 H); 3.29 (dd, J = 12.8, 3.8, 1 H); 3.13 (dd, H); 3.27 (dd, J = 12.8, 3.8, 1 H); 3.10 (dd, J = 12.8,
J = 12.8, 9.5, 1 H); 2.31 (s, 1 H). 13C-NMR: 169.5; 150.2; 9.2, 1 H). 13C-NMR: 141.5; 133.2; 131.6; 129.3; 127.6;
139.9; 133.1; 129.3; 127.4; 126.9; 121.6; 71.7; 38.3; 21.1.
ESI-MS: 353 (3.0, [M + NH4]+). HR-MS: 354.0601 MS: 373.9645 (C14H17BrNOSe+, [M + NH4]+; calc.
(C16H20NO3Se+, [M + NH4]+; calc. 354.0608).
373.9659).
1-(4-tert-Butylphenyl)-2-(phenylselanyl)ethanol (3d). Pale 2-(Phenylselanyl)cyclohexanol (3h) [18]. Pale yellow oil.
yellow oil. Yield: 69%. IR (film): 3600 – 3100, 3056, 1579, Yield: 61%. IR (film): 3600 – 3100, 3056, 1578, 1477,
121.7; 71.6; 38.3. ESI-MS: 374 (95, [M + NH4]+). HR-
1477, 1438, 1057, 1022, 833, 736, 691. 1H-NMR: 1437, 1065, 740, 693. 1H-NMR: 7.63 – 7.58 (m, 2 H);
7.58 – 7.52 (m, 2 H); 7.41 – 7.35 (m, 2 H); 7.32 – 7.25 (m, 7.37 – 7.25 (m, 3 H); 3.34 (td, J = 10.2, 4.3, 1 H);
5 H); 4.77 (dd, J = 9.3, 3.5, 1 H); 3.33 (dd, J = 12.8, 3.7, 1 2.95 – 2.86 (m, 1 H); 2.24 – 2.11 (m, 2 H); 1.76 – 1.71 (m,
H); 3.19 (dd, J = 12.8, 9.4, 1 H); 2.82 (s, 1 H); 1.33 (s, 9 1 H); 1.67 – 1.60 (m, 1 H); 1.46 – 1.20 (m, 4 H). 13C-
H). 13C-NMR: 150.9; 139.5; 133.0; 129.4; 129.2; 127.3; NMR: 136.1; 129.0; 128.1; 126.6; 72.3; 53.5; 33.9; 33.4; 26.8;
125.6; 125.4; 72.1; 38.2; 34.5; 31.32; 31.29. ESI-MS: 351
(46, [M + NH4]+). HR-MS: 352.1147 (C18H26NOSe+, 2-(Benzylselanyl)-1-phenylethanol (3i). Pale yellow oil.
[M + NH4]+; calc. 352.1180).
Yield: 89%. IR (film): 3600 – 3100, 3060, 3027, 1601,
1-(4-Fluorophenyl)-2-(phenylselanyl)ethanol (3e) [29]. Pale 1493, 1453, 1054, 1029, 759, 698. 1H-NMR: 7.42 – 7.24
yellow oil. Yield: 62%. IR (film): 3600 – 3100, 3071, 1604, (m, 10 H); 4.69 (dd, J = 8.8, 4.1, 1 H); 3.78 (s, 2 H); 2.88
24.4. ESI-MS: 273 (100, [M + NH4]+).
1509, 1223, 1157, 1060, 836, 731, 691. 1H-NMR: (dd, J = 13.0, 4.1, 1 H); 2.81 (dd, J = 13.0, 8.8, 1 H). 13C-
7.58 – 7.53 (m, 2 H); 7.34 – 7.27 (m, 5 H); 7.06 – 7.00 (m, NMR: 142.8; 138.9; 128.9; 128.6; 128.4; 127.8; 126.9;
2 H); 4.74 (dd, J = 9.2, 3.8, 1 H); 3.28 (dd, J = 12.8, 3.9, 1 125.7; 72.4; 34.1; 27.4. ESI-MS: 309 (11, [M + NH4]+).
H); 3.12 (dd, J = 12.8, 9.3, 1 H). 13C-NMR: 163.3; 161.4; HR-MS: 310.0701 (C15H20NOSe+, [M + NH4]+; calc.
138.25 (d, J = 2.6); 133.2; 129.3; 129.0; 127.5 (d, J = 8.1); 310.0710).
115.0; 71.6; 38.4. ESI-MS: 313 (23, [M + NH4]+).
1-(4-Chlorophenyl)-2-(phenylselanyl)ethanol (3f) [29]. Pale yellow oil. Yield: 71%. IR (film): 3600 – 3100, 3059, 3026,
1600, 1514, 1494, 1453, 1179, 1066, 818, 758, 698. 1H-
2-(Benzylselanyl)-1-(4-methylphenyl)ethanol (3j). Pale
yellow oil. Yield: 59%. IR (film): 3600 – 3100, 3057, 1578,
1491, 1478, 1091, 1014, 828, 737, 691. 1H-NMR: NMR: 7.40 – 7.18 (m, 9 H); 4.68 (dd, J = 8.7, 4.4, 1 H);
7.59 – 7.52 (m, 2 H); 7.33 – 7.25 (m, 7 H); 4.73 (dd, 3.78 (s, 2 H); 2.87 (dd, J = 13.0, 4.4, 1 H); 2.82 (dd,
J = 9.2, 3.8, 1 H); 3.27 (dd, J = 12.8, 3.9, 1 H); 3.10 (dd, J = 12.9, 8.7, 1 H); 2.39 (s, 1 H). 13C-NMR: 139.9; 138.9;
J = 12.9, 9.3, 1 H). 13C-NMR: 140.9; 133.5; 133.2; 129.3; 137.4; 129.1; 128.9; 128.5; 128.2; 127.8; 126.8; 125.6; 72.3;
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Helv. Chim. Acta 2016, 99, 1 – 5
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34.0; 27.4; 21.1. ESI-MS: 323 (47, [M + NH4]+). HR-MS:
324.0861 (C16H22NOSe+, [M + NH4]+; calc. 324.0867).
4-[2-(Benzylselanyl)-1-hydroxyethyl]phenyl acetate (3k). Pale
yellow oil. Yield: 72%. IR (film): 3600 – 3100, 3061, 3027,
[8] M. P. Rayman, Proc. Nutr. Soc. 2005, 64, 527.
[9] P. Erkekoglu, M.-W. Chao, W. Ye, J. Ge, L. J. Trudel, P. L.
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[10] K. B. Sharpless, R. F. Lauer, J. Am. Chem. Soc. 1973, 95, 2697.
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790.
1
1756, 1602, 1506, 1369, 1198, 1016, 912, 848, 759, 698. H-
NMR: 7.36 – 7.23 (m, 7 H); 7.07 (dd, J = 7.0, 1.6, 2 H);
4.64 (dd, J = 9.0, 4.0, 1 H); 3.79 (s, 2 H); 2.83 (dd,
J = 13.1, 4.0, 1 H); 2.76 (dd, J = 13.1, 9.1, 1 H); 2.31 (s, 3
H). 13C-NMR: 169.5; 150.1; 140.4; 138.8; 128.9; 128.6;
126.9; 126.8; 121.5; 71.9; 34.0; 27.6; 21.1. ESI-MS: 367
(6.5, [M + NH4]+). HR-MS: 368.0743 (C17H22NO3Se+,
[M + NH4]+; calc. 368.0765).
[12] M. Sevring, W. Dumont, L. Hevesi, A. Krief, Tetrahedron Lett.
1976, 17, 2647.
[13] D. Van Ende, W. Dumont, A. Krief, Angew. Chem., Int. Ed.
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Soc. 2000, 122, 6624.
[16] E. M. Treadwell, J. D. Neighbors, D. F. Wiemer, Org. Lett.
2002, 4, 3639.
2-(Benzylselanyl)-1-(4-chlorophenyl)ethanol (3l). Pale yel-
low oil. Yield: 55%. IR (film): 3600 – 3100, 3061, 3027,
1598, 1492, 1453, 1091, 1014, 829, 758, 697. 1H-NMR:
7.36 – 7.20 (m, 9 H); 4.61 (dd, J = 9.0, 4.0, 1 H); 3.79 (s, 2
H); 2.82 (dd, J = 13.1, 4.0, 1 H); 2.73 (dd, J = 13.1, 9.0, 1
H). 13C-NMR: 141.3; 138.7; 133.4; 128.9; 128.62; 128.57;
127.1; 127.0; 71.7; 34.0; 27.5. ESI-MS: 343.5 (21,
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7529.
[M + NH4]+).
[M + NH4]+; calc. 344.0320).
HR-MS:
344.0319
(C15H19ClNOSe+,
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Am. Chem. Soc. 1979, 101, 3704.
2-(Benzylselanyl)-1-(4-bromophenyl)ethanol (3m). Pale
yellow oil. Yield: 50%. IR (film): 3600 – 3100, 3060, 3026,
1592, 1490, 1453, 1069, 1010, 823, 758, 697. 1H-NMR:
7.50 – 7.46 (dd, J = 6.8, 1.7, 2 H); 7.36 – 7.25 (m, 5 H);
7.18 (d, J = 8.4, 2 H); 4.59 (dd, J = 9.0, 3.9, 1 H); 3.80 (s,
2 H); 2.82 (dd, J = 13.1, 4.0, 1 H); 2.73 (dd, J = 13.1, 9.0,
1 H). 13C-NMR: 141.8; 138.7; 131.5; 128.9; 128.6; 127.4;
127.0; 121.5; 71.7; 33.9; 27.5. ESI-MS: 388 (6.5,
[M + NH4]+). HR-MS: 387.9803 (C15H19BrNOSe+,
[M + NH4]+; calc. 387.9815).
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5363.
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8386.
2-(Benzylselanyl)cyclohexanol (3n) [27]. Pale yellow oil.
Yield: 58%. IR (film): 3600 – 3100, 3060, 3027, 1600.4;
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Synthesis 1992, 377.
1
1494, 1449, 1067, 758, 697. H-NMR: 7.36 – 7.19 (m, 5 H);
3.87 (dd, J = 19.1, 11.7, 1 H); 3.39 (td, J = 10.1, 4.4, 1 H);
2.68 – 2.61 (m, 1 H); 2.15 – 2.12 (m, 2 H); 1.78 – 1.75 (m,
1 H); 1.67 – 1.51 (m, 2 H); 1.33 – 1.20 (m, 3 H). 13C-
NMR: 139.2; 128.8; 128.6; 126.8; 72.8; 50.2; 34.0; 33.6; 26.9;
26.1; 24.5. ESI-MS: 287 (37, [M + NH4]+).
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Received April 29, 2016
Accepted May 23, 2016
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