PhI Catalyzed Acetoxyselenylation and Formyloxyselenylation of Alkenes

Article abstract of DOI:10.1002/hlca.201600306

With PhI as catalyst and mCPBA as oxidant, a novel and efficient catalytic procedure has been developed for the acetoxyselenylation and formyloxyselenylation of alkenes. In this protocol, PhI is first oxidized into hypervalent iodine intermediate, which promotes the cleavage of Se–Se bond in diselenides. The in?situ generated electrophilic selenium species then reacts with alkenes, affording 2-acetoxy-1-selenides and 2-formyloxy-1-selenides in high regioselectivity and good yields.

Full text of DOI:10.1002/hlca.201600306

Received Date: 22-Sep-2016
Revised Date: 26-Nov-2016
Accepted Date: 02-Dec-2016
Article Type: Full Paper
PhI Catalyzed Acetoxyselenylation and Formyloxyselenylation of Alkenes
by Yikun Zhang, Sixue Wu, and Jie Yan*
College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, P. R. of
China, Fax +86(571)88320238; E-mail: jieyan87@zjut.edu.cn
Abstract: With PhI as catalyst and mCPBA as oxidant, a novel and efficient catalytic procedure has
been developed for the acetoxyselenylation and formyloxyselenylation of alkenes. In this protocol,
PhI is first oxidized into hypervalent iodine intermediate, which promotes the cleavage of Se–Se bond
in diselenides. The in situ generated electrophilic selenium species then reacts with alkenes,
affording 2-acetoxy-1-selenides and 2-formyloxy-1-selenides in high regioselectivity and good yields.
Keywards: Acetoxyselenylation, Formyloxyselenylation, Hypervalent iodine intermediate, Alkene,
Catalysis
This article has been accepted for publication and undergone full peer review but has not been
through the copyediting, typesetting, pagination and proofreading process, which may lead to
differences between this version and the Version of Record. Please cite this article as doi:
10.1002/hlca.201600306
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Introduction The chemistry of hypervalent iodine organic compounds has experienced impressive
developments since the early 1990s. Because of the low toxicity, ready availability and easy
handling, especially the reactivity similar to that of heavy-metal reagents, they have been
broadly used in organic chemistry and frequently used in synthesis [1-7]. The hypervalent iodine
reagents are usually used as stoichiometric oxidants. However, after oxidations at least equimolar
amounts of iodoarenes are produced as by-products. Due to iodoarenes are expensive and most of
them are disposed of after the oxidations, which restrict hypervalent iodine reagents further
applications. In 2005, Ochiai et al. and Kita’s group independently reported the first hypervalent
iodine-catalyzed oxidative coupling reactions [8-9]. Since then, the substoichiometric utilization of
hypervalent iodine reagents has been increasing in importance, with growing interest in the
development of environmentally benign synthetic transformations [10-15]. In these catalyzed
reactions, a catalytic amount of an iodine-containing molecule together with a stoichiometric
oxidant is used. The oxidant generates the hypervalent iodine reagent in situ and, after the oxidative
transformation, the reduced iodine-containing molecule is re-oxidized.
In recent years, organoselenium compounds have been increasing in importance due to their
synthetic applications, biological activities and other properties [16-23]. The introduction of
organolselenium groups into organic molecules has been widely studied, in which the
oxyselenenylation reaction is a very useful procedure for the anti-l,2-addition of an organylselenium
group and an oxygen substituent (HO, RO, RCO2) to an olefin [24-26]. In the electrophilic addition,
the most common selenenylating reagent is normally available by the oxidation of cheaper and less
toxic diphenyl diselenide with oxidants. Tingoli’s group used hypervalent iodine reagent PhI(OAc)2 to
treat diphenyl diselenide, they found that the oxidative cleave the Se-Se bond was easily, and the
electrophilic addition of the in situ generated reactive electrophilic selenium species to alkenes
proceeded smoothly [27-29]. Although several papers about the further application of this
methodology in organic synthesis have recently been reported [30-34], the catalytic
oxyselenenylation using hypervalent iodine reagents as catalysts has been developed rarely.
Therefore, to extend the scope of catalytic application of hypervalent iodine reagents in organic
synthesis, we have investigated the oxyselenenylation of alkenes with iodobenzene (PhI) as catalyst.
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Herein, we would like to report the novel and effective catalytic acetoxyselenylation and
formyloxyselenylation of alkenes.
Results and Discussion
Recently, we have developed the acetoxyselenylation of alkenes use of inorganic haloid salts as
catalysts [35-36]. On the basis, we first explored the reaction of styrene 1a, diphenyl diselenide 2a
and oxidant m-chloroperbenzoic acid (mCPBA) in the presence of catalytic amount of PhI with AcOH
at room temperature. We found that only stirring the mixture of 1.0 equiv of 2a, 1.2 equiv of 1a and
mCPBA with 0.1 equiv of PhI in a mixed solvent of AcOH and EtOAc (1:1) for 3 h, the expected
addition product, 1-phenyl-2-(phenylselanyl)ethyl acetate 3a was obtained in 61% yield (Table 1,
entry 1). As a control experiment, 3a was observed in only 5% yield in the absence of PhI (entry 2).
Therefore, it was obvious that PhI played a key action in the reaction. Encouraged by this result, the
acetoxyselenenylation of 1.2 equiv of 1a and 1.0 equiv of 2a with mCPBA using PhI as catalyst at
room temperature for 3 h was then optimized (Table 1). As shown from Table 1, the yield decreased
when the ratio of AcOH decreased in the mixed solvent AcOH/EtOAc, meaning more AcOH should be
favorable for the reaction (entry 3). When AcOH was used as solvent, the yield increased greatly to
87%, so the neat AcOH was the suitable solvent for the reaction (entry 4). In AcOH (2.0 mL), the
amount of mCPBA was optimized, and 0.8 equiv of it showed the best effective to the reaction
(entries 4-7). Finally, the amount of catalyst was also determined: 0.1 equiv of it was the best choice
(entries 8-11).
Having established the optimal conditions, the acetoxyselenenylation of 1.2 equiv of alkenes 2 with
1.0 equiv of diselenides 1, 0.8 equiv of mCPBA and 0.1 equiv of PhI proceeded fluently in AcOH, and
a series of corresponding 2-acetoxy-1-selenenylation compounds 3a-3l were obtained. The results
are summarized in Table 2.
As shown in Table 2, the reaction was compatible with the studied styrene and a few derivatives,
which provided the corresponding products in good to excellent yields (entries 1-5). Similar to 2a,
dibenzyl diselenide 2b, an aliphatic diselenide, also reacted easily with these aromatic alkenes, giving
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good yield products (entries 7-11). It was obvious that when the groups on the benzene ring were
electron-donating groups, the alkenes had higher yields than those with electron-withdrawing
groups on benzene ring (entries 2-5, 8-11). Nevertheless, 4-acetoxystyrene, an oxygen-containing
substrate, failed to provide the desired product, only giving a complicated inseparable mixture.
Cyclohexene 1f, when it was treated under the same conditions, the addition proceeded in a trans
fashion and the stereoisomer mixtures were obtained in moderate to good yields (entries 6, 12).
Other aliphatic terminal alkenes were also checked, however, the reaction led to some complicated
mixtures which were not to be isolated, also the yields were not determined. Therefore, this
protocol is suitable for aromatic alkenes and aliphatic cyclic alkenes, resulting in the corresponding
products in high regioselectivity. In order to extent the content of this methodology, with the similar
manner we tried to investigate the formyloxyselenylation of alkenes which has not been reported
before. Unfortunately, the desired products were obtained in much low yields when acetic acid was
replaced by formic acid. While in a mixed solvent of formic acid and ethyl acetate (1:3), the
formyloxyselenylation was found to proceed well. Based on this success, three alkenes 1a, 1c and 1d
were selected as represents of alkenes to be treated in the formyloxyselenylation, and the
corresponding products 3m-3o were afforded in yields ranging from 37-69% (entries 13-15). As for
other acids, benzyl acid was used as represent to replace formic acid, but it was unreactive for the
reaction.
A proposed mechanism for the PhI catalyzed acetoxyselenenylation and formyloxyselenylation of
alkenes is shown in Scheme 1. PhI is first oxidized by mCPBA to hypervalent iodine reagent A, which
reacts smoothly with diselenide 2 to form the active intermediate B, following a rapid cleavage of
Se-Se bond. The in situ generated electrophilic selenium species reacts with alkene to produce the
unstable cyclic intermediate D. Another active intermediate C can also further transfer a second
equivalent of electrophilic selenium to alkenes to form the cyclic intermediate D. After a solvolysis of
D in AcOH, the desired product 3 as a single isomer is obtained via an SN1 mechanism for the
aromatic alkenes. While an aliphatic alkene 1f is used as substrate, the reaction provides the trans
stereoisomers via an SN2 mechanism. This result supports that the first formation of the cyclic
selenium intermediate D, then acetate anion attacks the cyclic intermediate affording the
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corresponding anti-l, 2-addition products 3f and 3l. To support the mechanism, Ishihara catalyst was
added in the reaction; however, no asymmetric induction had been achieved.
In summary, we have developed a novel and efficient catalytic processor for synthesis of
2-acetoxy-1-selenides and 2-formyloxy-1-selenides using PhI as catalyst. This method has some
advantages such as mild reaction conditions and simple procedure, which providing a series of
corresponding compounds with high regioselectivity and good yields. Furthermore, the scope of
catalytic use of hypervalent iodine reagent in organic synthesis could be extended.
Experimental Part
IR spectra were recorded on a Thermo Nicolet 6700 instrument. 1H-NMR and 13C-NMR spectra were
measured in CDCl3 on a Bruker Avance III (500MHz) spectrometer. Mass spectra were determined on
a Thermo ITQ 1100 mass spectrometer. Alkenes, diselenides, mCPBA, PhI and solvents were
commercially available.
Typical Procedure for the Catalytic Acetoxyselenenylation of Alkenes Using PhI as Catalytic: In
AcOH (2.0 mL), alkene 1 (0.48 mmol), diselenide 2 (0.2 mmol), PhI (0.04 mmol) and mCPBA (0.32
mmol) were added successively. The suspension mixture was vigorously stirred at r. t. for 3 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 compounds 3.
1-Phenyl-2-(phenylselanyl)ethyl acetate (3a) [27]
Colorless viscous oil, Yield: 97%.
IR (film): 3061, 3033, 1742, 1371, 1236, 1020, 738, 698.
1H-NMR: 7.52 (dd, J = 6.5, 2.9 Hz, 2H), 7.39-7.30 (m, 5H), 7.30-7.24 (m, 3H), 5.96 (dd, J = 8.0, 5.7 Hz,
1H), 3.40 (dd, J = 12.9, 8.0 Hz, 1H), 3.25 (dd, J = 12.9, 5.7 Hz, 1H), 2.04 (s, 3H).
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13C-NMR: 170.0, 139.4, 133.1, 129.8, 129.1, 128.5, 128.4, 127.2, 126.6, 75.2, 33.4, 21.0.
ESI-MS: 338 (4.8, [M + 18]), 261 (100).
2-(Phenylselanyl)-1-(4-tolyl)ethyl acetate (3b) [35]
Colorless viscous oil, Yield: 77%.
IR (film): 3055, 3027, 1742, 1370, 1236, 1020, 816, 738, 692.
1H-NMR: 7.64-7.42 (m, 2H), 7.28 (dd, J = 4.9, 1.7 Hz, 3H), 7.24 (d, J = 8.1 Hz, 2H), 7.17 (d, J = 8.0 Hz,
2H), 5.93 (dd, J = 7.9, 5.9 Hz, 1H), 3.40 (dd, J = 12.8, 8.0 Hz, 1H), 3.24 (dd, J = 12.8, 5.9 Hz, 1H), 2.36
(s, 3H), 2.02 (s, 3H). 13C-NMR: 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.
ESI-MS: 334 (6.5, M+), 194 (100).
1-(4-tert-Butylphenyl)-2-(phenylselanyl)ethyl acetate (3c) [35]
Colorless viscous oil, Yield: 75%.
IR (film): 3057, 2963, 1745, 1370.0, 1235, 1021, 828, 737, 691.
1H-NMR: 7.52-7.50 (m, 2H), 7.37-7.36 (m, 2H), 7.29-7.26 (m, 5H), 5.96 (dd, J = 8.0, 5.7 Hz, 1H), 3.40
(dd, J = 12.8, 8.1 Hz, 1H), 3.25 (dd, J = 12.8, 5.6 Hz, 1H), 2.03 (s, 3H), 1.33 (s, 9H).
13C-NMR: 169.5, 150.2, 139.9, 133.1, 129.3, 127.4, 126.9, 121.6, 71.7, 38.3, 21.1.
ESI-MS: 376 (14.1, M+), 219 (100).
1-(4-Chlorophenyl)-2-(phenylselanyl)ethyl acetate (3d) [35]
Pale yellow viscous oil, Yield: 62%.
IR (film): 3057, 1741, 1371, 1235, 1051, 1016, 824, 738, 692.
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1H-NMR: 7.54-7.44 (m, 2H), 7.33-7.29 (m, 2H), 7.29-7.20 (m, 5H), 5.93-5.85 (m, 1H), 3.42-3.30 (m,
1H), 3.26-3.14 (m, 1H), 2.02 (s, 3H).
13C-NMR: 169.9, 137.8, 134.2, 133.2, 129.5, 129.2, 128.7, 128.1, 127.4, 74.6, 33.1, 21.0.
ESI-MS: 354 (11.2, M+), 214 (100).
1-(4-Bromophenyl)-2-(phenylselanyl)ethyl acetate (3e) [35]
Pale yellow viscous oil, Yield: 69%.
IR (film): 3056, 1741, 1481, 1072, 1007, 823, 736, 690.
1H-NMR: 7.50-7.45 (m, 4H), 7.28-7.26 (m, 3H), 7.21-7.19 (m, 2H), 5.93-5.82 (m, 1H), 3.43-3.29 (m,
1H), 3.28-3.13 (m, 1H), 2.02 (s, 3H).
13C-NMR: 169.9, 138.3, 133.2, 131.6, 129.5, 129.2, 128.4, 127.4, 122.4, 74.7, 33.1, 21.0.
ESI-ES: 398 (58.5, M+), 338 (100).
2-(Phenylselanyl)cyclohexyl acetate (3f) [27]
Colorless viscous oil, Yield: 52%.
IR (film): 3056, 2936, 2858, 1738, 1373, 1238, 1036, 741, 693.
1H-NMR: 7.63-7.53 (m, 2H), 7.30-7.27 (m, 3H), 4.89-4.81 (m, 1H), 3.29-3.15 (m, 1H), 2.20-2.05 (m,
2H), 1.96 (s, 3H), 1.75-1.65 (m, 2H), 1.54-1.29 (m, 4H).
13C-NMR: 170.3, 135.0, 128.9, 128.7, 127.6, 75.4, 46.1, 32.3, 31.8, 25.8, 23.6, 21.1.
ESI-MS: 298 (4.5, M+), 81 (100).
2-(Benzylselanyl)-1-phenylethyl acetate (3g) [35]
Pale yellow viscous oil, Yield: 81%.
IR (film): 3061, 3029, 1739, 1371, 1237, 1018, 758, 698.
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1H-NMR: 7.50-7.09 (m, 10H), 5.83 (dd, J = 7.6, 6.3 Hz, 1H), 3.67 (d, J = 2.4 Hz, 2H), 2.92 (dd, J = 13.0,
7.7 Hz, 1H), 2.78 (dd, J = 13.0, 6.2 Hz, 1H), 2.09 (s, 3H).
13C-NMR: 169.9, 139.7, 138.9, 129.0, 128.5, 128.3, 126.9, 126.7, 75.5, 29.0, 27.8, 21.1.
ESI-MS: 352 (11.0, [M + 18]), 336 (100).
2-(Benzylselanyl)-1-(4-tolyl)ethyl acetate (3h) [35]
Pale yellow viscous oil, Yield: 71%.
IR (film): 3059, 3027, 1741, 1370, 1237, 1018, 817, 759, 698.
1H-NMR: 7.33-7.17 (m, 9H), 5.83 (dd, J = 7.5, 6.5 Hz, 1H), 3.72 (d, J = 3.2 Hz, 2H), 2.95 (dd, J = 12.9,
7.7 Hz, 1H), 2.80 (dd, J = 12.9, 6.3 Hz, 1H), 2.36 (s, 3H), 2.10 (s, 3H).
13C-NMR: 169.9, 139.0, 138.1, 136.7, 129.2 129.0, 128.5, 126.8 (d, J = 19.7 Hz), 75.4, 29.0, 27.8, 21.2.
ESI-MS: 348 (3.5, M+), 369 (100)
2-(Benzylselanyl)-1-(4-tert-butylphenyl)ethyl acetate (3i)
Pale yellow viscous oil, Yield: 87%.
IR (film): 3028, 2962, 1744, 1370, 1237, 1017, 829, 758, 698.
1H-NMR: 7.43-7.40 (m, 2H), 7.36-7.21 (m, 7H), 5.89 (dd, J = 7.9, 6.2 Hz, 1H), 3.73 (s, 2H), 2.98 (dd, J =
13.0, 8.0 Hz, 1H), 2.83 (dd, J = 13.0, 6.1 Hz, 1H), 2.13 (s, 3H), 1.36 (s, 9H).
13C-NMR: 169.9, 151.2, 138.8, 136.5, 128.9, 128.4, 126.7, 126.3, 125.3, 75.1, 34.5, 31.3, 28.8, 27.6,
21.1.
ESI-MS: 413 (3.5, [M + 23]), 369 (100).
HR-MS: calc. for C21H26NaO2Se [M + 23]: 413.0996; found: 413.0983.
2-(Benzylselanyl)-1-(4-chlorophenyl)ethyl acetate (3j) [35]
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Colorless viscous oil, Yield: 63%.
IR (film): 3061, 3028, 1739, 1371, 1236, 1015, 825, 759, 698.
1H-NMR: 7.35-7.12 (m, 9H), 5.82-5.66 (m, 1H), 3.77-3.62 (m, 2H), 2.89 (dd, J = 13.0, 7.6 Hz, 1H), 2.74
(dd, J = 13.0, 6.4 Hz, 1H), 2.08 (s, 3H).
13C-NMR: 169.8, 138.7, 138.2, 134.2, 129.0, 128.7, 128.6, 128.1, 126.9, 74.7, 28.7, 27.9, 21.1.
ESI-MS: 369 (13.0, [M + 1]), 289 (100).
2-(Benzylselanyl)-1-(4-bromophenyl)ethyl acetate (3k)
Colorless viscous oil, Yield: 61%.
IR (film): 3060, 3027, 2928, 1738, 1594, 1490, 1370, 1233, 1010, 819, 758, 697.
1H-NMR: 7.49 (d, J = 8.4 Hz, 1H), 7.35-7.23 (m, 5H), 7.19 (d, J = 8.4 Hz, 2H), 5.77 (t, J = 6.9 Hz, 1H),
3.78-3.65 (m, 2H), 2.91 (dd, J = 13.0, 7.6 Hz, 1H), 2.76 (dd, J = 13.0, 6.3 Hz, 1H), 2.11 (s, 3H).
13C-NMR: 169.8, 138.7, 138.6, 131.6, 129.0, 128.6, 128.4, 126.9, 122.3, 74.7, 28.6, 27.8, 21.1.
ESI-MS: 430 (3.8, [M + 18]), 274 (100).
HR-MS: calc. for C17H21BrNO2Se [M + 18]: 429.9921; found: 429.9903.
2-(Benzylselanyl)cyclohexyl acetate(3l)
Colorless viscous oil, Yield: 55%.
IR (film): 3061, 3027, 2935, 1736, 1601, 1494, 1451, 1373, 1238, 1035, 759, 697.
1H-NMR: 7.36-7.17 (m, 5H), 4.88 (td, J = 8.8, 4.1 Hz, 1H), 3.95-3.80 (m, 2H), 2.88 (td, J = 10.0, 4.1 Hz,
1H), 2.17- 2.06 (m, 3H), 2.10 (s, 3H), 1.75-1.54 (m, 3H), 1.47-1.25 (m, 3H).
13C-NMR: 170.2, 139.2, 128.9, 128.4, 126.6, 75.7, 42.3, 32.0, 31.2, 27.1, 25.5, 23.3, 21.3.
ESI-MS: 330 (17.0, [M + 18]), 229 (100).
HR-MS: calc. for C15H24NO2Se [M + 18]: 330.0972; found: 330.0983.
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1-Phenyl-2-(phenylselanyl)ethyl formate (3m)
Colorless viscous oil, Yield: 69%.
IR (film): 3060, 2928, 1723, 1579, 1478, 1438, 1154, 737, 698.
1H-NMR: 8.10 (s, 1H), 7.55-7.48 (m, 2H), 7.40-7.24 (m, 8H), 6.04 (dd, J = 7.5, 6.3 Hz, 1H), 3.42 (dd, J =
12.9, 8.0 Hz, 1H), 3.28 (dd, J = 12.9, 5.8 Hz, 1H).
13C-NMR: 159.9, 138.7, 133.3, 129.4, 129.2, 128.7, 128.6, 127.4, 126.7, 75.0, 33.1.
ESI-MS: 329 (16.8, [M + 23]), 274 (100)
HR-MS: calc. for C15H14NaO2Se [M + 23]: 329.0057; found: 329.0023.
1-(4-tert-Butylphenyl)-2-(phenylselanyl)ethyl formate (3n)
Colorless viscous oil, Yield: 37%.
IR (film): 3057, 2962, 2868, 1726, 1478, 1163, 830, 737, 691.
1H-NMR: 8.09 (s, 1H), 7.52-7.48 (m, 2H), 7.38 (d, J = 8.4 Hz, 2H), 7.32-7.23 (m, 5H), 6.03 (dd, J = 7.6,
6.2 Hz, 1H), 3.42 (dd, J = 12.9, 8.0 Hz, 1H), 3.28 (dd, J = 12.9, 5.8 Hz, 1H), 1.33 (s, 9H).
13C-NMR: 160.0, 151.7, 135.6, 133.2, 129.5, 129.1, 127.4, 126.4, 125.5, 74.9, 34.6, 33.1, 31.3.
ESI-MS: 362 (4.2, M+), 478 (100).
HR-MS: calc. for C19H22O2Se [M+]: 362.0777; found: 362.0771.
1-(4-Chlorophenyl)-2-(phenylselanyl)ethyl formate (3o)
Colorless viscous oil, Yield: 51%.
IR (film): 3057, 2930, 1724, 1493, 1154, 1092, 1015, 825, 737, 691.
1H-NMR: 8.07 (s, 1H), 7.51-7.45 (m, 2H), 7.35-7.23 (m, 7H), 5.98 (t, J = 6.9 Hz, 1H), 3.38 (dd, J = 12.9,
7.6 Hz, 1H), 3.23 (dd, J = 12.9, 6.3 Hz, 1H).
13C-NMR: 159.8, 137.1, 134.5, 133.3, 129.2, 129.1, 128.8, 128.1, 127.54, 74.3, 32.9.
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ESI-MS: 358 (8.0, [M + 18]), 301 (100).
HR-MS: calc. for C15H17ClNO2Se [M + 18]: 358.0113; found: 358.0101.
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Table 1
Optimization of the acetoxyselenenylation of styrene using PhI as catalyst
Yield
(%)a
61
5
Entry
mCPBA (equiv.)
PhI (equiv.)
Solvent
1
1.2
1.2
1.2
1.2
1.4
1.0
0.8
0.8
0.8
0.8
0.8
0.1
-
AcOH/EtOAc (1:1)
AcOH/EtOAc (1:1)
AcOH/EtOAc (1:2)
AcOH
2
3
0.1
0.1
0.1
0.1
0.1
0.2
0.3
0.05
0.02
41
87
91
92
97
94
93
68
43
4
5
AcOH
6
AcOH
7
AcOH
8
AcOH
9
AcOH
10
AcOH
11
AcOH
aIsolated yields.
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Table 2 Preparation of 2-acetoxy-1-selenenylation compounds 3
Diselenide
(2)
Yield
(%)a
Diselenide
(2)
Yield
(%)a
Entry
1
Alkene (1)
Product (3)
Entry
9
Alkene (1)
Product (3)
PhSeSePh
97
77
75
1c
2b
2b
2b
87
63
61
2a
1a
3a
3b
3i
3j
2
3
2a
2a
10
11
1d
1e
1b
1c
3k
3c
OAc
SePh
4
5
2a
2a
62
69
12
13
1f
2b
2a
78
Cl
1d
1e
3d
3e
3l
1a
69b
3m
6
7
2a
52
14
15
1c
2a
2a
37b
51b
1f
3f
3n
3o
(PhCH2Se)2
1a
81
71
1d
2b
3g
3h
8
1b
2b
a Isolated yields.
b The formyloxyselenylation was carried out in HCOOH (0.5mL) and EtOAc (1.5mL).
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Scheme 1 Proposed mechanism for the catalyzed acetoxyselenenylation of alkenes
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