Stereoselective synthesis of alkyl styryl selenides in one-pot: A straightforward approach by in situ dialkyl diselenide formation under transition metal-free conditions

Article abstract of DOI:10.1039/c5ra20883a

A simple procedure for the synthesis of alkyl styryl selenides was developed. This methodology involves the in situ generation of selenolate anions by a one-pot and three-step protocol where a nucleophilic substitution between KSeCN and alkyl halides affords the corresponding alkyl selenocyanate in the first step, giving dialkyl diselenide by a further K₃PO₄-assisted reaction. Subsequent reduction yields the alkyl selenolate anions which react with substituted (E,Z)-β-styryl halides to afford the corresponding vinyl selenides with retention of stereochemistry and from moderate to excellent yields. This procedure does not require a catalyst, proceeds under an air atmosphere and within a short reaction time, and is free from diselenide and malodorous and air-sensitive alkyl selenols as starting materials.

Full text of DOI:10.1039/c5ra20883a

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Stereoselective Synthesis of Alkyl Styryl Selenides in One-Pot: A
Straightforward Approach by in situ Dialkyl Diselenide Formation
under Transition Metal-Free Conditions
Received 00th January 20xx,
Accepted 00th January 20xx
Adrián A. Herediaa and Alicia B. Peñéñorya*
DOI: 10.1039/x0xx00000x
A simple procedure for the synthesis of alkyl styryl selenides was developed. This methodology involves the in situ
generation of selenolate anions by a one-pot and three-step protocol where a nucleophilic substitution between KSeCN
and alkyl halides affords the corresponding alkyl selenocyanate in the first step, giving dialkyl diselenide by a further
K3PO4-assisted reaction. Subsequent reduction yields the alkyl selenolate anions which react with substituted (E,Z)-β-styryl
halides to afford the corresponding vinyl selenides with retention of stereochemistry and from moderate to excellent
yields. This procedure does not require catalyst, proceeds under air atmosphere and within short reaction time, and is free
from diselenide and malodorous and air-sensitive alkyl selenols as starting materials.
www.rsc.org/
Introduction
availability of diaryldiselenide reagent.
Selenium containing compounds have attracted considerable
attention due to their versatility in organic synthetic
procedures and their potential biological activities.1 Among
them, vinyl selenides are important synthetic intermediates in
organic chemistry.2,3 In these molecules, it is possible to
combine known reactions of organoselenium compounds with
the ability to form new C-C bonds involving the double bond of
the vinyl selenides, since the selenium atom is able to stabilize
both negative and positive charges. Due to the relevance of
vinyl selenides, numerous synthetic methods have been
reported for their synthesis such as Wittig-type reactions,4
addition of nucleophilic and electrophilic selenium reagents to
alkynes5 and allenes,6 use of acetylenic selenides and direct
substitution of a halogen atom on the double bond by
selenolate anions.2,3,7 In many cases, the yield and
stereoselectivity of the reactions are controlled by the use of
transition-metal complexes such as Pd,8 Cu,9 Rh,10 La11 and Ni12
among others.13 Nevertheless, the requirement of specific
ligands and the air sensitivity of some catalytic systems involve
Recently we have reported a simple methodology for the
stereoselective synthesis of alkyl styryl sulfides by a one-pot
base-assisted procedure without transition metals. This
reaction proceeds under mild conditions at short times, and is
free from malodorous and air-sensitive alkyl thiols.15
Considering these previous results, we envisage the possibility
of extending the methodology above described to the
synthesis of alkyl styryl selenides, using potassium
selenocyanate (KSeCN, 1) as a selenium source. As in the case
of KSCOMe, KSeCN, it is easy to handle, commercially available
and widely used as a selenium source for the synthesis of
organic seleno- and isoselenocyanates, whose moderated
reactivity allows easy interconversion to other interesting
functional groups.16 We now report a simple and convenient
synthetic procedure for the preparation of alkyl arylvinyl
selenides, by employing KSeCN.
Results and discussion
a
common limitation to their industrial and large-scale
application. Some few examples of the preparation of vinyl
selenides from diaryldiselenide without using transition-metal
catalyst have also been reported.5a,14 However, this last
methodology is restricted to the commercial and synthetic
First, we explored the reactivity of KSeCN (
organic halides, in DMF as a solvent (Scheme 1). After 5 min at
room temperature, salt reacted with benzyl bromide
1) towards different
1
affording exclusively the substitution product benzyl
selenocyanate. On the other hand, its reactivity was moderate
towards primary alkyl halides, such as n-octyl bromide (2).
a.INFIQC, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad
Universitaria, X5000HUA Córdoba, Argentina,* penenory@fcq.unc.edu.ar.
† Footnotes relaꢀng to the ꢀtle and/or authors should appear here.
Electronic Supplementary Information (ESI) available:
Spectra(1H, 13C and 77Se
Thus, there was no reaction at room temperature after 5 min,
while the yield of n-octylselenocyanate was quantitative at 100
°C. Finally, (E)-β-bromostyrene (3a) did not react with 1 after 2
h at 100 °C.
NMR) for all the products (4a-l and Z4a).See DOI: 10.1039/x0xx00000x
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Table 1. Solvent screening for the one-pot synthesis of selenide 4a
solvent
100 ºC, N2
Se
Br
KSeCN
Ph
n-Oct
Ph
4a
3a
1
1) 10 min
2) NaBH4, 1h
n-Oct Se
n-Oct-Br
n-OctSe
2
2
6
2
5
entry
solventa
yield % 4ab
1
2
3
4
5
6
7
8
9
DMF
DMSO
MeCN
NMP
57c
56c
48c
59c
nd
Scheme 1. Reactivity of KSeCN (1)
These results suggest the possibility of generating the benzyl or
alkylselenolate anion (RSe−) from the corresponding organic
selenocyanate in the presence of styryl bromide. Furthermore,
these selenolate anions could react towards vinyl halides, such as
alkane thiolate analogues,15 giving the corresponding alkyl vinyl
selenides in a one-pot procedure. We selected n-octyl bromide (2)
as an alkylating reagent, (E)-β-bromostyrene (3a) as a model
substrate, and the polar DMF as a solvent to start this study.
Toluene
Dioxane
THF
nd
nd
Ethanol
<5
53c
PEG 300
aThe reaction was performed by using: 0.25 mmol of 3a and a ratio of 1 : 1.3
: 1.2 : 2.6 for 3a, 1, 2 and NaBH4, respectively. bQuantified by GC with
internal standard. nd: no detected. cTogether with ca. 20% of a mixture of 5
and 6 with a ratio 5/6 around 70/30-80/20.
The organic selenocyanates (RSeCN) can be reduced to the
corresponding RSe− anions, NaBH4 being one of the reagents more
frequently used for this purpose.17 With the aim of generating
selenolate anions, we performed the reaction in the presence of
this reduction reagent. Thus, a mixture of 1, 2 and 3a was allowed
to react at 100 °C for 10 min in DMF as a solvent, in order to assure
that the SN2 reaction between 1 and 2 was completed. After that
time, NaBH4 was added and the reaction mixture was heated at 100
°C for one hour under nitrogen atmosphere. Fortunately, n-octyl
styryl selenide (4a) was detected in 49% yield, together with the
symmetric selenoether di-n-octyl selenide (5) (Scheme 2).This by-
product probably comes from the nucleophilic attack of n-octyl
selenolate anion at carbon 1 of n-octylselenocyanate.18 To avoid
this secondary reaction we increased the amount of 1, 2 and NaBH4
in relation to 3a, and product 4 was obtained in 57% yield but with
a lower amount of compound 5 and a new secondary product 6,
indentified as di-n-octyldiselenide (Scheme 2, Table 1, entry 1).
Product 6 can proceed from a nucleophilic attack of the in situ
generated n-octyl selenolate anion at the selenium electrophilic
atom of n-octylselenocyanate.17
Finally, only traces of 4a were obtained when the reaction was
performed in the polar protic ethanol and its yield increased to 53%
in PEG 300 (Table 1, entries 8 and 9). The secondary products 5 and
6 were found in most of the solvents used, as minor by-products.
Also, the amount of n-octylselenocyanate, formed in the first step,
was detected in traces. It is important to mention that the
reduction of one equivalent of 6 by two equivalents of NaBH4 would
generate two equivalents of n-octylselenolate anions. On the other
hand, the presence of the secondary product 5 in moderate
concentration is a disadvantage since its generation implies a minor
availability of selenolate anions to react with styryl bromide 3a.
Then, for a detailed study of the generation of n-octylselenolate
anion from the corresponding alkylselenocyanate, diverse bases
and reducing agents were screened (Table 2). Using NaH as a
reducing species, the yield of 4a dropped to 22% in comparison
with that of the reaction performed employing NaBH4 (Table 2,
entries 1 and 2). When t-BuOK was used as a base instead of 4a, a
new product was obtained for the first time, indentified as n-octyl
(2-phenylethynyl) selenide (Table 2, entry 3). This product was not
detected in the previous reactions and its mechanistic study and
synthetic scope are currently being developed. In the presence of
other bases such as K3PO4, KOH, K2CO3 and DABCO, traces of 4a
were only detected in better conditions (Table 2, entries 4-7).
Although these results did not seem to be encouraging, a detailed
analysis of GC profiles showed that 6 was afforded as main product
when the reaction was conducted in the presence of K3PO4 (Table 2,
entry 4). In the presence of K2CO3, 6 was also obtained; yet, its yield
was notably lower than with K3PO4 (Table 2, entry 6). The fact that
neither 5 nor 6 were obtained in the presence of DABCO allows
excluding the participation of DMF as reducing agent for the
formation of selenolate anions from the alkyl selenocyanate. The
generation of selenolate anions was ascribed to base-catalysed
hydrolysis of n-octyl selenocyanate due to the presence of traces of
water in DMF.19,
Scheme 2. One-pot synthesis of n-octyl styryl selenide (4a)
After these preliminary results, we performed a screening of
solvents whose results are summarized in Table 1. Thus, the best
results were obtained in the non protic solvent such as DMF, DMSO,
MeCN and NMP, with 50-60% yields of 4a (Table 1, entries 1-4).
Conversely, the non polar toluene, dioxane and THF were not
effective for this reaction (Table 1, entries 5-7).
2 | J. Name., 2012, 00, 1-3
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Table 3.Optimization for the one-pot synthesis of 4aa
Table 2. Screening of reducing agents and bases
DMF
100 ºC, N2
DMF
Se
Br
Br
Se
100 ºC
KSeCN
KSeCN
Ph
n-Oct
Ph
Ph
Ph
n-Oct
4a
3a
4a
1
3a
1
1) 10 min
2) base
reducing agent, 1h
1) 10 min
2) K3PO4, 1h
3) NaBH4, t
n-Oct Se
n-Oct-Br
n-OctSe
n-Oct-Br
2
2
6
2
5
2
entry
red. /basea
NaBH4
NaH
4a %b
57
n-Oct-SeCN %b
(5 + 6)%, ratio 5/6b
17, 70/30
52, 100/0
65, 32/68
92, 0/100
98, 10/90
26, 0/100
nd
Ratioa
% Yieldb
4a
entry
Cond.
1
2
3c
6
3a: 1: 2: K3PO4: NaBH4
1.0 : 1.3 : 1.2 : 1.3 : 1.3
1.0 : 1.5 : 1.35 : 1.5 : 1.5
1.0 : 1.5 : 1.35 : 1.5 : 1.5
1.0 : 1.5 : 1.35 : 1.5 : 1.5
22
nd
<5
<5
nd
73
98
1
2
3
4
1 h, N2
1 h, N2
1 h, Air
2h, Air
66
t-BuOK
K3PO4
<5
75
4
<5
76
80 (71)c
5
KOH
<5
aThe reaction was performed by using: 0.25 mmol of 3 and a ratio as
indicated in the second column, in 2 mL of DMF. bQuantified by GC with the
internal standard. cIsolated yield.
6
K2CO3
nd
7
DABCO
nd
aThe reaction was performed by using: 0.25 mmol of 3 and a ratio of 1 : 1.3 :
1.2 : 2.6 for 3a, 1, 2 and reducing agent or base, respectively. bQuantified by
GC with internal standard; nd: not detected. cPhenylethynyl n-octyl selenide
was also obtained in 33% yield.
In addition, the oxidation of selenolate anions to afford 6 can be
excluded since these reactions were carried-out under an inert
atmosphere and formation of 6 is only attributed to the presence
of K3PO4 (Table 2, entry 4).
Next, we explored the scope and limitations of this methodology for
the synthesis of alkyl styryl selenides with a variety of substituted
styryl and alkyl halides (Table 4). In general, for different primary
alkyl halides, including methyl iodide, 3-butenyl bromide, n-octyl
bromide and cyclohexylmethyl bromide, the corresponding alkyl
styryl selenides were obtained from moderate to excellent (71-95%)
yields; n-octyltosylate afforded 4a in good isolated yield (Table 4,
entries 1-5). The secondary cyclohexyl bromide afforded only 21%
yield of 4e (Table 4, entry 6) while the tertiary tert-butyl chloride
failed to render the alkane selenolate anion. Both results are clear
evidences of a competitive E2 reaction, and this is the main
limitation of the present methodology. Benzyl bromide and p-
fluorobenzyl chloride afforded the corresponding selenides 4f and
4g in 44% and 48% yield, respectively, while for ortho-substituted
benzyl halides the yields of selenides 4h and 4i dropped to 25% and
21% respectively (Table 4, entries 7-10). These results can be
ascribed to steric hindrance and secondary reactions involving the
benzyl halide and benzyl selenocyanate under basic and reductive
conditions (results not shown). Some examples were also
performed in PEG 300 as solvent but the yields were not improved.
(Table 4, entries 2 and 5).
The results summarized in Table 2, evidence that under certain
conditions it is possible to obtain only 6 without any trace of 5. As
mentioned above, alkyl selenolate anions can be generated by
reduction of the corresponding dialkyldiselenide. In consequence,
we planned to perform the same reaction in three steps: first, the
SN2 reaction between alkyl halide and KSeCN to afford
alkylselenocyanate; then, the K3PO4-assisted generation of
dialkyldiselenide from the previously obtained alkylselenocyanate;
finally, the reduction of dialkyldiselenide to render alkylselenolate
anion and the nucleophilic substitution of vinyl halides.
Scheme 3 shows the general strategy for the one-pot synthesis of
alkyl vinyl selenide in three steps and Table 3 summarizes the
results for the optimization conditions. First, we performed the
reaction with a ratio of 1: 1.3 : 1.2 : 1.3 : 1.3 for 3a, 1, 2, K3PO4 and
NaBH4 as a reducing agent, and the reaction time for the three
previously mentioned steps was 10 min, 1 h and 1 h, respectively.
Under these conditions compound 4a was obtained in 66% yield
(Table 3, entry 1). To improve the performance of the reaction, the
equivalents of KSeCN and alkyl halide were increased to 1.5 and
1.35 relative to 3a, affording an increase of vinyl selenide 4a to 75%
yield. Furthermore, when the reaction was conducted under air, the
yield was not modified (76%) (Table 3, entries 2 and 3). The third
step was performed for 2 h and the yield of 4a increased to 80%
quantified by GC and 71% isolated by column chromatography
(Table 3, entry 4).
Finally, the reactivity of a variety of substituted styryl halides with
n-octyltosylate was also studied (Table 5). Both E-styryl bromide
and chloride afforded 4a in good isolated yields and Z-styryl
bromide gave the corresponding Z-isomer Z4a in 84% yield (Table 5,
entries 1-3). We also tested the effect of the substituents on the
styryl moiety. The p-chloro derivative 3c afforded the selenide 4j in
comparable yields with the unsubstituted styryl bromide (Table 5,
entry 4); however, as the electron donor ability of the substituent
increased (Me and MeO), the reactivity of the corresponding vinyl
bromide decreased (Table 5, entries 5 and 6). Furthermore the
presences of the MeO group at the ortho position decreased the
yield to 52% due to steric hindrance, (Table 5, entry 7).
DMF
100 ºC, atm
Br
Se
KSeCN
Ph
Ph
R
3a
4
1
1) 10 min
2) K3PO4, 1h
3) NaBH4, t
RX
Scheme 3. One-pot three-step synthesis of alkyl vinyl selenides
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Table 4. One-Pot Synthesis of Alkyl (E) Styryl Selenidesa
Table 5. One-Pot Synthesis of Arylvinyl n-Octyl Selenidesa
entry
R-X
n-OctylBr
n-OctylOTs
MeI
product, yield(%)b
entry
3a-e Y, X
H, Br 3a
product 4a, j-l, yield(%)b
1
2
4a 71
4a 83c
4b 95
Se
Se
Se
Se
1
2
3
4
5
6
7
4a 83
4a 70
(Z)4a 84d
4j 83
Ph
Ph
n-Oct
n-Oct
Ph
Ph
n-Oct
n-Oct
H, Cl 3b
Se
3
(Z)-H, Brc
Cl, Br 3c
Ph
Me
Se
Se
n-Oct
4
CH2=CHCH2CH2Br
Cy-CH2Br
CyBr
4c 71
4d 85d
4e 21
4f 44
4g 48
4h 25
4i 21
Ph
Cl
Se
Se
Se
Se
Oct
5
n-
Ph
Ph
Me, Br 3d
MeO, Br 3e
o-MeO, Br
4k 80
Me
n-Oct
6
4l 74
4m 52
MeO
Se
Ph
7
PhCH2Br
Ph
F
F
8
aReaction conditions unless otherwise stated: aryl vinyl halide (3a-e) (0. 25
mmol), KSeCN (1) (0.38 mmol), n-octyl tosylate (0.34 mmol), K3PO4
(0.38mmol) and NaBH4 (0.38 mmol) in 2 mL of DMF.bIsolated yields. cZ-Styryl
bromide. dThe starting (Z)-vinyl halide contained ca. 10% of (E)-isomer; this
led to ca. 10% of the trans-isomer in the product.
Se
Cl
Ph
I
I
9
Se
Br
Cl
Ph
Br
O
O
O
10
Br
Se
O
Ph
R
aReaction conditions unless otherwise stated: (E)-β−bromostyrene (3a) (0.
25 mmol), KSeCN (1) (0.38 mmol), alkyl halide (0.34 mmol), K3PO4
(0.38mmol) and NaBH4 (0.38 mmol) in 2 mL of DMF. bIsolated yields.
cPerformed in PEG 300, 51% isolated yield, with minor amount of 5 and 6.
dPerformed in PEG 300, 70% isolated yield, with minor amount of 5 and 6.
K3PO4
RSeCN
CN-
SN2
Se
Se
RSe-
RX
RSeCN
KSeCN
R
X-
R
Br
NaBH4
Ar
Se
RSe-
Se
Ar
R
Se
SNV
R
The effect of the substituents on the styryl halides, the
stereochemical outcome of the reaction (configuration retention)
and the occurrence of the reaction without catalysis suggest that
the reaction of arylvinyl halides with alkyl selenolate anion follows a
classical mechanism of concerted addition-elimination vinylic
nucleophilic substitution similar to their analogue alkyl thiolate
anion. Thus, the mechanism for the sequential one-pot synthesis of
alkyl vinyl selenides follows (Scheme 4). First, alkyl halide reacts
with KSeCN by a SN2 mechanism to afford the corresponding alkyl
selenocyanate. In the presence of K3PO4, this intermediate (RSeCN)
is hydrolyzed by traces of water present in DMF20 to produce alkyl
selenolate anion which fast attacks the selenium atom of another
molecule of RSeCN affording the corresponding dialkyl diselenide.
The dialkyl diselenide was then reduced by NaBH4 to yield alkane
selenolate anion able to react with the vinyl halide by a vinylic
nucleophilic substitution (SNV).21
Scheme 4. Proposed mechanism for one-pot formation of alkyl aryl
vinyl selenide.
Experimental
Materials and methods: KSeCN, alkyl and benzyl halides were all
high-purity commercial samples used without further purification.
(E) and (Z)-β-bromostyrenes were prepared from cinnamic acids
following literature procedures.22 Di-Octyl selane (5)23 and 1,2-
dioctyl diselane (6)24 were isolated from the reaction mixture by
column chromatography and exhibited physical properties identical
to those reported in the literature. DMF, acetonitrile and DMSO
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absolute grade were used without further purification and stored 129.2, 129.0, 128.7, 101.8, 32.8. 77Se NMR (76 MHz, CDCl3): δ =
over molecular sieves (4 Å). Toluene, dioxane, THF and pyridine 281.9. GC-MS (EI) m/z 91 (100) [M-SeCN]+, 65 (18).
were distilled by standard procedures and stored over molecular General experimental procedures for one-pot synthesis of alkyl
sieves (4 Å). PEG 300 and ethanol were used without further styryl selenides: The reactions were carried out in a 10 mL three-
purification. All the reaction products were isolated by radial necked Schlenk tube, equipped with a magnetic stirrer. The tube
chromatography (silica gel, petroleum/diethyl ether) from the was charged with DMF (2.0 mL). Potassium selenocyanate (0.375
reaction mixture and characterized by 1H, 13C and 77Se NMR and mmol), alkyl halide (0.335 mmol), β-halostyrene (0.25 mmol) were
1
mass spectrometry. H, 13C and 77Se NMR spectra were recorded at added and stirred for 10 min at 100 ºC. K3PO4 (0.375 mmol) was
400.16 and 100.62 MHz respectively on a Bruker 400 spectrometer, then added and the mixture was stirred for 1 h. Finally, NaBH4
and all spectra were reported in δ (ppm) relative to Me4Si, with (0.375 mmol) was also added and the mixture was stirred for 2 h.
CDCl3 as a solvent. The chemical shifts in 77Se specta were given in The reaction mixture was cooled to room temperature. Diethyl
ppm using diphenyl diselenide (PhSeSePh) diluted in CDCl3 as an ether (15 mL) and water (15 mL) were added and the mixture was
external standard (δ 463 ppm at 25 ºC). Gas chromatographic stirred. The organic layer was separated and the aqueous layer was
analyses were performed on Agilent 5890 with a flame-ionization extracted with diethyl ether (2 × 15 mL). The combined organic
detector, on 30 m capillary column of a 0.32 mm x 0.25 ꢀm film extract was dried over anhydrous Na2SO4 and the products were
thickness, with a 5% phenylpolysiloxane phase. GS-MS analyses isolated by radial chromatography from the crude reaction mixture.
1
were conducted on Agilent 7890 employing a 30 m x 0.25 mm x The identity of all the products was confirmed by H, 13C, 77Se NMR
0.25 ꢀm with a 5% phenylpolysiloxane phase column. HRMS spectra and EI MS.
were recorded on a GCT Premie orthogonal acceleration time-of- (E)-Octyl(styryl)selane (4a): Following the general procedure, using
flight (oa-TOF) GC mass spectrometer. Ionization was achieved by potassium selenocyanate (54.0 mg, 0.375 mmol), n-octyl tosylate
electronic impact (70eV) and detection setup positive mode.
(95.7 mg, 0.337 mmol), (E)-β-bromostyrene (45.5 mg, 0.25 mmol)
for 10 min at 100 ºC, potassium phosphate (79.9 mg, 0.375 mmol)
for 1 h at 100 ºC and sodium borohydride (14.2 mg, 0.375 mmol)
Synthetic procedures
for
2 h at 100 ºC. Purification was performed by radial
General experimental procedures for the reactions of 1 and chromatography (pentane) providing 4a as a pale yellow oil (61.4
1
benzyl, alkyl and vinyl bromides (Scheme 1). The reactions were mg, 83% yield). H NMR (400 MHz, CDCl3): δ = 7.33 – 7.24 (m, 4H),
carried out in a 10 mL three-necked Schlenk tube, equipped with a 7.24 – 7.15 (m, 1H), 7.04 (d, J = 15.9 Hz, 1H), 6.73 (d, J = 15.9 Hz,
magnetic stirrer. The tube was charged with DMF (2.0 mL). 1H), 2.81 (t, J = 7.3 Hz, 2H), 1.76 (q, J = 7.3 Hz, 2H), 1.46 – 1.37 (m,
Potassium selenocyanate (0.25 mmol) and benzyl, n-octyl or (E)-β- 2H), 1.34 – 1.23 (m, 8H), 0.88 (t, J = 6.9 Hz, 3H). 13C NMR (100 MHz,
styryl bromides (0.25 mmol) were added and stirred at the CDCl3): δ = 137.5, 132.1, 128.6, 127.1, 125.7, 119.5, 31.8, 30.4, 29.9,
corresponding temperature for 5 min (2 h for (E)-β-bromostyrene). 29.2, 29.1, 26.3, 22.7, 14.1. 77Se NMR (76 MHz, CDCl3): δ = 267.6.
The reaction mixture was cooled to room temperature. Diethyl GC-MS (EI) m/z 296 (69) [M]+, 184 (100), 102 (39), 91 (39), 77 (21),
ether (15 mL) and water (15 mL) were added and the mixture was 71 (39), 57 (75), 55 (33), 43 (82), 41 (70). HRMS (ESI-TOF) m/z calcd
stirred. The organic layer was separated and the aqueous layer was for C16H24Se [M]+ 296.1038, found 296.1040.
extracted with diethyl ether (2 × 15 mL). The combined organic (E)-Methyl(styryl)selane (4b): Following the general procedure,
extract was dried over anhydrous Na2SO4, and the product was using potassium selenocyanate (54.0 mg, 0.375 mmol), methyl
isolated by column chromatography (silica gel, eluent: hexane). The iodide (21.0 μL, 0.337 mmol), (E)-β-bromostyrene (45.5 mg, 0.25
1
identity of all the products was confirmed by H, 13C and 77Se NMR mmol) for 10 min at 100 ºC, potassium phosphate (79.9 mg, 0.375
and EI MS.
mmol) for 1 h at 100 ºC and sodium borohydride (14.2 mg, 0.375
mmol) for 2 h at 100 ºC. Purification was performed by radial
chromatography (pentane) providing 4b as a pale yellow oil (47.0
1-Selenocyanatooctane:25 Following the general procedure, using
potassium selenocyanate (36.0 mg, 0.25 mmol) and n-octyl bromide
(48.3 mg, 0.25 mmol) for 5 min at 100 ºC. Purification was
performed by column chromatography (pentane) providing the title
compound as a pale yellow oil (53.5 mg, 95% yield).1H NMR (400
MHz, CDCl3): δ = 3.06 (t, J = 7.4 Hz, 2H), 1.90 (quint, J = 7.3 Hz, 2H),
1
mg, 95% yield). H NMR (400 MHz, CDCl3): δ = 7.27 – 7.31 (m, 4H),
7.18 – 7.23 (m, 1H), 7.07 (d, J = 15.8 Hz, 1H), 6.61 (d, J = 15.8 Hz,
1H), 2.26 (s, 3H). 13C NMR (100 MHz, CDCl3): δ = 137.4, 130.4, 128.6,
127.0, 125.6, 120.0, 5.5. 77Se NMR (76 MHz, CDCl3): δ = 183.8. GC-
MS (EI) m/z 198 (89) [M]+, 183 (100), 102 (99), 77 (56), 63 (23), 51
(57). HRMS (ESI-TOF) m/z calcd for C9H10Se [M]+ 197.9942, found:
197.9943.
1.48 – 1.39 (m, 2H), 1.34 – 1.24 (m, 8H), 0.89 (t, J = 6.9 Hz, 3H). 13
C
NMR (100 MHz, CDCl3): δ = 101.5, 31.7, 30.8, 29.7, 29.1, 29.0, 28.8,
22.6, 14.0. 77Se NMR (76 MHz, CDCl3): δ = 207.6. GC-MS (EI) m/z 219
(72) [M]+, 137 (100), 101 (82), 75 (52), 50 (40).
(Selenocyanatomethyl)benzene:26
(E)-But-3-en-1-yl(styryl)selane (4c): Following the general
procedure, using potassium selenocyanate (54.0 mg, 0.375 mmol),
4-bromobut-1-ene (34.2 μL, 0.337 mmol), (E)-β-bromostyrene (45.5
mg, 0.25 mmol) for 10 min at 100 ºC, potassium phosphate (79.9
mg, 0.375 mmol) for 1 h at 100 ºC and sodium borohydride (14.2
mg, 0.375 mmol) for 2 h at 100 ºC. Purification was performed by
radial chromatography (pentane) providing 4c as a pale yellow oil
(72.2 mg, 71% yield). 1H NMR (400 MHz, CDCl3): δ = 7.32 – 7.28 (m,
4H), 7.24 – 7.18 (m, 1H), 7.04 (d, J = 15.9 Hz, 1H), 6.75 (d, J = 15.9
Following
the
general
procedure, using potassium selenocyanate (36.0 mg, 0.25 mmol)
and benzyl bromide (42.7 mg, 0.25 mmol) for 5 min at room
temperature.
Purification
was
performed
by
column
chromatography (pentane) providing the title compound as a white
solid (53.5 mg, 98% yield). 1H NMR (400 MHz, CDCl3): δ = 7.38 –
7.32 (m, 5H), 4.31 (s, 2H).13C NMR (100 MHz, CDCl3): δ = 135.4,
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Hz, 1H), 5.86 (ddt, J = 16.9, 10.2, 6.6 Hz, 1H), 5.11 (ddd, J = 16.9, 2.8, 4-fluorobenzyl chloride (48.7 mg, 0.337 mmol), (E)-β-bromostyrene
1.9 Hz, 1H), 5.07 (ddd, J = 10.2, 2.8, 1.3 Hz, 1H), 2.87 (t, J = 7.5 Hz, (45.5 mg, 0.25 mmol) for 10 min at 100 ºC, potassium phosphate
2H), 2.57 – 2.49 (m, 2H). 13C NMR (100 MHz, CDCl3): δ = 137.4, (79.9 mg, 0.375 mmol) for 1 h at 100 ºC and sodium borohydride
137.0, 132.8, 128.6, 127.2, 125.7, 119.0, 116.1, 34.5, 25.0. 77Se NMR (14.2 mg, 0.375 mmol) for 2 h at 100 ºC. Purification was performed
(76 MHz, CDCl3): δ = 270.2. GC-MS (EI) m/z 238 (45) [M]+, 183 (54), by radial chromatography (pentane) providing 4g as a yellow solid
182 (40), 157 (19), 129 (58), 116 (87), 102 (77), 91 (65), 77 (53), 55 (35.0 mg, 48% yield). 1H NMR (400 MHz, CDCl3): δ = 7.33 – 7.27 (m,
(100), 51 (37). HRMS (APCI) m/z calcd for C12H15Se [M+H]+ 6H), 7.23 (dt, J = 9.2, 4.2 Hz, 1H), 7.02 – 6.97 (m, 3H), 6.77 (d, J =
239.03338, found:239.03357.
15.8 Hz, 1H), 4.01 (s, 2H). 13C NMR (100 MHz, CDCl3): δ = 161.8 (d,
4
(E)-(Cyclohexylmethyl)(styryl)selane (4d): Following the general 1JC-F = 244.5 Hz), 137.2, 134.1, 134.1 (d, JC-F = 4.3 Hz), 130.4 (d, 3JC-F
2
procedure, using potassium selenocyanate (54.0 mg, 0.375 mmol), = 8.1 Hz), 128.7, 127.5, 125.8, 118.5, 115.5 (d, JC-F = 21.4 Hz), 29.1.
bromomethyl cyclohexane (46.9 μL, 0.337 mmol), (E)-β- 77Se NMR (76 MHz, CDCl3): δ = 343.1. GC-MS (EI) m/z 292 (6) [M]+,
bromostyrene (45.5 mg, 0.25 mmol) for 10 min at 100 ºC, 183 (7), 109 (100), 102 (8), 77 (3), 51 (4). HRMS (APCI) m/z calcd for
potassium phosphate (79.9 mg, 0.375 mmol) for 1 h at 100 ºC and C15H12FSe [M-H]+ 291.00832, found 291.00867.27 HRMS (APPI) m/z
sodium borohydride (14.2 mg, 0.375 mmol) for 2 h at 100 ºC. calcd for C15H13FSe [M]+ 292.01669, found 292.01742.
Purification was performed by radial chromatography (pentane) (E)-(2-Iodobenzyl)(styryl)selane (4h): Following the general
providing 4d as a pale yellow oil (59.5 mg, 85% yield).1H NMR (400 procedure, using potassium selenocyanate (54.0 mg, 0.375 mmol),
MHz, CDCl3): δ = 7.31 – 7.28 (m, 4H), 7.24 – 7.17 (m, 1H), 7.03 (d, J = 2-iodobenzyl chloride (84.6 mg, 0.337 mmol), (E)-β-bromostyrene
15.9 Hz, 1H), 6.72 (d, J = 15.9 Hz, 1H), 2.73 (d, J = 6.8 Hz, 2H), 1.93 – (45.5 mg, 0.25 mmol) for 10 min at 100 ºC, potassium phosphate
1.85 (m, 2H), 1.79 – 1.69 (m, 2H), 1.69 – 1.63 (m, 1H), 1.63 – 1.55 (79.9 mg, 0.375 mmol) for 1 h at 100 ºC and sodium borohydride
(m, 1H), 1.32 – 1.20 (m, 2H), 1.19 – 1.09 (m, 1H), 1.06 – 0.94 (m, (14.2 mg, 0.375 mmol) for 2 h at 100 ºC. Purification was performed
2H). 13C NMR (100 MHz, CDCl3): δ = 137.6, 131.7, 128.6, 127.0, by radial chromatography (pentane) providing 4h as a yellow solid
1
125.6, 120.3, 38.6, 34.4, 33.5, 26.3, 26.1. 77Se NMR (76 MHz, CDCl3): (25.0 mg, 25% yield). H NMR (400 MHz, CDCl3): δ = 7.84 (d, J = 7.3
δ = 239.4. GC-MS (EI) m/z 280 (12) [M]+, 184 (32), 97 (28), 91 (12), Hz, 1H), 7.41 – 7.17 (m, 7H), 7.08 (d, J = 15.8 Hz, 1H), 6.91 (td, J =
55 (100), 41 (22). HRMS (ESI-TOF) m/z calcd for C15H20Se [M]+ 7.7, 1.6 Hz, 1H), 6.79 (d, J = 15.8 Hz, 1H), 4.13 (s, 2H). 13C NMR (100
280.0725, found: 280.0734.
MHz, CDCl3): δ = 141.3, 139.9, 137.2, 134.8, 129.9, 128.7, 128.6,
(E)-Cyclohexyl(styryl)selane (4e): Following the general procedure, 128.5, 127.5, 125.9, 118.3, 100.6, 35.6. 77Se NMR (76 MHz, CDCl3): δ
using potassium selenocyanate (54.0 mg, 0.375 mmol), = 338.4. GC-MS (EI) m/z 400 (21) [M]+, 217 (100), 183 (23), 102 (28),
bromocyclohexane (40.9 μL, 0.337 mmol), (E)-β-bromostyrene (45.5 91 (65), 90 (65), 89 (35), 77 (11), 63 (21), 51 (13). HRMS (ESI-TOF)
mg, 0.25 mmol) for 10 min at 100 ºC, potassium phosphate (79.9 m/z calcd for C15H13INaSe [M+Na]+ 422.9120, found: 422.9113.
mg, 0.375 mmol) for 1 h at 100 ºC and sodium borohydride (14.2 (E)-5-Bromo-6-((styrylselanyl)methyl)benzo[d][1,3]dioxole
mg, 0.375 mmol) for 2 h at 100 ºC. Purification was performed by Following the general procedure, using potassium selenocyanate
radial chromatography (pentane) providing 4e as a pale yellow oil (54.0 mg, 0.375 mmol), 5-bromo-6-
(4i):
1
(14.0 mg, 21% yield). H NMR (400 MHz, CDCl3): δ = 7.35 – 7.29 (m, (bromomethyl)benzo[d][1,3]dioxole (99.0 mg, 0.337 mmol), (E)-β-
4H), 7.22 (td, J = 5.8, 2.6 Hz, 1H), 7.11 (d, J = 15.9 Hz, 1H), 6.83 (d, J bromostyrene (45.5 mg, 0.25 mmol) for 10 min at 100 ºC,
= 15.9 Hz, 1H), 3.27 – 3.16 (m, 1H), 2.12 (d, J = 10.1 Hz, 2H), 1.78 potassium phosphate (79.9 mg, 0.375 mmol) for 1 h at 100 ºC and
(dd, J = 9.0, 4.3 Hz, 2H), 1.63 (dd, J = 10.3, 3.7 Hz, 2H), 1.43 – 1.26 sodium borohydride (14.2 mg, 0.375 mmol) for 2 h at 100 ºC.
(m, 4H).13C NMR (100 MHz, CDCl3): δ = 137.6, 134.1, 128.6,0 127.2, Purification was performed by radial chromatography (pentane)
125.8, 118.3, 41.6, 34.4, 26.8, 25.7. 77Se NMR (76 MHz, CDCl3): δ = providing 4i as a yellow solid (20.8 mg, 21% yield). 1H NMR (400
338.4. GC-MS (EI) m/z266 (32) [M]+, 184 (96), 102 (32), 91 (22), 77 MHz, CDCl3): δ = 7.35 – 7.27 (m, 4H), 7.24 – 7.19 (m, 1H), 7.10 (d, J =
(16), 55 (100), 51 (12), 41 (36). HRMS (APCI) m/z calcd for C14H19Se 15.8 Hz, 1H), 7.00 (s, 1H), 6.85 (s, 1H), 6.79 (d, J = 15.8 Hz, 1H), 5.96
[M+H]+ 267.06469, found: 267.06476.
(s, 2H), 4.07 (s, 2H). 13C NMR (100 MHz, CDCl3): δ = 147.6, 147.5,
(E)-Benzyl(styryl)selane (4f): Following the general procedure, 137.2, 134.4, 131.2, 128.6, 127.4, 125.9, 118.4, 114.8, 112.9, 110.2,
using potassium selenocyanate (54.0 mg, 0.375 mmol), benzyl 101.8, 30.4. 77Se NMR (76 MHz, CDCl3): δ = 342.3. GC-MS (EI) m/z
bromide (64.1 mg, 0.337 mmol), (E)-β-bromostyrene (45.5 mg, 0.25 396 (2) [M]+, 215 (100), 213 (93), 104 (17), 102 (22), 78 (37), 77 (25),
mmol) for 10 min at 100 ºC, potassium phosphate (79.9 mg, 0.375 76 (32), 75 (29), 51 (24), 50 (22). HRMS (ESI-TOF) m/z calcd for
mmol) for 1 h at 100 ºC and sodium borohydride (14.2 mg, 0.375 C16H13BrNaO2Se [M+Na]+ 418.9154, found 418.9145.
mmol) for 2 h at 100 ºC. Purification was performed by radial (Z)-Octyl(styryl)selane (Z4a): Following the general procedure,
chromatography (pentane) providing 4f as a light yellow solid (30.1 using potassium selenocyanate (54.0 mg, 0.375 mmol), n-octyl
1
mg, 44% yield). H NMR (400 MHz, CDCl3): δ = 7.38 – 7.26 (m, 8H), tosylate (95.7 mg, 0.337 mmol), (Z)-β-bromostyrene (45.5 mg, 0.25
7.25 – 7.19 (m, 2H), 7.03 (d, J = 15.9 Hz, 1H), 6.78 (d, J = 15.9 Hz, mmol) for 10 min at 100 ºC, potassium phosphate (79.9 mg, 0.375
1H), 4.04 (s, 2H).13C NMR (100 MHz, CDCl3): δ = 138.3, 137.3, 133.6, mmol) for 1 h at 100 ºC and sodium borohydride (14.2 mg, 0.375
128.9, 128.6, 128.6, 127.3, 127.1, 125.8, 118.9, 29.9. 77Se NMR (76 mmol) for 2 h at 100 ºC. Purification was performed by radial
MHz, CDCl3): δ = 340.9. GC-MS (EI) m/z 274 (10) [M]+, 183 (5), 91 chromatography (pentane) providing Z4a as a pale yellow oil (62.2
(100), 65 (13). HRMS (ESI-TOF) m/z calcd for C15H14Se [M]+ mg, 84% yield). The starting (Z)-vinyl halide contained ca. 10% of
274.0256, found 274.0260.
(E)-isomer; this led to ca. 10% of the trans-isomer in the product.1H
(E)-(4-Fluorobenzyl)(styryl)selane (4g): Following the general NMR (400 MHz, CDCl3): δ = 7.46 – 7.15 (m, 5H), 6.87 (d, J = 10.6 Hz,
procedure, using potassium selenocyanate (54.0 mg, 0.375 mmol), 1H), 6.60 (d, J = 10.6 Hz, 1H), 2.78 (t, J = 7.3 Hz, 2H), 1.75 (q, J = 7.3
6 | J. Name., 2012, 00, 1-3
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Hz, 2H), 1.44 – 1.35 (m, 2H), 1.29 (m, 8H), 0.88 (t, J = 6.9 Hz, 3H). 13
C
(E)-(2-Methoxystyryl)(octyl)selane (4m): Following the general
procedure, using potassium selenocyanate (54.0 mg, 0.375 mmol),
n-octyl tosylate (95.7 mg, 0.337 mmol), (E)-1-(2-bromovinyl)-2-
methoxybenzene (53.2 mg, 0.25 mmol) for 10 min at 100 ºC,
potassium phosphate (79.9 mg, 0.375 mmol) for 1 h at 100 ºC and
sodium borohydride (14.2 mg, 0.375 mmol) for 2 h at 100 ºC.
Purification was performed by radial chromatography (pentane)
NMR (100 MHz, CDCl3): δ = 137.7, 129.3, 128.3, 126.8, 123.2, 31.8,
30.7, 29.7, 29.2, 29.1, 22.6, 14.1. 77Se NMR (76 MHz, CDCl3): δ =
263.1. GC-MS (EI) m/z 296 (58) [M]+, 184 (97), 102 (59), 91 (30), 71
(36), 43 (100), 41 (55). HRMS (ESI-TOF) m/z calcd for C16H24Se [M]+
296.1038, found 296.1041.
(E)-(4-Chlorostyryl)(octyl)selane (4j): Following the general
procedure, using potassium selenocyanate (54.0 mg, 0.375 mmol),
n-octyl tosylate (95.7 mg, 0.337 mmol), (E)-1-(2-bromovinyl)-4-
chlorobenzene (54.4 mg, 0.25 mmol) for 10 min at 100 ºC,
potassium phosphate (79.9 mg, 0.375 mmol) for 1 h at 100 ºC and
sodium borohydride (14.2 mg, 0.375 mmol) for 2 h at 100 ºC.
Purification was performed by radial chromatography (pentane)
1
providing 4m as pale yellow oil (42.4 mg, 52% yield). H NMR (500
MHz, CDCl3): δ = 7.34 (dd, J = 7.6, 1.7 Hz, 1H), 7.19 (ddd, J = 8.2, 7.5,
1.7 Hz, 1H), 7.09 (d, J = 16.0 Hz, 1H), 7.03 (d, J = 16.0 Hz, 1H), 6.91
(td, J = 7.5, 1.0 Hz, 1H), 6.85 (dd, J = 8.2, 0.8 Hz, 1H), 3.84 (s, 3H),
2.85 – 2.78 (m, 2H), 1.76 (q, J = 7.4 Hz, 2H), 1.47 – 1.38 (m, 2H), 1.35
– 1.23 (m, 8H), 0.88 (t, J = 7.0 Hz, 3H). 13C NMR (126 MHz, CDCl3): δ
= 156.0, 128.1, 127.2, 126.6, 126.5, 120.7, 120.1, 110.9, 55.4, 31.8,
30.4, 29.9, 29.2, 29.1, 26.2, 22.7, 14.1. 77Se NMR (76 MHz, CDCl3): δ
= 269.6. GC-MS (EI) m/z 326 (57) [M]+, 214 (29), 198 (27), 183 (23),
134 (59), 119 (43), 105 (43), 91 (38), 77 (21), 57 (38), 41 (100).
HRMS (APCI) m/z calcd for C17H27OSe [M+H]+ 327.12222, found
327.12075.
1
providing 4j as a pale yellow oil (68.5 mg, 83% yield). H NMR (400
MHz, CDCl3): δ = 7.28 – 7.19 (m, 4H), 7.04 (d, J = 15.9 Hz, 1H), 6.66
(d, J = 15.9 Hz, 1H), 2.82 (t, J = 6.8 Hz, 2H), 1.76 (q, J = 6.8 Hz, 2H),
1.47 – 1.37 (m, 2H), 1.30 (m, 8H), 0.88 (t, J = 6.8 Hz, 3H). 13C NMR
(100 MHz, CDCl3): δ = 136.0, 132.6, 130.5, 128.8, 126.8, 120.6, 31.8,
30.3, 29.8, 29.2, 29.1, 26.3, 22.6, 14.1. 77Se NMR (76 MHz, CDCl3): δ
= 271.6. GC-MS (EI) m/z 330 (40) [M]+, 218 (28), 183 (40), 102 (20),
71 (51), 57 (78), 43 (100), 41 (71). HRMS (APCI) m/z calcd for
C
16H24ClSe [M+H]+ 331.07241, found: 331.07245.
Conclusions
(E)-(4-Methylstyryl)(octyl)selane (4k): Following the general
procedure, using potassium selenocyanate (54.0 mg, 0.375 mmol),
n-octyl tosylate (95.7 mg, 0.337 mmol), (E)-1-(2-bromovinyl)-4-
methylbenzene (49.2 mg, 0.25 mmol) for 10 min at 100 ºC,
potassium phosphate (79.9 mg, 0.375 mmol) for 1 h at 100 ºC and
sodium borohydride (14.2 mg, 0.375 mmol) for 2 h at 100 ºC.
Purification was performed by radial chromatography (pentane)
providing 4k as pale yellow oil (62.0 mg, 80% yield). 1H NMR (400
MHz, CDCl3): δ = 7.20 (d, J = 8.1 Hz, 2H), 7.10 (d, J = 8.1 Hz, 2H), 6.97
(d, J = 15.9 Hz, 1H), 6.71 (d, J = 15.9 Hz, 1H), 2.80 (t, J = 7.3 Hz, 2H),
2.31 (s, 3H), 1.75 (q, J = 7.3 Hz, 2H), 1.46 – 1.37 (m, 2H), 1.35 – 1.22
(m, 8H), 0.88 (t, J = 6.9 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ =
136.9, 134.8, 132.5, 129.3, 125.6, 118.0, 31.8, 30.4, 29.9, 29.9, 29.1,
26.3, 22.6, 21.2, 14.1. 77Se NMR (76 MHz, CDCl3): δ = 264.3. GC-MS
(EI) m/z 310 (82) [M]+, 198 (61), 197 (29), 183 (65), 115 (63), 105
(19), 91 (20), 71 (36), 57 (64), 43 (100), 41 (86).HRMS (ESI-TOF) m/z
calcd for C17H26Se [M]+ 310.1195, found: 310.1169.
In summary, we have developed a new one-pot methodology for
the stereoselective synthesis of alkyl arylvinyl selenides in
moderate to excellent yields, free of any transition metal/ligand
systems, from malodorous and air-sensitive selenolate anions and
diselenide as starting reagents. This procedure employs the
commercially available potassium selenocyanate, DMF as a solvent,
short reaction time and air atmosphere
Acknowledgements
This work was supported partly by Consejo Nacional de
Investigaciones Científicas y Técnicas (CONICET) and Fondo de
Ciencia
y Tecnología (FONCYT), Argentina. A. A. H. gratefully
acknowledges the receipt of a fellowship from CONICET.
SUPPORTING INFORMATION: Spectra (1H, 13C and 77Se NMR)
for all the products (4a-m and Z4a).
(E)-(4-Methoxystyryl)(octyl)selane (4l): Following the general
procedure, using potassium selenocyanate (54.0 mg, 0.375 mmol),
n-octyl tosylate (95.7 mg, 0.337 mmol), (E)-1-(2-bromovinyl)-4-
methoxybenzene (53.2 mg, 0.25 mmol) for 10 min at 100 ºC,
potassium phosphate (79.9 mg, 0.375 mmol) for 1 h at 100 ºC and
sodium borohydride (14.2 mg, 0.375 mmol) for 2 h at 100 ºC.
Purification was performed by radial chromatography (pentane)
providing 4l as a white solid (60.3 mg, 74% yield). 1H NMR (400
MHz, CDCl3): δ = 7.26 – 7.21 (m, 2H), 6.87 (d, J = 15.8 Hz, 1H), 6.84 –
6.82 (m, 2H), 6.71 (d, J = 15.8 Hz, 1H), 3.80 (s, 3H), 2.79 (t, J = 6.8 Hz,
2H), 1.75 (q, J = 6.8 Hz, 2H), 1.46 – 1.37 (m, 2H), 1.34 – 1.22 (m, 8H),
0.88 (t, J = 6.9 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ = 158.9, 132.5,
130.5, 126.9, 116.3, 114.1, 55.3, 31.8, 30.4, 29.8, 29.2, 29.1, 26.4,
22.6, 14.1. 77Se NMR (76 MHz, CDCl3): δ = 262.1. GC-MS (EI) m/z 326
(25) [M]+, 214 (16), 198 (11), 134 (100), 57 (12), 43 (26), 41
(23).HRMS (ESI-TOF) m/z calcd for C17H26OSe [M+Na]+ 349.1042,
found 349.1050.
Notes and references
1
a) Rappoport, Ed. The Chemistry of Organic Selenium and
Tellurium Compounds; John Wiley & Sons: Chichester, 2014
(Vol. 4). b) Z. Rappoport, Ed. The Chemistry of Organic
Selenium and Tellurium Compounds; John Wiley & Sons:
Chichester, 2012 (Vol. 3). c) Wirth, T. Ed. Organoselenium
Chemistry. Modern Development in Organic Synthesis in
Topics in Current Chemistry 208, Springer-Verlag Berlin
Heidelberg, 2000.
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3
G. Perin, E. J. Lenardão, R. G. Jacob, and R. B. Panatieri,
Chem. Rev. 2009, 109, 1277.
a) F. Alonso, I. P. Beletskaya and M. Yus, Chem. Rev. 2004,
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O. Boutureira, M. I. Matheu, Y. Diaz and S. Castillon,
Carbohydr. Res. 2007, 342, 736.
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5
a) E. J. Lenardao, M. S. Silva, M. Sachini, R. G. Lara, R. G.
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