Synthesis and reactivity of divinylselenium dichlorides and dibromides

Article abstract of DOI:10.1055/s-0030-1258395

Regio- and stereospecific electrophilic addition reactions of selenium tetrachloride and selenium tetrabromide to propargyl alcohols are reported. (Z,Z)-Bis(β-chlorovinyl)selenium dichlorides were isolated in high yields, and their reactivity was dependen

Full text of DOI:10.1055/s-0030-1258395

PAPER
577
Synthesis and Reactivity of Divinylselenium Dichlorides and Dibromides
D
ivinylseleniu
a
m
D
ihalide
m
s
uel Braverman,* Tatiana Pechenick-Azizi, Hugo E. Gottlieb, Milon Sprecher
Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900, Israel
Fax +972(3)7384053; E-mail: bravers@mail.biu.ac.il
Received 15 November 2010
OH
R2
R1
Abstract: Regio- and stereospecific electrophilic addition reactions
of selenium tetrachloride and selenium tetrabromide to propargyl
alcohols are reported. (Z,Z)-Bis(b-chlorovinyl)selenium dichlorides
were isolated in high yields, and their reactivity was dependent on
their substitution pattern. Products derived from unsubstituted,
a-methyl-, or a,a-dimethylpropargyl alcohols readily underwent
transfer of chlorine atoms to one of the two double bonds. (Z,Z)-
Bis(b-chlorovinyl)selenium dichlorides derived from g-phenyl- or
g-isopropenylpropargyl alcohols underwent cyclization to form
benzoselenophene derivatives; this was accompanied by the forma-
tion of the corresponding dichloro-substituted allylic alcohols. In
contrast, selenium tetrachloride reacts with g-phenylpropargyl alco-
hol exclusively as a chlorinating agent, giving (3-chloroprop-1-yn-
1-yl)benzene quantitatively. Products of regio- and stereospecific
electrophilic addition of selenium tetrabromide are also described.
Reaction mechanisms are proposed.
R3
½ SeCl2
THF, r.t.
[Se + SO2Cl2]
Cl
Cl
Cl
Cl
Se
Se Se
R1
R3
R3
R3
R1
R3
OH
R1
R2
R1
OH R2
major
+
R2
OH
minor
R2
OH
Scheme 1
product was likely to be of synthetic interest because of
the presence of a reactive selenium dichloride moiety.
Key words: electrophilic additions, alkynes, alcohols, selenium, Addition reactions of tetravalent selenium reagents
halides
(SeCl4, SeBr4, ArSeCl3, or ArSeBr3) to alkenes have re-
ceived some attention,6–10 and they have been found to be
generally nonregioselective.
Our past experience with reactions of propargyl alcohols
Although, dialkyl- and diarylselenium dihalides have
been known for many years,11 and are employed as inter-
mediates for the synthesis of other organoselenium com-
pounds, isolated divinylselenium dichlorides are almost
unknown. More than forty years ago, bis(2-chlorovi-
nyl)selenium dichloride and bis(2-chloro-2-phenylvi-
nyl)selenium dichloride were prepared in 9 and 73%
yields, respectively, by treatment of acetylene or phenyl-
acetylene, respectively, with SeCl4, but the stereochemis-
try of the products was not reported.12a
with electrophilic sulfur reagents such as sulfur dichloride
(SCl2)1 or disulfur dichloride (S2Cl2)2 led us to examine
the reactions of the corresponding selenium analogues.
Selenium dichloride (SeCl2) was prepared, according to a
recently reported procedure, from elemental selenium and
sulfuryl chloride (SO2Cl2) in tetrahydrofuran.3 Its reac-
tions with various propargyl alcohols showed some sur-
prising results. Unlike sulfur dichloride, selenium
dichloride readily undergoes 1,2-addition to the triple
bond of propargyl alcohols, resulting in the formation of
functionalized (Z,Z)-bis(b-chlorovinyl)selenides in high
yields and with complete regio- and stereospecificity
(Scheme 1).4,5 In some cases, the selenide is accompanied
by the corresponding diselenide. Furthermore, and con-
trary to expectations, the divinylselenides and diselenides
are the products of syn-addition with anti-Markovnikov
orientation. The hydroxy group of the reactants appears to
be responsible for this behavior. We recently proposed a
possible mechanism for electrophilic addition of selenium
dichloride to the triple bond of a propargyl alcohol that in-
volves selenirenium ion intermediates.5 Prompted by
these results, we decided to investigate the addition of se-
lenium tetrachloride to propargyl alcohols with the hope
of obtaining the corresponding divinylselenium dichlo-
rides in a regio- and stereospecific manner. The expected
Some three decades ago, it was reported that the reaction
of phenylacetylene derivatives with SeCl4 and SeBr4 leads
to the corresponding benzoselenophene derivatives.12b–d
Recently, a stereospecific synthesis of (E,E)-bis(2-chloro-
vinyl) selenide from selenium tetrachloride and acetylene
has been reported,13a,b but no bis(2-chlorovinyl)selenium
dichloride was isolated. Electrophilic additions of SeBr4
and SeCl4 to diorganyl(diethynyl)silanes13c–g and diorgan-
yl(diethynyl)germanes13g,h have been reported to result in
regio- and stereoselective formation of a new class of un-
saturated five-membered heterocycles. It was proposed
that, initially, SeCl4 and SeBr4 participate in the reaction
as halogenation agents, leading to the formation of the in-
termediate ethynyl(1,2-dihalovinyl)silanes or -germanes
and selenium dihalides. This is followed by Markovnikov
trans-addition of the resulting selenium dihalide to the tri-
ple bond, followed by anti-Markovnikov addition of the
selenenyl halide to the dihalovinyl moiety.
SYNTHESIS 2011, No. 4, pp 0577–0584
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x
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Advanced online publication: 11.01.2011
DOI: 10.1055/s-0030-1258395; Art ID: P17010SS
© Georg Thieme Verlag Stuttgart · New York

578
S. Braverman et al.
PAPER
To the best of our knowledge, no addition of SeX4 to pro- conditions mentioned above were different from those
pargyl alcohols has been reported. Because of the synthet- used for the reaction of propargyl alcohols with SeCl2. In
ic potential of divinylselenium dichlorides as inter- the present case, for convenience, the alcohol was added
mediates in organoselenium chemistry, and the fact that to a suspension of SeCl4 in dry chloroform, and the reac-
the hydroxy group plays an important role in the regio- tion proceeded at a lower temperature and in a shorter
and stereospecific addition of SeCl2,4,5 we were interested time. The use of chloroform as a solvent made it possible
in exploring the addition reactions of SeCl4 and SeBr4 to determine the end point of the reaction from the com-
with propargyl alcohols, and the stereochemistry of these plete disappearance of the solid SeCl4. The reaction of
reactions.
but-3-yn-2-ol (a-methylpropargyl alcohol) with SeCl4 led
to a similar type of product 3b, which was obtained as a
mixture of four diastereomers because of the presence of
two chiral centers. The diastereomers were separated by
column chromatography and found to be stable even after
refluxing in chloroform solution for three hours. To reca-
pitulate, the addition of SeCl4 to the triple bond of these
propargyl alcohols was found to be syn with an anti-
Markovnikov orientation.
The reaction of 2-methylbut-3-yn-2-ol (a,a-dimethylpro-
pargyl alcohol) with commercially available selenium tet-
rachloride in dry chloroform under argon at 0 °C for 30
minutes gave a product that was not the expected divi-
nylselenium dichloride 2a (Scheme 2). H and 13C NMR
1
spectra showed two CH peaks, one olefinic (7.08, 128.87
ppm, respectively) and one aliphatic (6.36, 77.29 ppm, re-
spectively), as well as four signals for different methyl
groups. On the basis of the JC–Se values14 (143.07 ppm, In sharp contrast to the above, the electrophilic addition of
1JC–Se = 124.2 Hz and 86.88 ppm, 1JC–Se = 113.9 Hz), the TeCl4 to propargyl alcohols led to the corresponding
13C NMR spectrum shows that two quaternary carbons (chlorovinyl)tellurium trichlorides, which were obtained
(one olefinic and one aliphatic) are attached to the selenium as mixtures of regio- and stereoisomers.5
1
atom. Two CH carbons show corresponding 2JC–Se values
(128.87 ppm, JC–Se = 28.2 Hz and 77.29 ppm, JC–Se
Interestingly, the unsymmetrical selenide 3a underwent
2
2
=
slow disproportionation upon heating for 2.5 hours in re-
fluxing chloroform, or more slowly at room temperature,
to give a mixture of (3E)-3,4-dichloro-2-methylbut-3-en-
2-ol (5a) and, apparently, the vinylselenenyl chloride 4
(Scheme 3). When the reaction was performed in the pres-
ence of triethylamine for three hours at the reflux, alcohol
5a was obtained as the sole organic product, accompanied
by precipitation of selenium. We conclude that the two
chlorine atoms in alcohol 5a have an anti orientation, be-
cause no NOE interaction between the methyl and vinyl
hydrogen atoms was observed.
13.0 Hz). The new product had an unsymmetrical struc-
ture with one chiral center and only one double bond. On
the basis of the 1H and 13C NMR spectra and a high-reso-
lution mass spectrometric elemental analysis, we con-
clude that this product is (3Z)-4-chloro-3-{[1-chloro-1-
(dichloromethyl)-2-hydroxy-2-methylpropyl]selanyl}-2-
methylbut-3-en-2-ol (3a; Scheme 2). The stereochemistry
of the double bond was determined by a NOESY experi-
ment in which a NOE interaction between methyl and ole-
finic hydrogen atoms was detected; their chemical shifts
were assigned by heteronuclear multiple bond correlation
(HMBC) and heteronuclear single quantum coherence
(HMQC) experiments.
Cl
Cl
Cl
Cl
H
Cl
Se
Se
Cl
Cl
+
H
Cl
H
OH
CDCl3
Cl
Cl
Cl
R3
Cl
OH
OH
R2
R1
Cl
5a
½ SeCl4
heat, 2.5 h
OH
3a
OH
Se
R1
OH
R3
R3
4
R1
R2
0 °C, 30 min
CHCl3
CDCl3, heat, 3 h, Et3N
OH
R2
1a; R1 = R2 = Me, R3 = H
1b; R1 = Me, R2 = H, R3 = H
Scheme 3
3a; 100%, 3b; 78%
Cl
Cl
Cl Cl
Se
The formation of 4 and 5a involves the 1,2-elimination of
selenium and chlorine, and could be initiated by attack by
a chloride ion on selenium (Scheme 3).
R3
R1
R3
OH
R1
R2
OH
R2
The vinylselenenyl chloride 4 was identified in the reac-
tion mixture by using 1H and 13C NMR spectroscopy, and
its presence was confirmed by two-dimensional NMR ex-
periments, as well as by high-resolution mass spectro-
scopic analysis. Attempts at isolation by silica gel
chromatography gave the (Z,Z)-divinyl diselenide 6
(Scheme 4).4,5 On addition of a,a-dimethylpropargyl al-
cohol 1a to the reaction mixture, the intermediate 4 was
immediately converted into the corresponding (Z,Z)-divi-
nyl selenide 7a.4,5
2a,b
Scheme 2
The formation of the selenide 3a can be explained in terms
of spontaneous transfer of chlorines in the corresponding
divinylselenium dichloride intermediate 2a to one of the
two double bonds. Selenide 3a was unstable, especially in
the crude mixture, and required immediate purification by
column chromatography. After isolation, product 3a
could be stored at –18 °C for several days. The reaction
Synthesis 2011, No. 4, 577–584 © Thieme Stuttgart · New York

PAPER
Divinylselenium Dihalides
579
Cl
In addition, during the workup, unsubstituted ethyl- and
phenyldivinylselenium dichlorides were easily converted
into the corresponding selenoxide 8c–e by rapid hydroly-
sis with 10% aqueous sodium bicarbonate, followed by
extraction with ethyl acetate (Scheme 5). The selenoxides
were stable solids and were easily purified and identified
spectroscopically. The characteristic NMR splitting pat-
tern of diastereotopic methylene protons caused by the
chirality of selenoxides, as well as the IR and high-resolu-
tion mass spectra support this structure. This reaction rep-
resents a simple method for preparing stable vinylic
selenoxides in a regio- and stereospecific manner. An al-
ternative preparation of divinylic selenoxides by oxida-
tion of the selenides has been recently reported by us,4,5
and their synthetic applications will be discussed sepa-
rately.
Cl
Cl
Cl
Cl
Se
Se Se
Se
1a
SiO2
r.t.
Cl
CDCl3
r.t.
<1 min
OH
OH
OH
HO
OH
7a
4
6
Scheme 4
To study the scope and limitation of the reactivity of the
putative divinylselenium dichlorides intermediates, we
examined the reaction of SeCl4 with unsubstituted and g-
substituted propargyl alcohols. Furthermore, the isolation
of the divinylselenium dichloride intermediate would
demonstrate that products of type 3 may indeed be formed
as a result of transfer of chlorine from an intermediate 2 to
one of the two double bonds. In principle, and like the re-
cently reported electrophilic addition of selenium tetra-
halides to diorganyldiethynylsilanes,13 the formation of
product 3 might be explained to result from direct chlori-
nation of half the propargyl alcohol by SeCl4 (0.5 equiva-
lents), leading to 2,3-dichloroprop-2-en-1-ol and SeCl2,
followed by addition of the latter to the second half of the
propargyl alcohol to form (2-chlorovinyl)selenenyl chlo-
ride, the electrophilic addition of which to 2,3-dichloro-
prop-2-en-1-ol should yield 3.
In keeping with the above, when a chloroform solution of
divinylselenium dichloride 2c was stirred overnight the
unsymmetrical selenide 3c (Scheme 6) was obtained; this
was found to be stable, even on refluxing in chloroform
for two hours.
Cl
Cl
Cl
Cl
Cl Cl
Se
Cl
H
CHCl3
Se
H
H
Cl
H
r.t., overnight
OH
OH
OH
OH
3c; 51%
In the event, by careful low-temperature workup, we suc-
ceeded in isolating high yields of the divinylselenium
dichlorides 2c–e derived from unsubstituted, g-ethyl- and
g-phenyl-substituted propargyl alcohols (Scheme 5), and
we were able to characterize these products. These unsta-
ble products, upon standing in acetone-d6 solution at room
temperature for 2–8 hours underwent dechlorination to
form the corresponding selenides 7c–e with the same re-
gio- and stereochemistry as the products obtained from
the reaction of the corresponding propargyl alcohols with
2c
Scheme 6
In the case of 3-phenylprop-2-yn-1-ol (g-phenylpropargyl
alcohol), the corresponding (Z,Z)-divinylselenium
dichloride 2e gave (3-chloro-1-benzoselenophen-2-
yl)methanol (12) and (2E)-2,3-dichloro-3-phenylprop-2-
en-1-ol (5e) (Scheme 7). In addition, during silica gel
chromatography benzoselenophene 12 underwent partial
substitution of the hydroxy group by chlorine to form 3-
chloro-2-(chloromethyl)-1-benzoselenophene (12a), pos-
sibly because of to the presence of traces of hydrogen
chloride. On the basis of an absence of a NOE interaction
between the phenyl and methylene hydrogen atoms, we
believe that the two chlorine atoms in alcohol 5e have an
anti orientation. Interestingly, the reaction of the same al-
cohol with SeCl2 gave the corresponding divinyl selenide,
and no cyclization product was observed.4,5
4,5
SeCl2 (Scheme 5). Compound 7c also formed from 2c
in the presence of triethylamine (two equivalents) in chlo-
roform at room temperature for two days. A similar
dechlorination reaction of saturated selenium dichloride
in refluxing acetone has been reported.15
Cl
Cl
Cl Cl
Se
½ SeCl4
OH
R2
R1
R3
R3
R3
OH
R1
R2
R1
0 °C, 30 min
CHCl3
1c; R1 = R2 = R3 = H
As mentioned above, the reaction of phenylacetylene de-
rivatives with selenium tetrachloride or tetrabromide to
give the corresponding benzoselenophenes has been re-
ported before.12 However, in these cases, benzosele-
nophenes were formed through cyclization of the
corresponding (E)-b-chloro-vinylselenium trihalide inter-
mediate, accompanied by release of HX and X2. In con-
trast, in the present case the (Z,Z)-configuration of the
divinyl selenium dichloride 2e prevents the immediate di-
rect ring closure form to the corresponding benzosele-
nophene. Conversion of 2e into 12 and 5e is a multistep
reaction whose details are as yet undetermined, although
the following mechanism might rationalize the formation
of the thermodynamically desirable product 12
(Scheme 7).
OH
R2
1d; R1 = R2 = H, R3 = Et
1e; R1 = R2 = H, R3 = Ph
2c; 91%, 2d; 83%, 2e; 92%
10% aq NaHCO3
< 1 min
acetone-d6
r.t.
Cl
Cl
Cl
O
Cl
Se
R1
Se
R3
R1
R3
R3
OH
R3
OH
R1
R2
R1
R2
OH
R2
OH
R2
8c; 54%
8d; 67%
8e; 44%
7c,* 8 h; 7d, 2.5 h; 7e, 2 h
*alternatively, 7c formed using
Et3N (2 equiv), CHCl3, r.t., 2 d
Scheme 5
Synthesis 2011, No. 4, 577–584 © Thieme Stuttgart · New York

580
S. Braverman et al.
PAPER
CHCl3
r.t.
Br
Br
Br
H
Cl
Cl
Cl Cl
Se
Ph
Se
overnight
Se
R3 = H
H
Br
OH
Cl
Ph
HO
Ph
Cl
+
– HCl
OH
OH
½ SeBr4
OH
Cl
OH
2e
HO
13; 85%
5e
12
total yield 51%
– HCl
0 °C, 30 min
CH2Cl2
Ph
Br
Se
R3 = Ph
– H2O
R3
Br
Br
+
1c, 1e
Cl
Cl
Cl
Br
HO
Ph
Cl
Se
Se
14
15
Ph
OH
total yield 60%
Cl
OH
OH
Cl
11
Scheme 8
3e
2,4-dichloro-5-(chloromethyl)-3-methylselenophene (18)
were successfully purified and identified (Scheme 9). The
formation of selenophene 16 is similar to the formation of
benzoselenophene 12, whereas the formation of seleno-
phene 17 involves electrophilic aromatic substitution of
the a-carbon atom by chlorinating species. Selenophene
18 may be the product of reaction of selenophene 17 with
hydrogen chloride.
Cl
Cl
Se
Cl
Ph
Ph
Cl Cl
Se
Ph
Cl
Ph
Cl
OH
Cl
OH
Cl
OH
10
OH
9
Scheme 7
OH
The research was then extended to SeBr4. The reaction of
unsubstituted propargyl alcohol with selenium tetrabro-
mide in dry dichloromethane solution under argon at 0 °C
for 30 min gave product 13, which is presumably formed
by spontaneous transfer of bromine atoms from selenium
to one of the two double bonds of the corresponding divi-
nylselenium dibromide intermediate (Scheme 8). In con-
trast to the analogous chloro-substituted product 3c,
which is stable even in refluxing chloroform, product 13
was found to be stable only at –18 °C. Because of this in-
stability, our attempts to perform a NOESY experiment to
determine the configuration of the double bond failed.
However, on the basis of the strong similarity between the
1H and 13C NMR spectra of the product 13 and those of the
chloro-substituted analogue 3c, especially the chemical
shifts of the allylic methylene groups, we conclude that
syn-addition occurred. Reaction of 3-phenylprop-2-yn-1-
ol (1e) with SeBr4 under the above conditions led directly
to the formation of 3-bromo-2-(bromomethyl)-1-benzo-
selenophene (14) and (2E)-2,3-dibromo-3-phenylprop-2-
en-1-ol (15) (Scheme 8). An anti orientation of the two
bromine atoms in the latter was assigned, because no NOE
interaction was observed between the phenyl and methyl-
ene hydrogen atoms. In both cases, and in contrast with
the chloro-substituted analogue, the corresponding divi-
nylselenium dibromide intermediates could not be isolat-
ed, their reaction being much faster at lower temperatures
(30 min at 0 °C) than was the case with 2c and 2e (over-
night at room temperature).
Cl
Cl
Cl Cl
Se
½ SeCl4
a
CHCl3 SiO2
0 °C, 30 min
CHCl3
r.t.
overnight
OH
OH
1f
2f
H
Cl
+
Cl
Se
Se
Cl
Se
Cl
OH
OH
+
Cl
Cl
16
17
18
total yield 52%
a Products 16–18 were identified after silica gel chromatography
Scheme 9
The reaction of 1-phenylprop-2-yn-1-ol with SeCl4 under
the above conditions led to the formation of the corre-
sponding a-phenylpropargyl chloride 2116 in quantitative
yield without any acetylene–allene isomerization, and no
product of SeCl4 addition to the triple bond (Scheme 10).
The reaction of the same alcohol with SeCl2 led to the for-
mation of the corresponding divinyl selenide.4,5 It is
known that SeCl4 reacts with saturated a-phenylalkyl al-
cohols by an SN1-like mechanism.17 In this connection it
may be noted that reaction of substituted 1-phenylprop-2-
yn-1-ol with hydrogen bromide leads to the corresponding
allenyl bromide by an SN2¢ mechanism, exclusively.18
In conclusion, selenium tetrahalides were found to under-
go electrophilic addition with propargyl alcohols in a re-
gio- and stereospecific manner. A range of novel (Z,Z)-
bis(b-chlorovinyl)selenium dichlorides and dibromides
were prepared. Syn-addition and anti-Markovnikov orien-
tation were shown to occur by means of NOESY experi-
Prompted by the results that we obtained with 3-phenyl-
prop-2-yn-1-ol, we reacted 4-methylpent-4-en-2-yn-1-ol
with SeCl4. Although, the corresponding divinylselenium
dichloride could not be isolated, the cyclization products
(3-chloro-4-methylselenophen-2-yl)methanol (16), (3,5-
dichloro-4-methylselenophen-2-yl)methanol (17), and
1
2
ments and from the values of JC–Se and JC–Se
respectively. These compounds undergo halogen transfer
,
Synthesis 2011, No. 4, 577–584 © Thieme Stuttgart · New York

PAPER
Divinylselenium Dihalides
581
1H NMR (300 MHz, CDCl3): d = 7.26 (t, J = 1.5 Hz, 2 H), 4.95 (d,
J = 1.5 Hz, 4 H), 2.95 (br s, 2 H).
½ SeCl4
Ph
H
Ph
H
OH
Cl
0 °C, 30 min
CHCl3
13C NMR (75 MHz, CDCl3): d =145.3 (1JC–Se = 104.0 Hz, =C-),
132.7 (2JC–Se = 17.8 Hz, =CH–), 59.7 (-CH2-).
1g
21; 100%
– SeOCl2
MS (CI/CH4): m/z (%) = 334 (24) [M+], 262 (40), 154 (45), 83
(100).
– HCl ½ SeCl4
SeOCl3
Ph
HRMS: m/z [M+] calcd for C6H8O235Cl237Cl278Se: 333.8392; found:
Ph
H
OSeCl3
333.8391.
H
– SeOCl3
(2Z,2¢Z)-2,2¢-(Dichloro-l4-selanediyl)bis(3-chloropent-2-en-1-
ol) (2d)
20
19
Yellow viscous liquid; yield: 83%.
IR (neat): 1012, 1136, 1457, 1602, 2980, 3384 cm–1
Scheme 10
1H NMR (300 MHz, CDCl3): d = 4.90 (s, 4 H), 4.02 (br s, 2 H), 2.88
(q, J = 7.2 Hz, 4 H), 1.36 (t, J = 7.2 Hz, 6 H).
13C NMR (75 MHz, CDCl3): d =151.7 (=C–), 137.7 (1JC–Se = 102.0
Hz, =C-), 63.2 (-CH2-), 33.4 (-CH2-), 12.0 (-CH3).
to one of the two double bonds and fragmentation/cycliza-
tion to form benzoselenophene derivatives. Isolated (Z,Z)-
bis(b-chlorovinyl)selenium dichlorides can be hydrolyzed
to the corresponding selenoxides by aqueous sodium bi-
carbonate or reduced to the corresponding selenides in
acetone.
MS: (Failed because of the instability of the compound.)
(2Z,2¢Z)-2,2¢-(Dichloro-l4-selanediyl)bis(3-chloro-3-phenyl-
prop-2-en-1-ol) (2e)
CHCl3 and CH2Cl2 were distilled from P2O5 and stored under argon.
THF was distilled from Na by using benzophenone. SeBr4 was pre-
pared according to the known procedure.13e 4-methylpent-4-en-2-
yn-1-ol (1f, 100%), which is commercially available, was prepared
from the corresponding alkyne and paraformaldehyde by using
TMEDA and BuLi in dry THF (30 min, –78 °C; 1.5 h, r.t.). All other
solvents and reagents were commercially available and were used
without further purification. Column chromatography was per-
formed on silica gel 60 (230–400 mesh), and TLC was performed
on precoated Merck 60 F254 silica gel plates (2.00 mm). Melting
points were determined on a Thomas Hoover melting point appara-
tus and are uncorrected. IR spectra were recorded on a Bruker Ten-
sor 27 FTIR instrument. Mass spectra were recorded on an Auto
flex TOF/TOF MALDI instrument (Bruker, Germany). HRMS
were obtained on a VG-Fison Autospec instrument. NMR spectra
were recorded at 298 K by using 300-, 600-, or 700-MHz spectrom-
eters (13C NMR frequencies of 75.5, 150.9, or 176.1 MHz, respec-
tively) in CDCl3 or other deuterated solvents with TMS as the
internal standard. Chemical shifts are reported in ppm, and coupling
constants in Hz. The Se–C coupling constants were measured from
the 77Se satellites in the 13C NMR spectra. The Se–H coupling con-
stants were measured from the 77Se satellites in the 1H NMR spec-
tra. In some cases the structures were unambiguously determined
with the aid of two-dimensional techniques, such as COSY,
HMQC, or HMBC. The stereochemistry of the double bond was as-
signed by using the NOESY technique.
Light yellow sticky liquid; yield: 92%.
IR (neat): 1031, 1068, 1216, 1590, 1608, 3013, 3375 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.53–7.41 (m, 10 H), 4.99 (s, 4 H),
3.40 (br s, 2 H).
13C NMR (75 MHz, CDCl3): d = 146.0 (=C–), 140.0 (=C–), 136.1
(=C–), 131.6 (=CH–), 128.9 [=CH– (×2)], 128.6 [=CH– (×2)],
63.02 (–CH2–).
MS: (Failed because of the instability of the compound.)
(3Z)-4-Chloro-3-{[1-chloro-1-(dichloromethyl)-2-hydroxy-2-
methylpropyl]selanyl}-2-methylbut-3-en-2-ol (3a)
The product was isolated by chromatography [silica gel, hexanes–
EtOAc (4:1)] followed by washing with CDCl3.
White solid; yield: quant (1H NMR), 39% (isolated); mp 78.5 0.5
°C.
IR (neat): 1142, 1177, 1365, 1459, 1559, 1708, 2983, 3345 cm–1.
1H NMR (700 MHz, CDCl3): d = 7.08 (s, 1 H), 6.36 (s, 1 H), 3.47
(br s, 2 H), 1.73 (s, 3 H), 1.64 (s, 3 H), 1.62 (s, 3 H), 1.60 (s, 3 H).
13C NMR (176 MHz, CDCl3): d = 143.1 (1JC–Se = 124.2 Hz, =C-),
128.9 (2JC–Se = 28.2 Hz, =CH–), 86.9 (1JC–Se = 113.9 Hz, -C-Cl),
78.8 (-C-C-Cl), 77.3 (2JC–Se = 13.0 Hz, -CH-), 73.2 (-C-), 28.5
(-CH3), 28.0 (-CH3), 27.7 (-CH3), 27.6 (-CH3).
MS (CI/CH4): m/z (%) = 388 (4) [M+], 294 (34), 199 (22), 182 (24),
181 (26).
Reactions of SeCl4 and SeBr4 with Propargyl Alcohols; General
Procedure
HRMS: m/z [M+] calcd for C10H16O235Cl480Se: 387.9070; found:
The appropriate propargyl alcohol (2 mmol) was added to a soln of
SeCl4 or SeBr4 (1 mmol) in anhyd CHCl3 or anhyd CH2Cl2 (12 mL)
at 0 °C under argon, and the mixture was stirred at 0 °C for 30 min.
This reaction taken to be complete when the insoluble SeCl4 and
SeBr4 had disappeared. The solvent was then removed under re-
duced pressure. In the case of the addition reactions of SeCl4 with
alcohols 1c, 1e, or 1f, the products were dissolved in CDCl3 and al-
lowed to stand at r.t. overnight.
387.9070.
(3Z)-4-Chloro-3-{[1-chloro-1-(dichloromethyl)-2-hydroxypro-
pyl]selanyl}but-3-en-2-ol (3b)
The products were isolated by chromatography [silica gel, hexanes–
EtOAc (5:1)] as a mixture of four stereoisomers in the ratio
6.6:4.6:2.1:1.0; total isolated yield: 78%.
First stereoisomer: colorless liquid.
(2Z,2¢Z)-2,2¢-(Dichloro-l4-selanediyl)bis(3-chloroprop-2-en-1-
ol) (2c)
IR (neat): 1064, 1126, 1172, 1287, 1373, 1449, 1587, 2982, 3358
cm–1.
White solid; yield: 91%. (Because of instability at r.t., the mp could
not been measured).
IR (neat): 1026, 1072, 1455, 1594, 2935, 3331 cm–1.
1H NMR (700 MHz, CDCl3): d = 6.84 (d, J = 0.9 Hz, 1 H), 6.22 (s,
1 H), 5.09 (qd, J = 6.6, 0.9 Hz, 1 H), 4.25 (q, J = 6.3 Hz, 1 H), 4.14
(br s, 2 H), 1.51 (d, J = 6.6 Hz, 3 H), 1.31 (d, J = 6.3 Hz, 3 H).
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13C NMR (176 MHz, CDCl3): d = 136.2 (1JC–Se = 123.0 Hz, =C-),
128.9 (2JC–Se = 16.0 Hz, =CH–), 85.7 (1JC–Se = 110.0 Hz, -C-), 75.9
(2JC–Se = 29.5 Hz, -CH-), 73.2 (-CH-), 65.9 (-CH-), 22.4
(-CH3), 18.9 (-CH3).
(3E)-3,4-Dichloro-2-methylbut-3-en-2-ol (5a)
The product was isolated by chromatography [silica gel, hexanes–
EtOAc (5:1)] as a yellow liquid; yield: quant (1H NMR), 35% (iso-
lated).
IR (neat): 1140, 1177, 1367, 1461, 1612, 2985, 3399 cm–1.
MS (CI/CH4): m/z (%) = 364 (9) [M+], 307 (100), 271 (23), 253
(29).
1H NMR (700 MHz, CDCl3): d = 6.60 (s, 1 H), 2.78 (br s, 1 H), 1.48
(s, 6 H).
HRMS: m/z [M+] calcd for C8H12O235Cl237Cl280Se: 363.8698;
found: 363.8716.
13C NMR (176 MHz, CDCl3): 143.1 (=C–Cl), 115.0 ( =CH–), 74.3
Second stereoisomer: yellow liquid.
(-C-), 28.6 (-CH3).
IR (neat): 1067, 1123, 1261, 1374, 1450, 1586, 2982, 3384 cm–1.
MS (CI/CH4): m/z (%) = 154 (5) [M+], 139 (64) [M – OH]+, 137
(100) [M – OH]+.
1H NMR (700 MHz, CDCl3): d = 6.90 (d, J = 0.9 Hz, 1 H), 6.32 (s,
1 H), 5.01 (qd, J = 6.3, 0.9 Hz, 1 H), 4.49 (q, J = 6.3 Hz, 1 H), 2.84
(br s, 2 H), 1.57 (d, J = 6.3 Hz, 3 H), 1.36 (d, J = 6.3 Hz, 3 H).
HRMS: m/z [M+] calcd for C5H8O35Cl2 153.9952; found: 153.9913.
(3-Chloro-1-benzoselenophen-2-yl)methanol (12) and (2E)-2,3-
Dichloro-3-phenylprop-2-en-1-ol (5e)
The products were isolated by chromatography [silica gel, hexanes–
EtOAc (5:1 to 4:1 to 2:1)] as a 1:1 mixture; total isolated yield for
12, 12a, and 5e: 51%.
13C NMR (176 MHz, CDCl3): d = 136.9 (1JC–Se = 123.5 Hz, = C-),
129.2 (2JC–Se = 19.0 Hz, =CH–), 83.5 (1JC–Se = 110.0 Hz, -C-), 77.6
(-CH-), 73.6 (2JC–Se = 13.5 Hz, -CH-), 66.6 (2JC–Se = 25.5 Hz,
-CH-), 22.1 (-CH3), 20.2 (-CH3).
MS (CI/CH4): m/z (%) = 366 (8) [M – 2H]+, 307 (100), 271 (20),
252 (34).
From the mixture of 12 and 5a (yellow liquid):
HRMS: m/z [M – 2H]+ calcd for C8H10O237Cl480Se: 365.8482;
found: 365.8489.
12
1H NMR (700 MHz, CDCl3): d = 7.824–7.813 (m, 1 H7), 7.821–
7.807 (m, 1 H4), 7.45–7.43 (m, 1 H5), 7.33–7.31 (m, 1 H6), 5.01 (s,
2 H), 3.32 (br s, 1 H).
Third stereoisomer: from the mixture of the third and fourth stereo-
isomers (yellow liquid).
13C NMR (176 MHz, CDCl3): 141.8 (1JC–Se = 110.5 Hz, =C–
CH2OH), 138.6 (=C–C-Cl), 137.4 (1JC–Se = 102.3 Hz, =C–Se-C-
CH2OH), 125.5 (2JC–Se = 14.7 Hz, =CH7-), 125.2 (=CH6-), 124.9
(=CH5-), 123.5 (=CH4-), 117.4 (=C–Cl), 60.0 (2JC–Se = 13.5 Hz, -
CH2-).
MS (CI/CH4): m/z (%) = 244 (55) [M+], 229 (100).
HRMS: m/z [M+] calcd for C9H7O35Cl78Se: 243.9358; found:
1H NMR (600 MHz, CDCl3): d = 7.13 (d, J = 1.2 Hz, 1 H), 6.20 (s,
1 H), 5.12 (qd, J = 6.3, 1.2 Hz, 1 H), 4.29 (q, J = 6.3 Hz, 1 H), 3.63
(br s, 2 H), 1.63 (d, J = 6.3 Hz, 3 H), 1.34 (d, J = 6.3 Hz, 3 H).
13C NMR (75 MHz, CDCl3): d = 136.1 (1JC–Se = 127.5 Hz, =C-),
130.1 (2JC–Se = 16.0 Hz, =CH–), 83.9 (-C-), 77.5 (-CH-), 73.1
(-CH-), 66.4 (-CH-), 22.8 (-CH3), 20.4 (-CH3).
Fourth stereoisomer: from the mixture of the third and fourth stereo-
isomers (yellow liquid).
243.9374.
1H NMR (600 MHz, CDCl3): d = 6.90 (d, J = 1.2 Hz, 1 H), 6.15 (s,
1 H), 5.04 (qd, J = 6.6, 1.2 Hz, 1 H), 4.49 (q, J = 6.0 Hz, 1 H), 3.63
(br s, 2 H), 1.46 (d, J = 6.0 Hz, 3 H), 1.36 (d, J = 6.6 Hz, 3 H).
13C NMR (75 MHz, CDCl3): d = 137.0 (=C–), 129.5 (2JC–Se = 21.5
Hz, =CH–), 84.0 (-C-), 77.7 (-CH-), 74.1 (-CH-), 66.4 (-CH-),
22.0 (-CH3), 19.1 (-CH3).
5e
1H NMR (700 MHz, CDCl3): d = 7.51–7.50 (m, 2 H), 7.41–7.37 (m,
3 H), 4.66 (s, 2 H), 3.32 (br s, 1 H).
13C NMR (176 MHz, CDCl3): 136.2 (=C– ipso), 129.9 (=C–Ph),
129.1 ( =CH– para), 128.8 (=CH– ortho), 128.6 (=C–CH2OH),
128.0 (=CH– meta), 63.5 (-CH2-).
MS (CI/CH4): m/z (%) = 204 (16) [M+], 187 (42), 185 (50).
HRMS: m/z [M+] calcd for C9H8O35Cl37Cl 203.9923; found:
Mixture of the third and fourth stereoisomers
IR (neat): 1065, 1126, 1374, 1451, 1581, 2981, 3284 cm–1.
MS (CI/CH4): m/z (%) = 358 (10%) [M+], 307 (100), 271 (24), 253
203.9903.
(7).
Mixture of 12 and 5e
IR (neat): 1032, 1115, 1252, 1445, 1631, 3385 cm–1.
HRMS: m/z [M+] calcd for C8H12O235Cl478Se: 357.8764; found:
357.8766.
3-Chloro-2-(chloromethyl)-1-benzoselenophene (12a)
Isolated by using the conditions described above as a yellow liquid.
IR (neat): 1020, 1110, 1252, 1303, 1433, 1690, 3057 cm–1.
(2Z)-3-Chloro-2-{[1,2,2-trichloro-1-(hydroxymethyl)ethyl]sela-
nyl}prop-2-en-1-ol (3c)
The product was isolated by chromatography [silica gel, hexanes–
1H NMR (300 MHz, CDCl3): d = 7.79–7.74 (m, 2 H), 7.42–7.37 (m,
EtOAc (5:1)] as a light yellow liquid; yield: 51%.
IR (neat): 1075, 1230, 1364, 1455, 1593, 1704, 2933, 3338 cm–1.
1 H), 7.33–7.27 (m, 1 H), 4.88 (s, 2 H, 3JSe–H = 9.0 Hz).
13C NMR (75 MHz, CDCl3): 138.2 (1JC–Se = 102.8 Hz, =C–), 138.0
(=C–), 136.5 (1JC–Se = 110.5 Hz, =C–), 126.4 (=CH–), 125.6
(2JC–Se = 15.0 Hz, =CH–), 125.4 (=CH–), 124.5 (=CH–), 122.0 (=C–),
43.3 (-CH2-).
MS (CI/CH4): m/z (%) = 264 (35) [M+], 229 (100) [M – Cl]+.
HRMS: m/z [M+] calcd for C9H635Cl278Se: 261.9020; found:
1H NMR (300 MHz, CDCl3): d = 6.96 (t, J = 1.5 Hz, 1 H), 6.36 (s,
1 H), AB system: 4.73 and 4.32 (dd, J = 13.8, 1.5 Hz, 1 H each),
4.52 (br s, 2 H), ABq: 3.98 and 3.86 (d, J = 12.9 Hz, 1 H each).
13C NMR (75 MHz, CDCl3): d = 130.6 (1JC–Se = 119.1 Hz, =C–),
129.9 (2JC–Se = 17.5 Hz, =CH–), 82.6 (1JC–Se = 105.2 Hz, -C-), 75.8
(2JC–Se = 26.9 Hz, -C-,), 66.9 (-CH2-), 61.8 (-CH2-).
MS (CI/CH4): m/z (%) = 332 (38) [M+], 279 (100), 154 (94).
261.9037.
HRMS: m/z [M+] calcd for C6H8O235Cl237Cl276Se: 331.8411; found:
331.8408.
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Divinylselenium Dihalides
583
(2Z)-3-Bromo-2-{[1,2,2-tribromo-1-(hydroxymethyl)ethyl]sela-
nyl}prop-2-en-1-ol (13)
The product was isolated by chromatography [silica gel, hexanes–
EtOAc (3:1)] as a yellow liquid; yield: 85% (isolated).
1H NMR (300 MHz, CDCl3): d = 7.50 (q, J = 1.0 Hz, 1 H, 2JSe–H
=
47.7 Hz), 4.82 (s, 2 H, 3JSe–H = 7.7 Hz), 2.39 (br s, 1 H), 2.16 (d, J =
1.0 Hz, 3 H).
13C NMR (150 MHz, CDCl3): d = 142.0 (1JC–Se = 114.0 Hz, =C–),
137.5 (=C–), 123.5 (=C–), 123.0 (1JC–Se = 109.7 Hz, =CH–), 60.2
(2JC–Se = 15.5 Hz, -CH2-), 17.0 (-CH3).
MS (CI/CH4): m/z (%) = 210 (32) [M+], 193 (100).
HRMS: m/z [M+] calcd for C6H7O35Cl80Se: 209.9351; found:
IR (neat): 1060, 1129, 1242, 1450, 1582, 2992, 3384 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.26 (t, J = 1.5 Hz, 1 H), 6.34 (s,
1 H), 5.00 (br s, 2 H), AB system: 4.67 and 4.34 (dd, J = 14.1, 1.5
Hz, 1 H each), ABq: 4.12 and 3.99 (d, J = 13.2 Hz, 1 H each).
13C NMR (75 MHz, CDCl3): d = 133.1 (1JC–Se = 121.6 Hz, =C–),
118.7 (2JC–Se = 16.0 Hz, =CH–), 76.4 (1JC–Se = 109.5 Hz, -C-), 68.4
(-CH2-), 64.1 (-CH2-), 50.0 (2JC–Se = 24.9 Hz, -CH-).
209.9349.
(3,5-Dichloro-4-methylselenophen-2-yl)methanol (17)
White solid; mp 73 1 °C.
IR (neat): 1047, 1315, 1343, 1475, 2920, 3263 cm–1.
MS (CI/CH4): m/z (%) = 512 (1) [M+], 494 (1), 432 (1), 413 (4).
HRMS: m/z [M+] calcd for C6H8O279Br281Br280Se: 511.6382; found:
511.6409.
1H NMR (600 MHz, CDCl3): d = 4.81 (d, J = 6.0 Hz, 2 H, 3JSe–H
7.3 Hz), 2.11 (s, 3 H), 2.08 (t, J = 6.0 Hz, 1 H).
=
3-Bromo-2-(bromomethyl)-1-benzoselenophene (14) and (2E)-
2,3-Dibromo-3-phenylprop-2-en-1-ol (15)
The products were obtained as a 1:1 mixture; total isolated yield for
14 and 15: 60%. The products were separated and isolated chroma-
tography [silica gel, hexane (100%) then hexanes–EtOAc (10:1 to
5:1)].
13C NMR (75 MHz, CDCl3): d = 139.8 (1JC–Se = 112.5 Hz, =C–),
134. 8 (=C–), 126.1 (1JC–Se = 123.2 Hz, =C–), 121.7 (=C–,), 60.1
(2JC–Se = 14.0 Hz, -CH2-), 14.2 (-CH3).
MS (CI/CH4): m/z (%) = 242 (25) [M+], 227 (100).
HRMS: m/z [M+] calcd for C6H6O35Cl278Se: 241.8969; found:
241.8980.
(2E)-2,3-Dibromo-3-phenylprop-2-en-1-ol (14)
White solid; mp 106.5 0.5 °C.
IR (neat): 1090, 1205, 1245, 1293, 1433, 3028 cm–1.
1H NMR (700 MHz, CDCl3): d = 7.84 (dm, J = 8.4 Hz, 1 H), 7.81
(dm, J = 8.4 Hz, 1 H), 7.47–7.44 (m, 1 H), 7.37–7.35 (m, 1 H), 4.86
(s, 2 H, 3JSe–H = 10.5 Hz).
2,4-Dichloro-5-(chloromethyl)-3-methylselenophene (18)
Yellow liquid
IR (neat): 1021, 1041, 1259, 1325, 1481, 1561, 2923 cm–1.
1H NMR (600 MHz, CDCl3): d = 4.76 (s, 2 H, 3JSe–H = 9.3 Hz), 2.13
(s, 3 H).
13C NMR (176 MHz, CDCl3): d = 139.5 (=C–), 139.0 (1JC–Se = 102.7
Hz, =C–), 137.8 (1JC–Se = 110.0 Hz, =C–), 126.4 (3JC–Se = 9.0 Hz,
=CH–), 126.0 (=CH–), 125.6 (=CH–), 125.5 (2JC–Se = 15.6 Hz,
=CH–), 111.7 (=C–), 28.3 (2JC–Se = 20.8 Hz, -CH2-).
MS (CI/CH4): m/z (%) = 354 (12) [M+], 273 (100).
HRMS: m/z [M+] calcd for C9H681Br278Se: 353.7968; found:
13C NMR (150 MHz, CDCl3): d = 135.1 (1JC–Se = 112.3 Hz, =C–),
134.8 (=C–), 128.1 (1JC–Se = 123.9 Hz, =C–), 125.7 (=C–), 40.0
(2JC–Se = 17.9 Hz, -CH2-), 14.4 (-CH3).
MS (EI+):(%) = 264 (9) [M+], 227 (100).
HRMS: m/z [M+] calcd for C6H535Cl37Cl278Se: 263.8571; found:
263.8576.
353.7967.
Preparation of Divinyl Selenoxides from Divinylselenium
Dichlorides: General Procedure
EtOAc (70 mL) was added to the reaction mixture containing the
freshly prepared divinylselenium dichloride (1 mmol), and the mix-
ture was washed with 10% aq NaHCO3 (15 mL). The organic phase
was dried (MgSO4) and the solvent was removed under reduced
pressure.
(2E)-2,3-Dibromo-3-phenylprop-2-en-1-ol (15)
Yellow liquid.
IR (neat): 1031, 1085, 1201, 1245, 1443, 2930, 3357 cm–1.
1H NMR (700 MHz, CDCl3): d = 7.39–7.31 (m, 5 H), 4.84 (br d,
J = 3.9 Hz, 2 H), 2.82 (br t, J = 3.9 Hz, 1 H).
13C NMR (176 MHz, CDCl3): 140.0 (=C–), 129.1 (=CH–), 128.9
[=CH– (×2)], 128.4 [=CH– (×2)], 122.2 (=C–), 118.5 (=C–), 67.7
(-CH2-).
MS (CI/CH4): m/z (%) = 292 (49) [M+], 275 (100), 273 (68), 213
(68), 211 (73), 131 (42).
(2Z,2¢Z)-2,2¢-Seleninylbis(3-chloroprop-2-en-1-ol) (8c)
The product was isolated by chromatography [silica gel, hexanes–
EtOAc (3:1 to 2:1) and EtOAc–MeOH (1:1)], followed by crystal-
lization (CHCl3) as a white solid; yield: 54% (isolated); mp 70
°C.
1
HRMS: m/z [M+] calcd for C9H8O79Br81Br 291.8921; found:
291.8923.
IR (neat): 798 (Se=O), 1031, 1054, 1421, 1454, 1618, 2920, 3242
cm–1.
(3-Chloro-4-methylselenophen-2-yl)methanol (16), (3,5-Dichlo-
ro-4-methylselenophen-2-yl)methanol (17), and 2,4-Dichloro-5-
(chloromethyl)-3-methylselenophene (18)
The products, obtained in a total isolated yield of 52%, were sepa-
rated and isolated by chromatography [silica gel, hexanes–EtOAc
(10:1)].
1H NMR (300 MHz, CD3OD): d = 6.95 (t, J = 1.5 Hz, 2 H), 4.83 (br
s, 2 H), AB system: 4.69 and 4.46 (dd, J = 14.4, 1.5 Hz, 2 H each).
13C NMR (75 MHz, CD3OD): d = 145.7 (1JC–Se = 118.3 Hz, -C=),
126.2 (2JC–Se = 19.0 Hz, =CH–), 57.7 (-CH2).
MS MALDI [DCTB(AN)]: [M+] 278.918 ([MH+], 1517.40).
(2Z,2¢Z)-2,2¢-Seleninylbis(3-chloropent-2-en-1-ol) (8d)
The product was isolated by chromatography [silica gel, hexanes–
EtOAc (2:1 to 1:1) then EtOAc–MeOH (3:1)], followed by crystal-
lization (pentane–CHCl3) as a white solid; yield: 67% (isolated); mp
87.5 0.5 °C.
(3-Chloro-4-methylselenophen-2-yl)methanol (16)
Yellow liquid.
IR (neat): 1000, 1048, 1139, 1341, 1435, 2920, 3333 cm–1.
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584
S. Braverman et al.
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(7) Migalina, Yu. V.; Galla-Bobik, S. V.; Khripak, S. M.;
IR (neat): 817 (Se=O), 1014, 1133, 1458, 1622, 2979, 3280 cm–1.
Staninets, V. I. Khim. Geterotsikl. Soedin. 1982, 911; Chem.
Abstr. 1982, 97, 162496.
1H NMR (300 MHz, CDCl3): AB system: 4.81 (dd, J = 13.5, 6.6 Hz,
2 H) and 4.67 (dd, J = 13.5, 6.3 Hz, 2 H), 4.55 (dd, J = 6.6, 6.3 Hz,
2 H), AB system: 2.70 and 2.58 (dq, J = 14.5, 7.2 Hz, 2 H each),
1.26 (t, J = 7.2 Hz, 3 H).
13C NMR (75 MHz, CDCl3): d = 145.9 (2JC–Se = 20.4 Hz, -C=),
136.6 (1JC–Se = 120.2 Hz, =C–), 58.7 (-CH2-), 31.5 (-CH2-), 12.2
(-CH3).
(8) Migalina, Yu. V.; Galla-Bobik, S. V.; Ershova, I. I.;
Staninets, V. I. Zh. Obshch. Khim. 1982, 52, 1559; Chem.
Abstr. 1982, 97, 162292.
(9) Engman, L. J. Org. Chem. 1987, 52, 4086.
(10) Garratt, D. G.; Schmid, G. H. Can. J. Chem. 1974, 52, 3599.
(11) Magnus, P. D. In Comprehensive Organic Chemistry, Vol.
3; Barton, D. H. R.; Ollis, W. D., Eds.; Pergamon: Oxford,
1979, 489.
MS (CI/CH4): m/z (%) = 335 (7) [M + H]+, 318 (35) [M – O]+, 299
(32), 283 (39), 265 (59), 247 (32).
(12) (a) Riley, R. F.; Flato, J.; Bengels, D. J. Org. Chem. 1962,
27, 2651. (b) Migalina, Yu. V.; Galla-Bobik, S. V.; Lendel,
V. G.; Staninets, V. I. Khim. Geterotsikl. Soedin. 1981,
1283; Chem. Abstr. 1982, 96, 6522. (c) Minh, T. Q.;
Christiaens, L.; Renson, M. Bull. Soc. Chim. Fr. 1974,
2239. (d) Riley, R. F.; Flato, J.; McIntyre, P. J. Org. Chem.
1963, 28, 1138.
HRMS: m/z [M+] calcd for C10H17O335Cl280Se: 334.9720; found:
334.9715.
(2Z,2¢Z)-2,2¢-Seleninylbis(3-chloro-3-phenylprop-2-en-1-ol)
(8e)
The product was isolated by chromatography [silica gel, hexanes–
EtOAc (1:1) then EtOAc–MeOH (4:1)] as a white solid; yield: 44%
(isolated); mp 151.5 0.5 °C.
(13) (a) Martynov, A. V.; Ivanov, A. V.; Amosova, S. V.;
Potapov, V. A. Russ. J. Org. Chem. 2006, 42, 1083.
(b) Potapov, V. A.; Khuriganova, O. I.; Musalov, M. V.;
Larina, L. I.; Amosova, S. V. Russ. J. Gen. Chem. 2010, 80,
541. (c) Potapov, V. A.; Amosova, S. V.; Belozerova, O. V.;
Albanov, A. I.; Yarosh, O. G.; Voronkov, M. G. Chem.
Heterocycl. Compd. (N. Y., NY, U. S.) 2003, 39, 551.
(d) Amosova, S. V.; Shagun, V. A.; Martynov, A. V.;
Makhaeva, N. A.; Larina, L. I.; Lysenko, K. A.; Voronkov,
M. G. J. Organomet. Chem. 2007, 692, 3307. (e) Amosova,
S. V.; Martynov, A. V.; Mahaeva, N. A.; Belozerova, O. V.;
Penzik, M. V.; Albanov, A. I.; Yarosh, O. G.; Voronkov, M.
G. J. Organomet. Chem. 2007, 692, 946. (f) Amosova, S.
V.; Penzik, M. V.; Martynov, A. V.; Zhilitskaya, L. V.;
Voronkov, M. G. Russ. J. Gen. Chem. 2009, 79, 221.
(g) Amosova, S. V.; Martynov, A. V. Mini-Rev. Org. Chem.
2010, 7, 23. (h) Amosova, S. V.; Penzik, M. V.; Martynov,
A. V.; Makhaeva, N. A.; Yarosh, N. O.; Voronkov, M. G.
J. Organomet. Chem. 2008, 693, 3346.
IR (neat): 812 (Se=O), 1091, 1181, 1243, 1358, 1444, 1620, 2927,
3361 cm–1.
1H NMR (600 MHz, CDCl3): d = 7.41–7.36 (m, 2 H), 7.30–7.25 (m,
4 H), 7.11–7.09 (m, 4 H), 5.24 (br s, 2 H), ABq: 4.97 and 4.77 (d,
J = 13.8 Hz, 2 H each).
13C NMR (150 MHz, CDCl3): d = 142.3 (2JC–Se = 23.4 Hz, -C=),
139.7 (1JC–Se = 123.9 Hz, =C–), 135.5 (=C–), 130.6 ( =CH–), 128.9
[=CH– (×2)], 128.7 [=CH– (×2)], 58.9 (-CH2-).
MS MALDI (DHB(AN)): [M+] 430.972 ([MH+] 1367.75).
Acknowledgment
This research was supported by The Israel Science Foundation
(Grant No. 919-05).
(14) Duddeck, H. Prog. Nucl. Magn. Reson. Spectrosc. 1995, 27,
1.
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