Reactions of areneselenenamides with alkenes in the presence of phosphorus(V) and sulfur(IV) oxyhalides. New synthesis of β-Haloalkyl Selenides

Article abstract of DOI:10.1134/S1070428009060062

A new procedure was proposed for activation of areneselenenamides with phosphorus(V) and sulfur (IV) oxyhalides. According to the ¹H, ¹³C, and ³¹P NMR data, areneselenenamide reacts with phosphorus oxyhalide to form interm

Full text of DOI:10.1134/S1070428009060062

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 6, pp. 842–847. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © R.L. Antipin, V.N. Klak, E.K. Beloglazkina, N.V. Zyk, 2009, published in Zhurnal Organicheskoi Khimii, 2009, Vol. 45, No. 6,
pp. 857–862.
Reactions of Areneselenenamides with Alkenes
in the Presence of Phosphorus(V) and Sulfur(IV) Oxyhalides.
New Synthesis of β-Haloalkyl Selenides
R. L. Antipin, V. N. Klak, E. K. Beloglazkina, and N. V. Zyk
Faculty of Chemistry, Moscow State University, Vorob’evy gory 1, Moscow, 119992 Russia
e-mail: antipin@org.chem.msu.ru
Received February 7, 2007
Abstract—A new procedure was proposed for activation of areneselenenamides with phosphorus(V) and sul-
1
fur(IV) oxyhalides. According to the H, 13C, and 31P NMR data, areneselenenamide reacts with phosphorus
oxyhalide to form intermediate adduct in which the phosphorus atom is coordinated at the selenium. Arene-
selenenamides activated by phosphorus(V) oxyhalides react with alkenes (norbornene and norbornadiene) with
high trans-stereoselectivity. Their reactions with terminal olefins are regioselective, and they lead to preferen-
tial formation of the corresponding Markovnikov adducts.
DOI: 10.1134/S1070428009060062
Arylselenenation of unsaturated compounds attracts
considerable interest from the synthetic viewpoint.
Successive selenenation–deselenenation provides a con-
venient method of synthesis of compounds having
a functional substituent at double carbon–carbon bond.
Selenium-containing fragments are commonly intro-
duced into alkene and alkyne molecules via addition of
the corresponding selenenyl halides [1–5], which leads
to the formation of β-halo-substituted alkyl aryl sele-
nides in 65–80% yield. These reactions are usually
regio- and stereoselective, and the major products
formed under thermodynamic control (MeCN, 25°C)
are Markovnikov adducts, while the corresponding
anti-Markovnikov adducts are obtained as minor prod-
ucts. The latter become the major products under con-
ditions of kinetic control (THF, –78°C) [2].
selenenyl halides. Over the past few years we devel-
oped a procedure for activation of weak sulfur-con-
taining electrophiles (sulfenamides, sulfenates [6, 7],
thio- and dithiobisamines [8, 9]) with phosphorus and
sulfur halides and oxyhalides. The procedure is based
on the transformation of weakly polar initial sulfur(II)
compound into strongly polarized or ionic intermediate
via reaction with appropriate Lewis acid. Phosphorus
and sulfur oxyhalides were selected as Lewis acids,
taking into account their mildness (according to
Pearson), in contrast to traditionally used hard activa-
tors such as sulfuric anhydride and metal halides.
Sulfur compound polarized in this way becomes cap-
able of adding at a double C=C bond.
Selenenamides are milder Lewis bases than sulfen-
amides, and their reactions with phosphorus or sulfur
oxyhalides may be expected to produce electrophilic
complexes capable of adding to unsaturated com-
pounds. In fact, we recently found that N,N-diethylben-
zeneselenenamide reacts with alkenes in the presence
From the practical viewpoint, an important problem
is development of effective procedures for halosele-
nenation of olefins with the goal of improving the
yield and regioselectivity in the addition of arene-
Scheme 1.
SePh
CH2Cl2, –40°C
PhSeNR2
+
XOHlgn
+
–P(O)(NR2)Hlgn –1
Hlg
I, II
III–XV
I, R = Et; II, R2N = morpholino; XOHlgn = POCl3, POBr3, SOCl2.
842

REACTIONS OF ARENESELENENAMIDES WITH ALKENES
843
of POCl3 or SOCl2 to give the corresponding 1,2-halo-
selenenation products in high yield [10]. In the present
article we report on the results of chloro- and bromo-
selenenation of a number of model cyclic and acyclic
olefins having various substituents at the double C=C
bond. Benzeneselenenamides I and II reacted with
olefins in the presence of POCl3, POBr3, or SOCl2 ac-
cording to Scheme 1.
atoms in initial selenenamide I (δC 11.4, 42.9 ppm),
Cl2P(O)NEt2 (δC 13.0 ppm, d, J ≈ 2.1 Hz; 40.5 ppm, d,
J ≈ 2.0 Hz), and the electrophilic complex (δC 44.8,
13.0 ppm). Thus the NMR data indicate coordination
of phosphorus-containing Lewis acid at the selenium
atom of initial selenenamide I with formation of struc-
ture A (Scheme 2) in which the selenium atom has
a positive charge and should be strongly electrophilic.
Complex A is capable of adding at olefinic C=C bond
to give β-halo-substituted alkyl phenyl selenide. If the
reaction mixture contains no olefinic substrate, the
second molecule of initial areneselenenamide (which
is always present in the reaction mixture) can act as
nucleophile. In this case, the final products are
Cl2P(O)NEt2 and the corresponding diaryl diselenide,
which are formed in nearly quantitative yield.
We previously showed that activation of arenesul-
fenamides with phosphorus oxyhalides involves coor-
dination of the Lewis acid at the sulfur atom of sul-
fenamide [11]. In the reactions with selenenamides co-
ordination of phosphorus- or sulfur-containing Lewis
acid at both selenium and nitrogen atom of initial
selenenamide may be presumed. Quantum-chemical
calculations of donor–acceptor complexes formed
from selenenamide I and POBr3 (their geometric pa-
rameters were optimized using semiempirical SCF
PM3 approximation) gave similar heats of formation
of two possible structures (39.90 kcal/mol for the
formation of P–N bond and 42.25 kcal/mol for the
formation of P–Se bond).
Scheme 2.
Et2N
Ph
O
PhSeNEt2
+
POCl3
Cl–
Se
P
Cl
Cl
I
A
The structure of the reactive intermediate was
determined on the basis of the NMR data. The 31P
NMR spectrum of a mixture of phosphoryl chloride
and N,N-diethylbenzeneselenenamide (I) in CDCl3,
prepared at –30°C, showed considerable decrease in
the intensity of the POCl3 signal at δP 8.6 ppm [12],
and a new strong signal appeared at δP 17.0 ppm. The
latter was assigned to Et2NP(O)Cl2 whose formation
was proved by independent synthesis from POCl3 and
Et2NH (see Experimental). In addition, the 31P NMR
spectrum contained a signal at δP 29.5 ppm, which is
likely to belong to the selenium reagent. This signal
was a singlet, indicating the absence of 31P–1H spin–
spin coupling in the reagent. The same followed from
the 1H NMR data. The 1H NMR spectrum of a POCl3–
PhSeNEt2 mixture at –30°C contained only one multi-
plet due to coupling with 31P, δ 3.30 ppm, which was
assigned to Cl2P(O)NEt2; the corresponding protons
in the electrophilic reagent resonated at δ 3.48 ppm.
Apart from Cl2P(O)NEt2 and the reagent, the mixture
contained 40% of initial selenenamide I. This means
that the reaction of I with POCl3 is reversible. The
1H NMR spectrum of the same mixture, recorded at
20°C, contained no signal at δ 3.48 ppm, and only
signals assignable to Cl2P(O)NEt2 and diphenyl disele-
nide were present.
PhSeCH2CH2Cl
+ Cl2P(O)NEt2
PhSeNEt2
PhSeSePh
+ Cl2P(O)NEt2
The results of reactions of benzeneselenenamides
with phosphorus oxyhalides and alkenes also suggest
an alternative mechanism involving preliminary
formation of benzeneselenenyl halide which then adds
to olefinic substrate (Scheme 3).
Scheme 3.
ArSeNR2
+
POHlg3
ArSeHlg
SePh
Hlg
However, TLC analysis of the reaction mixture
containing areneselenenamide and phosphorus oxy-
halide showed the absence of a compound with Rf 0.26
(petroleum ether–ethyl acetate, 3:1), typical of ben-
zeneselenenyl halide. The fact that areneselenenyl
halide is not formed during the process is additionally
supported by the observed regioselectivity in the reac-
Likewise, in the 13C NMR spectrum of POCl3–
PhSeNEt2 we observed signals from ethyl carbon
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 6 2009

ANTIPIN et al.
844
Reactions of benzeneselenenamides I and II with alkenes in the presence of phosphorus(V) and sulfur(IV) oxyhalides
Alkene
ArSeNR2 XOHlg3
Product
Yield, % (ratio a:b)
Hex-1-ene
Hex-1-ene
Hex-1-ene
Hex-1-ene
Hex-1-ene
Cyclohexene
I
POCl3
84 (9:1)
93 (8.5:1)
98 (9:1)
95 (9:1)
98 (8:1)
73
C4H9CH(Cl)CH2SePh (IIIa) + C4H9CH(SePh)CH2Cl (IIIb)
I
POBr3 C4H9CH(Br)CH2SePh (IVa) + C4H9CH(SePh)CH2Br (IVb)
I
SOCl2
POCl3
IIIa + IIIb
IIIa + IIIb
II
II
I
POBr3 IVa + IVb
SePh
POCl3
(V)
Cl
Cyclohexene
Cyclohexene
I
I
SOCl2
POBr3
V
98
97
SePh
Br
(VI)
Cyclohexene
Cyclohexene
Styrene
II
II
I
POCl3
V
91
POBr3 VI
POCl3 PhCH(Cl)CH2SePh (VIIa) + PhCH(SePh)CH2Cl (VIIb)
POBr3 PhCH(Br)CH2SePh (VIIIa) + PhCH(SePh)CH2Br (VIIIb)
97
74 (1:1)
86 (1:1)
75 (1:1)
79
Styrene
I
Styrene
II
I
POCl3
POCl3
VIIa + VIIb
Allyl chloride
Allyl chloride
Allyl chloride
Allyl chloride
Norbornene
ClCH2CH(SePh)CH2Cl (IX)
I
POBr3 ClCH2CH(SePh)CH2Br (X)
80
II
II
I
POCl3
POBr3
POCl3
IX
X
78
83
82
SePh
SePh
(XI)
Cl
Br
Norbornene
I
POBr3
POCl3
91
(XII)
Norbornene
Norbornene
Norbornadiene
II
II
I
XI
81
POBr3 XII
90
POCl3
75 (1:5)
Cl
SePh
(XIIIa) +
(XIIIb)
SePh
Br
I
I
POBr3
59
52
(XIV)
SePh
Br
CF3
Ph
CF3
POBr3
Ph
(XV)
SePh
Br
NO2
NO2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 6 2009

REACTIONS OF ARENESELENENAMIDES WITH ALKENES
845
tions of areneselenenamide–phosphorus oxyhalide with
terminal alkenes. In our case, the addition direction is
opposite to that reported for the addition of selenenyl
halides (see below). The results of reactions of sele-
nenamides I and II with olefins are summarized in
table. These data allowed us to formulate some general
relations holding therein.
products were analyzed by GC–MS on a Finnigan
MAT SSQ-7000 instrument [electron impact, 70 eV;
OV-1 quartz capillary column, 25 m; oven temperature
programming from 70°C (2 min) to 280°C (10 min) at
a rate of 20 deg/min].
Quantum-chemical calculations were performed in
terms of the semiempirical SCF PM3 approximation
[13] using HyperChem software package (HyperCube
Inc., FL, USA); geometric parameters were optimized
with a convergence gradient of ≤10 cal Å–1 mol–1.
The reactions performed in the presence of POBr3
usually provide higher yields than those in analogous
reactions promoted by POCl3. Thionyl chloride en-
sured better results as compared to phosphoryl chlo-
ride. Finally, N,N-diethylamide I is more reactive than
morpholide II. Obviously, the presence of additional
donor centers in the initial selenenamide molecule is
undesirable because of concurrent coordination of
Lewis acid at those centers.
Addition of N,N-diethylbenzeneselenenamide (I)
to olefins in the presence of phosphorus(V) and
sulfur(IV) oxyhalides (general procedure). A solu-
tion of 2.5 mmol of selenenamide I in 10 ml of anhy-
drous methylene chloride was cooled to –30°C, a solu-
tion of 2.5 mmol of phosphoryl chloride or bromide or
thionyl chloride in 10 ml of anhydrous methylene
chloride was added under stirring, the mixture was
stirred for 5 min, and a solution of 2.5 mmol of the
corresponding olefin in 10 ml of the same solvent was
added. The mixture was allowed to warm up to room
temperature and filtered through a column charged
with silica gel (5 cm in height). Removal of the solvent
from the filtrate gave a yellow oily substance.
As follows from the results of reactions with nor-
bornene and norbornadiene, the addition is strictly
trans-stereoselective. trans Orientation of the chlorine
atom and phenylselanyl group in adducts XI–XIII un-
ambiguously follows from the coupling constant for
the corresponding protons (J = 3.7 Hz). The fact that
no rearrangement products were detected in the reac-
tions with norbornene and norbornadiene suggests low
effective electrophilicity of reactive complex A.
1
2-Chloro-1-phenylselanylhexane (IIIa). H NMR
The regioselectivity in the reactions under study
depends on the substitution pattern at the double
carbon–carbon bond in initial olefin. As a rule, elec-
tron-withdrawing substituents at the double bond in
terminal olefin favor formation of the corresponding
anti-Markovnikov adducts (see table). For example,
the isomer ratio in the reaction with hex-1-ene is 9:1.
It should be noted that the addition of benzenesele-
nenyl halide is characterized by the reverse selectivity
(15:85) [2]. The addition to styrene was not selective,
while the reaction with allyl chloride gave only the
corresponding anti-Markovnikov adduct.
spectrum, δ, ppm: 0.86 t (3H, CH3, J 7.3 Hz), 1.3 m
(4H, CH2), 1.7 m (1H, 3-H), 2.0 m (1H, 3-H), 3.17 d.d
(1-H, J = 8.5, 12.4 Hz), 3.26 d.d (1-H, J = 5.2,
12.4 Hz), 4.0 m (1H, 2-H), 7.4 m (5H, Harom). 13C NMR
spectrum, δC, ppm: 15.25, 22.85, 29.10, 35.95, 38.50
(CSe), 63.40 (CCl), 127.36, 129.25, 136.65.
1
1-Chloro-2-phenylselanylhexane (IIIb). H NMR
spectrum, δ, ppm: 0.84 t (3H, CH3, J = 7.3 Hz), 1.34 m
(4H, CH2), 1.74 m (1H, 3-H), 2.05 m (1H, 3-H),
3.2 d.d (1-H, J- = 8.5, 12.4 Hz), 3.28 d.d (1-H, J = 5.2,
12.4 Hz), 4.06 m (1H, 2-H), 7.4 m (5H, Harom). Mass
spectrum (IIIa/IIIb), m/z (Irel, %): 276 (45) [M]+, 278
(13) [M + 2]+.
Thus the proposed procedure for selenenation of
alkenes using the system areneselenenamide–phos-
phorus(V) [or sulfur(IV)] oxyhalide is convenient for
the preparation of β-halo-substituted alkyl aryl sele-
nides. The procedure ensures higher yields of the target
products, as compared to traditionally used addition of
areneselenenyl halides, and in some cases makes it
possible to vary ratio of isomeric products.
1
2-Bromo-1-phenylselanylhexane (IVa). H NMR
spectrum, δ, ppm: 0.80 t (3H, CH3, J = 7.3 Hz), 1.25 m
(4H, CH2), 1.65 m (1H, 3-H), 2.10 m (1H, 3-H),
3.20 d.d (1-H, J = 8.5, 12.4 Hz), 3.30 d.d (1-H, J = 5.2,
12.4 Hz), 3.80 m (1H, 2-H), 7.4 m (5H, Harom).
1
1-Bromo-2-phenylselanylhexane (IVb). H NMR
spectrum, δ, ppm: 0.83 t (3H, CH3, J = 7.3 Hz), 1.32 m
(4H, CH2), 1.72 m (1H, 3-H), 2.12 m (1H, 3-H),
3.23 d.d (1-H, J = 8.5, 12.4 Hz), 3.35 d.d (1-H, J = 5.2,
12.4 Hz), 3.87 m (1H, 2-H), 7.4 m (5H, Harom). Mass
spectrum (IVa/IVb), m/z (Irel, %): 319 (43) [M]+, 321
(39) [M + 2]+.
EXPERIMENTAL
The NMR spectra were recorded on Bruker Avance
400 and Varian VXR-400 spectrometers (400 MHz for
1H and 100 MHz for 13C) using CDCl3 as solvent. The
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 6 2009

ANTIPIN et al.
846
trans-1-Chloro-2-phenylselanylcyclohexane (V).
(1H, 3-H, J = 3.2, 3.7 Hz), 4.18 d.t (1H, 2-H, J = 1.7,
3.7 Hz), 7.21–7.51 m (5H, Harom). Mass spectrum, m/z
(Irel, %): 285 (43) [M]+, 287 (39) [M + 2]+.
1H NMR spectrum, δ, ppm: 1.40 m (2H, 4-H), 1.60 m
(2H, 5-H), 1.7 m (2H, 3-H), 2.30 d.d.t (2H, 6-H),
3.50 d.d (1H, 2-H, J = 6, 10.1 Hz), 4.15 d.d (1H, 1-H,
J = 7, 10.1 Hz), 7.40 m (5H, Harom). 13C NMR spec-
trum, δC, ppm: 22.95, 25.30, 32.67, 34.15, 50.32 (CSe),
64.10 (CCl), 127.85, 129.78, 136.30. Mass spectrum,
m/z (Irel, %): 274 (35) [M]+, 276 (32) [M + 2]+.
endo-2-Bromo-exo-3-phenylselanylbicyclo[2.2.1]-
1
heptane (XII). H NMR spectrum, δ, ppm: 1.69 d.t
(1H, 7-H, J = 10.3 Hz), 1.85 m (2H, 5-H), 2.15 d (1H,
4-H, J = 3.5 Hz), 2.25 t (1H, 1-H, J = 3.5 Hz), 3.05 d.d
(1H, 3-H, J = 3.2, 3.5 Hz), 3,21 d.t (1H, 2-H, J = 1.6,
3.5 Hz), 7.20–7.56 m (5H, Harom). Mass spectrum, m/z
(Irel, %): 329 (35) [M]+, 331 (19) [M + 2]+.
trans-1-Bromo-2-phenylselanylcyclohexane (VI).
1H NMR spectrum, δ, ppm: 1.32 m (2H, 4-H), 1.58 m
(2H, 5-H), 1.67 m (2H, 3-H), 2.35 d.d.t (2H, 6-H),
3.41 d.d (1H, 2-H, J = 6, 10.1 Hz), 3.84 d.d (1H, 1-H,
J = 7, 10.1 Hz), 7.4 m (5H, Harom). Mass spectrum, m/z
(Irel, %): 317 (40) [M]+, 319 (14) [M + 2]+.
exo-2-Chloro-endo-3-phenylselanylbicyclo[2.2.1]-
1
hept-2-ene (XIIIa). H NMR spectrum, δ, ppm:
1.87 d.t (1H, 7-H, J = 1.6, 9.5 Hz), 2.14 d (1H, 7-H,
J = 9.5 Hz), 3.16 br.s (2H, 1-H, 4-H), 3.66 t (1H, 2-H,
J = 2.4 Hz), 3.97 t (1H, 3-H, J = 2.4 Hz), 6.22 d.d (1H,
6-H, J = 3.4, 5.6 Hz), 6.28 d.d (1H, 5-H, J = 2.7,
5.6 Hz), 7.20–7.55 m (5H, Harom).
1-Chloro-1-phenyl-2-phenylselanylethane (VIIa).
1H NMR spectrum, δ, ppm: 3.50 d.d (1H, 2-H, J = 9.4,
12.6 Hz), 3.52 d.d (1H, 2-H, J = 6.1, 12.6), 4.98 d.d
(1H, 1-H, J = 6.1, 9.4 Hz), 7.10–7.55 m (10H, Harom).
endo-2-Chloro-exo-3-phenylselanylbicyclo[2.2.1]-
1
2-Chloro-1-phenyl-1-phenylselanylethane
(VIIb). 1H NMR spectrum, δ, ppm: 3.49 d.d (1H, 2-H,
J = 9.4, 12.6 Hz), 3.62 d.d (1H, 2-H, J = 6.1, 12.6 Hz),
4.57 d.d (1H, 1-H, J = 6.1, 9.4 Hz), 7.30–7.68 m (10H,
hept-2-ene (XIIIb). H NMR spectrum, δ, ppm:
1.69 d.t (1H, 7-H, J = 1.6, 10.3 Hz), 2.15 d (1H, 4-H,
J = 3.5 Hz), 2.25 t (1H, 1-H, J = 3.5 Hz), 3.05 d.d
(1H, 3-H, J = 3.2, 3.5 Hz), 3,21 d.t. (1H, 2-H, J = 1.6,
3.5 Hz), 6.18 t (1H, 5-H), 6.30 t (1H, 6-H, J = 3.2 Hz),
7.20–7.56 m (5H, Harom). Mass spectrum (XIIIa/
XIIIb), m/z (Irel, %): 327 (34) [M]+, 329 (32) [M + 2]+.
H
arom). Mass spectrum (VIIa/VIIb), m/z (Irel, %): 295
(33) [M]+, 297 (35) [M + 2]+.
1-Bromo-1-phenyl-2-phenylselanylethane
1
(VIIIa). H NMR spectrum, δ, ppm: 3.38 d.d (1H,
endo-2-Bromo-exo-3-phenylselanyl-endo-5-tri-
2-H, J = 9.5, 12.6 Hz). 3.44 d.d (1H, 2-H, J = 6.8,
12.8 Hz), 4.65 d.d (1H, 1-H, J = 6.8, 9.4 Hz), 7.05–
7.45 m (10H, Harom).
1
fluoromethylbicyclo[2.2.1]heptane (XIV). H NMR
2
spectrum, δ, ppm: 1.69 d.d.t (1H, anti-7-H, J = 11.1,
J7,3 = 3.1, J7,1 = 1.6, J7,4 = 1.6 Hz), 1.93 d.d.d.d (1H,
2
2-Bromo-1-phenyl-1-phenylselanylethane
exo-6-H, J = 13.4, J6,5 = 11.9, J6,1 = 5.1, J6,2
=
=
1
2
(VIIIb). H NMR spectrum, δ, ppm: 3.58 d.d (1H,
1.9 Hz), 2.09 d.d.t (1H, syn-7-H, J = 10.9, J7,endo-6
2-H, J = 9.5, 12.6 Hz). 3.69 d.d (1H, 2-H, J = 6.8,
12.8 Hz), 4.69 d.d (1H, 1-H, J = 6.8, 9.4 Hz), 7.36–
7.57 m (10H, Harom). Mass spectrum (VIIIa/VIIIb),
m/z (Irel, %): 340 (44) [M]+, 342 (39) [M + 2]+.
2.7, J7,1 = J7,4 = 1.1 Hz), 2.24 d.d.d (1H, endo-6-H,
2J = 13.4, J6,5 6.7, J6,syn-7 = 2.6 Hz), 2.55 br.s
(1H, 1-H), 2.57 m (1H, 4-H), 2.58 d.d.d.q (1H, 5-H,
J5,exo-6 = 11.9, JHF = 10.3, J5,endo-6 = 6.5, J5,4 = 3.6 Hz),
3.78 d.d (1H, 3-H, J3,2 = 4.3, J3,anti-7 = 2.8 Hz), 4.12 d.t
(1H, 2-H, J2,3 = J2,1 = 4.1, J2,exo-6 = 1.9 Hz), 7.37 m
(5H, Harom). Mass spectrum, m/z (Irel, %): 347 (43)
[M]+, 349 (39) [M + 2]+.
1,3-Dichloro-2-phenylselanylpropane (IX).
1H NMR spectrum, δ, ppm: 3.52 q (1H, 2-H, J =
5.7 Hz), 3.87 d (4H, 1-H, 3-H, J = 5.7 Hz), 7.18–
7.47 m (5H, Harom). Mass spectrum, m/z (Irel, %): 267
(35) [M]+, 269 (14) [M + 2]+.
endo-2-Bromo-endo-5-nitro-exo-6-phenyl-exo-3-
1
1-Bromo-3-chloro-2-phenylselanylpropane (X).
1H NMR spectrum, δ, ppm: 3.36 d.d (1H, 2-H, J = 5.6,
6.4 Hz), 3.66 d (2H, 3-H, J = 6.4 Hz), 3.84 d (2H, 1-H,
J = 5.6 Hz), 7.07–7.35 m (5H, Harom). Mass spectrum,
m/z (Irel, %): 312 (33) [M]+, 314 30 [M + 2]+.
phenylselanylbicyclo[2.2.1]heptane (XV). H NMR
2
spectrum, δ, ppm: 2.12 d.d.t (1H, anti-7-H, J = 12.1,
J7,3 = 2.7, J7,1 = J7,4 = 1.7 Hz), 2.28 d.d.t (1H, syn-7-H,
2J = 12.1, J7,6 = 2.5, J7,1 = J7,4 = 1.7 Hz), 2.91 d.q
(1H, 1-H, J1,2 = 4.6, J1,syn-7 = J1,anti-7 = J1,4 = 1.7 Hz),
3.12 d.q (1H, 4-H, J4,5 = 4.5, J4,syn-7 = 1.7, J4,anti-7 = J4,1
=
endo-2-Chloro-exo-3-phenylselanylbicyclo[2.2.1]-
heptane (XI). H NMR spectrum, δ, ppm: 1.75 d.t
(1H, 7-H, J = 10.3 Hz), 1.98 m (2H, 5-H), 2.45 t (1H,
1-H, J = 3.7 Hz), 2.30 d (1H, 4-H, J = 3.7 Hz), 3.11 d.d
1
1.6 Hz), 3.39 d.d (1H, 3-H, J3,2 = 4.4, J3,anti-7 = 2.6 Hz),
4.23 t (1H, 2-H, J2,3 = J2,1 = 4.4 Hz), 4.27 d.d (1H,
6-H, J6,5 = 5.3, J6,syn-7 = 2.7 Hz), 4.89 d.d (1H, 5-H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 6 2009

REACTIONS OF ARENESELENENAMIDES WITH ALKENES
847
5. Uehlin, L. and Wirth, T., Org. Lett., 2001, vol. 3, no. 18,
J5,6 = 5.2, J5,4 = 4.8 Hz), 7.18–7.47 m (5H, Harom).
Mass spectrum, m/z (Irel, %): 406 (26) [M]+, 408 (29)
[M + 2]+.
p. 2931.
6. Zyk, N.V., Beloglazkina, E.K., Gazzaeva, R.A., Tyu-
rin, V.S., and Titanyuk, I.D., Phosphorus, Sulfur Silicon
Relat. Elem., 1999, vol. 155, p. 33.
7. Beloglazkina, E.K., Tyurin, V.S., Titanyuk, I.D.,
Zyk, N.V., and Zefirov, N.S., Dokl. Ross. Akad. Nauk,
1995, vol. 344, p. 487.
8. Zyk, N.V., Vatsadze, S.Z., Beloglazkina, E.K., Dubin-
skaya, Yu.A., Titanyuk, I.D., and Zefirov, N.S., Dokl.
Ross. Akad. Nauk, 1997, vol. 357, p. 209.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 05-03-32737) and by the Presidium of the Russian
Academy of Science (program “Theoretical and Exper-
imental Studies on the Nature of Chemical Bond and
Mechanisms of Chemical Reactions and Proceses”).
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