Synthesis of oxazolidinylphosphine chalcogenides from aminoethyl vinyl ethers

Article abstract of DOI:10.1007/s11172-013-0015-3

N-(2-Vinyloxyethyl)phosphinothioamides and -phosphinoselenoamides prepared by oxidative cross-coupling of 2-vinyloxyethylamine with secondary phosphine chalcogenides undergo thermal (75-100 C) cyclization into the corresponding 3-(diorganylchalcogenophosp

Full text of DOI:10.1007/s11172-013-0015-3

Russian Chemical Bulletin, International Edition, Vol. 62, No. 1, pp. 107—110, January, 2013
107
Synthesis of oxazolidinylphosphine chalcogenides from aminoethyl vinyl ethers
P. A. Volkov,a N. I. Ivanova,a N. K. Gusarova,a L. A. Oparina,a L. I. Larina,a O. V. Vysotskaya,a
N. A. Kolyvanov,a I. Yu. Bagryanskaya,b and B. A. Trofimova
aA. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences,
1 ul. Favorskogo, 664033 Irkutsk, Russian Federation.
Eꢀmail: boris_trofimov@irioch.irk.ru
bN. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences,
9 prosp. Akad. Lavrent´eva, 630090 Novosibirsk, Russian Federation
Nꢀ(2ꢀVinyloxyethyl)phosphinothioamides and ꢀphosphinoselenoamides prepared by oxiꢀ
dative crossꢀcoupling of 2ꢀvinyloxyethylamine with secondary phosphine chalcogenides unꢀ
dergo thermal (75—100 C) cyclization into the corresponding 3ꢀ(diorganylchalcogenophosꢀ
phoryl)ꢀ2ꢀmethylꢀ1,3ꢀoxazolidines in 80—90% yields.
Key words: vinyl ethers, amino alcohols, phosphinochalcogenoic acids, intramolecular
cyclization, 1,3ꢀoxazolidines, organophosphorus compounds.
The chemistry of 1,3ꢀoxazolidines and their derivaꢀ
tives has been extensively developed in the last decade.1—16
They are used as precursors to drugs,5—7,13,16 monomers
and comonomers for the synthesis of specialꢀpurpose polyꢀ
mer materials,17—20 and building blocks in organic synꢀ
thesis.4,8,13,21 For instance, the antitumor drug docetaxel
is prepared from substituted 1,3ꢀoxazolidineꢀ5ꢀcarboxyꢀ
lates3,16 and functionalized 1,3ꢀoxazolidinꢀ4ꢀones serve
as selective cyclooxygenaseꢀ2 inhibitors.10 1,3ꢀOxazoliꢀ
dine structures are part of compounds exhibiting cardioꢀ
protectant,5 antidiabetic,22 antispasmodic,23 antimicroꢀ
bial,6,9,24 herbicidal,25 fungicidal,11 and anthelmintic12
activity. Oxazolidineꢀcontaining urethane formulations
and the corresponding materials are highly resistant to
hydrolysis.8,17,19,20 1,3ꢀOxazolidines are components of
epoxy resins employed as impregnants for strengthening
solid surfaces.18
fragment 2´ꢀC6H4PPh2 in position 2 are employed as
P,Nꢀligands in the synthesis of efficient Ptꢀ and Pdꢀbased
metal complex catalysts for asymmetric allylic alkylaꢀ
tion30,33—35 and the Diels—Alder reaction.32,33 1,3ꢀOxꢀ
azolidines containing the organophosphorus substituent
P(=X)R2 directly bound to the N atom have not been
documented prior to our investigations.36
In the present work, we propose a convenient route to
earlier unknown 3ꢀ(diorganylchalcogenophosphoryl)ꢀ2ꢀ
methylꢀ1,3ꢀoxazolidines that involves thermal isomerizaꢀ
tion of Nꢀ(2ꢀvinyloxyethyl)phosphinothioamides and ꢀ
phosphinoselenoamides. The latter have recently become
accessible through efficient oxidative crossꢀcoupling of
secondary phosphine chalcogenides with 2ꢀvinyloxyethylꢀ
amine36 (Scheme 1).
Scheme 1
A general method of constructing the 1,3ꢀoxazolidine
heterocycle involves cyclocondensation of ꢀamino alcoꢀ
hols with aldehydes or ketones (aminoacetalization).1,6,9,13
The synthesis of 1,3ꢀoxazolidines by isomerization (intraꢀ
molecular cyclization) of ꢀaminoalkyl vinyl ethers (in
the presence of Lewis acids) or that of organic acid amides
containing the 2ꢀvinyloxyethyl group has been reported.
The latter isomerization is catalyzed by protic acids. In
addition, the 1,3ꢀoxazolidine ring can be constructed by
thermal treatment (160—200 C) of some functionalized
Nꢀ(2ꢀvinyloxyethyl)amides of carboxylic,26 carbamic,27
and dithiocarbamic28,29 acids (in most cases, this process
occurs during vacuum distillation of these amides).
The literature data on functionalized 1,3ꢀoxazolidines
containing organophosphorus substituents are scarce.30—35
It has been reported that 1,3ꢀoxazolidines with the
R = Ar, ArCH2CH2; X = O, S, Se
We found that heating of Nꢀ(2ꢀvinyloxyethyl)amides
1a—e (75—100 C, 3.5—15 h, toluene, inert atmosphere)
causes their easy and smooth cyclization into isomeric
3ꢀ(diorganylchalcogenophosphoryl)ꢀ2ꢀmethylꢀ1,3ꢀoxazoꢀ
lidines 2a—e in preparative 80—90% yields (Scheme 2,
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 0107—0110, January, 2013.
1066ꢀ5285/13/6201ꢀ107 © 2013 Springer Science+Business Media, Inc.

108
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 1, January, 2013
Trofimov et al.
Table 1). The reaction proceeds as noncatalytic regioꢀ
selective intramolecular hydroamination of the vinylꢀ
oxy group.
O
Scheme 2
N
S
P
R = Ph (a, b), Ph(CH2)2 (c, d), PhCH(Me)CH2 (e)
X = S (a, c), Se (b, d, e)
Fig. 1. One of two crystallographically independent molecules
of compound 2a according to Xꢀray diffraction data.
Conditions: 75—100 C, 3.5—15 h.
The course of the reactions was monitored using
31P NMR spectroscopy: the integral intensities of the sigꢀ
nals for the starting compounds 1a—e (P 58—66) deꢀ
crease, with simultaneously increasing integral intensities
of the signals for Nꢀphosphorylated 2ꢀmethylꢀ1,3ꢀoxazoꢀ
lidines 2a—e (P 64—72).
Because of the strong electronꢀwithdrawing effect of
the chalcogenophosphoryl group, Nꢀ(2ꢀvinyloxyethyl)ꢀ
amides 1a—e are stronger NH acids than amides of carbꢀ
oxylic and carbamic acids26—29 and hence more easily
undergo intramolecular electrophilic addition. It can be
seen in Table 1 that the cyclization rate of selenophosꢀ
phorylꢀcontaining amides 1b,d is higher than that of thioꢀ
phosphorylꢀcontaining amides 1a,c, which can be attribꢀ
uted to better stabilization of the transition state by the
bulky group R2P=Se.
The structures of compounds 2a—e were proved by
1H, 13C, 31P, and 77Se NMR spectroscopy and 2D NMR
experiments (HMBC, 13C—1H HSQC, and 15N—1H
HMBC). The 15N—1H HMBC spectra of these comꢀ
pounds show crossꢀpeaks for the N atom and the protons
of the methyl and OCH2 groups (for compounds 2c—e, an
additional crossꢀpeak reveals a correlation between the
N atom and the PCH2 protons).
One of two crystallographically independent molecules
of compound 2a is depicted in Fig. 1 (Xꢀray diffraction
data). The phenyl rings are planar; the fiveꢀmembered
ring adopts a conformation of a slightly distorted enveꢀ
lope. The molecular packing of compound 2a in the crysꢀ
tal shows no shortened van der Waals contacts. Numerous
intermolecular H...ꢀinteractions are worth noting (the
distances from the H atoms to the planes of the adjacent
ꢀsystems are 2.74—2.94 Å).
To sum up, we conducted and studied the intramolecꢀ
ular cyclization of Nꢀ(2ꢀvinyloxyethyl)diorganylphosꢀ
phinochalcogenoamides. The reactions proceed quantitaꢀ
tively at 75—100 C to give 3ꢀ(diorganylchalcogenophosꢀ
phoryl)ꢀ2ꢀmethylꢀ1,3ꢀoxazolidines, which are promising
ligands for the preparation of metal complex catalysts,
potential drug precursors, and reactive building blocks for
use in organic synthesis.
Experimental
IR spectra were recorded on a Bruker Vertex spectrometer
1
(thin film and KBr pellets). H, 13C, 15N, 31P, and 77Se NMR
spectra were recorded on Bruker DPXꢀ400 and Bruker AVꢀ400
Table 1. Isomerization of Nꢀ(2ꢀvinyloxyethyl)diorganylphosphinochalcogenoamides into the correspondꢀ
ing 2ꢀmethylꢀ1,3ꢀoxazolidines
Entry
1a—e
R
X
T/C
/h
Oxazolidine
Yield
(%)
2a—e
1
2
3
4
5
1a
1b
1c
1d
1e
Ph
Ph
S
Se
S
Se
Se
75
75
75
75
100
15
7
10
3.5
12
2a
2b
2c*
2d*
2e
86
90
80
90
89
Ph(CH2)2
Ph(CH2)2
PhCH(Me)CH2
* The synthesis of compounds 2c and 2d has been briefly described in the study36 dealing with oxidative
crossꢀcoupling of aminoalkyl vinyl ethers with secondary phosphine chalcogenides.

3ꢀChalcogenophosphoryloxazolidines
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 1, January, 2013
109
spectrometers (400.13, 100.62, 40.56, 161.98, and 76.31 MHz,
respectively) in CDCl3 with reference to SiMe4 (1H, 13C),
MeNO2 (15N), H3PO4 (31P), and Me2Se (77Se). For signal
assignments and determination of the structures of the comꢀ
pounds obtained, heteronuclear 2D NMR procedures were used
(13C—1H HSQC and HMBC). 15N NMR spectra were recorded
using 2D NMR experiments (15N—1H HMBC). All steps of
experimental work were carried out under an inert atmoꢀ
sphere (argon). Toluene was used as a solvent without further
purification.
128.3—128.7 (m, Cm); 131.5—132.5 (m, Co, Cp); 133.5 (d, Cipso,
1JP,C = 105.7 Hz); 134.1 (d, Cipso, 1JP,C = 103.2 Hz). 15N NMR,
: –311.9. 31P NMR, : 66.4.
3ꢀ(Diphenylselenophosphoryl)ꢀ2ꢀmethylꢀ1,3ꢀoxazolidine (2b).
Yield 195 mg (90%), m.p. 71—72 C (from hexane). Found (%):
C, 54.82; H, 5.15; N, 4.01; P, 8.54; Se, 22.49. C16H18NOPSe.
Calculated (%): C, 54.87; H, 5.18; N, 4.00; P, 8.84; Se, 22.54.
IR, /cm–1: 1179, 1128, 1099, 1072 (O—C—N); 695 (P—N—C);
1
3
584 (P=Se). H NMR, : 1.05 (d, 3 H, Me, JH,H = 5.4 Hz);
3.13—3.23, 3.40—3.48 (both m, 1 H each, NCH2); 3.92—4.02
3
Single crystals of compound 2a were obtained by crystallizaꢀ
tion from hexane. An Xꢀray diffraction experiment was perꢀ
formed with a single crystal (0.70×0.25×0.03 mm) on a Bruker
KAPPA APEX II diffractometer equipped with a CCD area
detector (MoꢀK radiation, graphite monochromator, — scan
mode, 2  50) at –73 C. The crystals of compound 2a are
triclinic, a = 9.334(1) Å, b = 12.715(2) Å, c = 13.950(2) Å,
(m, 2 H, CH2O); 5.05 (dq, 1 H, CHMe, JP,H = 10.5 Hz,
3JH,H = 5.4 Hz); 7.43—7.51 (m, 6 H, Hm, Hp); 8.06, 8.13 (both
dd, 2 H each, Ho, 3JP,H = 13.2 Hz, 3JH,H = 7.8 Hz). 13C NMR,
3
: 22.0 (d, Me, JP,C = 5.6 Hz); 47.3 (NCH2); 66.3 (d, CH2O,
2
3JP,C = 3.2 Hz); 88.2 (d, CMe, JP,C = 3.2 Hz); 128.3, 128.6
3
4
(both d, Cm, JP,C = 12.8 Hz); 132.0 (d, Cp, JP,C = 2.8 Hz);
2
132.4, 132.7 (both d, Co, JP,C = 11.2 Hz); 133.0 (d, Cipso
,
3
 = 90.340(6),  = 93.266(6),  = 108.219(5), V = 1569.6(4) Å ,
1JP,C = 80.4 Hz). 15N NMR, : –315.8. 31P NMR, : 66.8 (s and
space group P–1, Z = 4, C16H18NOPS, dcalc = 1.284 g cm–3
,
d of the satellites, JP,Se = 763 Hz). 77Se NMR, : –333.5
1
 = 0.303 mm–1. The intensities of 5619 unique reflections were
measured. Absorption corrections were applied with the
SADABS program37 (transmittance 0.53—0.97). The structure
was solved by the direct methods with the SHELXSꢀ97 proꢀ
gram38 and refined anisotropically by the fullꢀmatrix leastꢀ
squares method with the SHELXLꢀ97 program.38 In each reꢀ
finement cycle, the H atoms were located geometrically with
respect to the coordinates of their parent carbon atoms. Final
(d, 1JP,Se = 763 Hz).
3ꢀ[Bis(2ꢀphenylethyl)thiophosphoryl]ꢀ2ꢀmethylꢀ1,3ꢀoxazolꢀ
idine (2c). Yield 174 mg (80%), viscous oil. Found (%): C, 66.79;
H, 7.23; N, 3.87; P, 8.59; S, 8.88. C20H26NOPS. Calculated (%):
C, 66.83; H, 7.29; N, 3.90; P, 8.62; S, 8.92. IR, /cm–1: 1161,
1124, 1106, 1074 (O—C—N); 698 (P—N—C); 619 (P=S).
1H NMR, : 1.32 (d, 3 H, Me, 3JH,H = 5.2 Hz); 2.06—2.25 (m, 4 H,
PCH2); 2.80—3.02 (m, 4 H, CH2Ph); 3.08—3.16, 3.40—3.48
(both m, 1 H each, NCH2); 3.76—3.82, 3.96—4.00 (both m,
refinement of the structure was performed for all F2 (wR2
=
3
= 0.2596, S = 1.10); the number of parameters refined is 363
(R = 0.0898 for 3947 F > 4). The rather high R factor is due to
the poor quality of the crystals; the peak widths are 2.5—3.0
(unfortunately, better crystals were unavailable). The CIF file
comprising comprehensive data on structure 2a has been deꢀ
posited with the Cambridge Structural Database (CCDC
No. 906645).*
The starting compounds Nꢀ(2ꢀvinyloxyethyl)phosphinoꢀ
chalcogenoamides 1a—e were prepared as described earlier.36
3ꢀ(Diorganylchalcogenophosphoryl)ꢀ2ꢀmethylꢀ1,3ꢀoxazoꢀ
lidines (2a—e) (general procedure). A solution of Nꢀ(2ꢀvinylꢀ
oxyethyl)phosphinochalcogenoamide 1a—e (0.6 mmol) in toluꢀ
ene (2.3 mL) was heated in a sealed tube (75—100 C, 3.5—15 h,
argon) (see Table 1). The resulting reaction mixture was passed
through a short column with Al2O3 (Brockmann activity II,
column height 1.5 cm, toluene as an eluent). The solvent was
removed under reduced pressure. The residue was evacuated to
give compounds 2a—e.
1 H each, CH2O); 5.42 (dq, 1 H, CHMe, JP,H = 10.0 Hz,
3JH,H = 5.2 Hz); 7.12—7.22 (m, 6 H, Ho, Hp); 7.24 (dd, 4 H, Hm,
3
3JH,H = 8.4 Hz, JH,H = 7.2 Hz). 13C NMR, : 22.8 (d, Me,
3JP,C = 3.6 Hz); 28.3, 28.5 (both d, PhCH2, 2JP,C = 2.4 Hz and
1
2JP,C = 2.8 Hz, respectively); 34.2, 34.6 (both d, CH2P, JP,C
=
= 61.1 Hz and 1JP,C = 64.3 Hz, respectively); 44.8 (NCH2); 65.8
(d, CH2O, 3JP,C = 4.0 Hz); 87.4 (d, CMe, 2JP,C = 3.2 Hz); 126.3
(Cp); 128.1 (d, Co, 4JP,C = 6.0 Hz); 128.5 (d, Cm, 5JP,C = 0.8 Hz);
140.4 (d, Cipso, 3JP,C = 15.2 Hz). 15N NMR, : –317.9. 31P NMR,
: 72.1.
3ꢀ[Bis(2ꢀphenylethyl)selenophosphoryl]ꢀ2ꢀmethylꢀ1,3ꢀoxꢀ
azolidine (2d). Yield 219 mg (90%), viscous oil. Found (%):
C, 59.02; H, 6.47; N, 3.43; P, 7.56; Se, 19.38. C20H26NOPSe.
Calculated (%): C, 59.11; H, 6.45; N, 3.45; P, 7.62; Se, 19.43.
IR, /cm–1: 1156, 1124, 1105, 1078 (O—C—N); 698 (P—N—C);
1
3
580 (P=Se). H NMR, : 1.22 (d, 3 H, Me, JH,H = 5.1 Hz);
2.30—2.43 (m, 4 H, PCH2); 2.91—3.05 (m, 4 H, CH2Ph);
3.16—3.19, 3.51—3.53 (both m, 1 H each, NCH2); 3.89—3.90,
4.04—4.05 (both m, 1 H each, CH2O); 5.38 (dq, 1 H, CHMe,
3ꢀ(Diphenylthiophosphoryl)ꢀ2ꢀmethylꢀ1,3ꢀoxazolidine (2a).
Yield 163 mg (86%), m.p. 76—77 C (from hexane). Found (%):
C, 63.29; H, 5.96; N, 4.61; P, 10.17; S, 10.54. C16H18NOPS.
Calculated (%): C, 63.35; H, 5.98; N, 4.62; P, 10.21; S, 10.57.
IR, /cm–1: 1151, 1124, 1104, 1075 (O—C—N); 696 (P—N—C);
3JP,H = 10.1 Hz, JH,H = 5.1 Hz); 7.19—7.26 (m, 6 H, Ho, Hp);
7.31 (dd, 4 H, Hm, 3JH,H = 8.6 Hz, 3JH,H = 7.1 Hz). 13C NMR,
: 22.8 (d, Me, 3JP,C= 4.8 Hz); 29.2, 29.3 (both s, PhCH2); 35.0,
35.5 (both d, CH2P, JP,C = 55.1 Hz and JP,C = 53.8 Hz, reꢀ
spectively); 45.6 (NCH2); 65.9 (d, CH2O, 3JP,C = 4.0 Hz); 88.1
(d, CMe, 2JP,C = 2.8 Hz); 126.4 (Cp); 128.2 (d, Co, 4JP,C = 6.0 Hz);
3
1
1
1
3
615 (P=S). H NMR, : 1.07 (d, 3 H, Me, JH,H = 5.4 Hz);
3.18—3.27, 3.39—3.48 (both m, 1 H each, NCH2); 3.90—3.92,
3.94—3.96 (both m, 1 H each, CH2O); 5.12 (dq, 1 H, CHMe,
3JP,H = 10.9 Hz, 3JH,H = 5.4 Hz); 7.39—7.47 (m, 6 H, Hm, Hp);
7.99, 8.07 (both dd, 2 H each, Ho, 3JP,H = 13.3 Hz, 3JH,H = 7.2 Hz).
128.7 (Cm); 140.4 (d, Cipso
,
3JP,C = 15.2 Hz). 15N NMR,
: –320.8. 31P NMR, : 68.2 (s and d of the satellites, JP,Se
=
1
= 742 Hz). 77Se NMR, : –334.7 (d, 1JP,Se = 742 Hz).
3
13C NMR, : 22.1 (d, Me, JP,C = 5.5 Hz); 46.6 (NCH2); 66.5
3ꢀ[Bis(2ꢀphenylpropꢀ1ꢀyl)selenophosphoryl]ꢀ2ꢀmethylꢀ1,3ꢀ
oxazolidine (2e). Yield 238 mg (89%), viscous oil. Found (%):
C, 60.78; H, 6.95; N, 3.20; P, 7.06; Se, 18.09. C22H30NOPSe.
Calculated (%): C, 60.83; H, 6.96; N, 3.22; P, 7.13; Se, 18.18.
IR, /cm–1: 1157, 1142, 1105, 1087 (O—C—N); 706 (P—N—C);
3
2
(d, CH2O, JP,C = 2.6 Hz); 87.5 (d, CMe, JP,C = 2.2 Hz);
* The data can be made available free of charge from the webꢀ
site: www.ccdc.cam.ac.uk/data_request/cif.

110
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 1, January, 2013
Trofimov et al.
532 (P=Se). 1H NMR, : 1.07, 1.22, 1.24, 1.41, 1.43 (all d, 6 H,
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3
3
3
MeCHPh, JH,H = 6.9 Hz, JH,H = 7.2 Hz, JH,H = 7.1 Hz,
3
3JH,H = 7.4 Hz, JH,H = 7.8 Hz, respectively); 1.16, 1.17, 1.30,
3
3
1.33 (all d, 3 H, C(2)Me, JH,H = 5.2 Hz, JH,H = 5.3 Hz,
3JH,H = 6.4 Hz, JH,H = 5.6 Hz, respectively); 1.88—1.96,
3
1.99—2.08, 2.10—2.24, 2.27—2.54 (all m, 4 H, CH2P); 2.96—2.99,
3.05—3.11, 3.24—3.32, 3.39—3.45, 3.51—3.61, 3.64—3.70,
3.74—3.87 (all m, 6 H, CHMe, NCH2, CH2O); 5.08—5.14,
5.21—5.27, 5.32—5.39 (all m, 2 H, C(2)H); 7.04—7.34 (m, 10 H,
3
Ph). 13C NMR, : 22.4 (d, MeCHPh, JP,C = 3.5 Hz); 22.7
3
(d, MeCHPh, JP,C = 4.8 Hz); 23.8—23.9 (four d, MeCHPh,
3JP,C = 11.9 Hz, 3JP,C = 11.2 Hz, 3JP,C = 11.0 Hz, 3JP,C = 12.3 Hz);
3
3
24.7—24.8 (four d, MeCHPh, JP,C = 10.2 Hz, JP,C = 9.2 Hz,
3JP,C = 11.4 Hz, JP,C = 11.2 Hz); 34.5, 34.8, 35.7, 36.0 (all d,
C(2)Me, 3JP,C = 3.1 Hz, 3JP,C = 3.5 Hz, 3JP,C = 1.5 Hz, 3JP,C
= 4.2 Hz); 39.9, 40.4, 40.9, 42.1 (all d, CH2P, JP,C = 55.7 Hz,
1JP,C = 57.7 Hz, 1JP,C = 51.6 Hz, 1JP,C = 51.3 Hz, respectively);
41.5, 41.6, 41.9, 42.4 (all s, PhCH); 44.7, 44.9, 45.0, 45.2 (all s,
3
=
1
2
NCH2); 65.4, 65.5, 65.6, 65.8 (all d, NCH2, JP,C = 3.4 Hz,
24. S. N. Sriharsha, S. Shashikanth, Heterocycl. Commun., 2006,
12, 213.
25. J. Zhang, F. Ye, X. Jin, Zhiwu Baohu, 2007, 33, 72; Chem.
Abstrs, 2008, 150, 415610.
2JP,C = 4.7 Hz, JP,C = 4.0 Hz, JP,C = 4.7 Hz, respectively);
2
2
87.7, 88.2, 88.3, 88.4 (all d, C(2), 3JP,C = 5.8 Hz, 3JP,C = 4.4 Hz,
3JP,C = 4.5 Hz, JP,C = 2.2 Hz); 126.2—128.9 (m, Co, Cm, Cp);
3
145.4, 146.4 (both m, Cipso). 15N NMR, : –322.9, –320.9,
–320.4, –318.2. 31P NMR, : 64.3 (s and d of the satellites,
1JP,Se = 730 Hz); 66.4 (s and d of the satellites, 1JP,Se = 740 Hz);
26. O. A. Tarasova, B. A. Trofimov, M. L. Al´pert, N. I. Ivaꢀ
nova, S. V. Amosova, M. G. Voronkov, Zh. Org. Khim., 1981,
17, 2628 [J. Org. Chem. USSR (Engl. Transl.), 1981, 17].
27. N. A. Nedolya, T. N. Rakhmatulina, L. Ya. Rappoport, O. P.
Gavrilova, Zh. Org. Khim., 1986, 22, 1333 [J. Org. Chem.
USSR (Engl. Transl.), 1986, 22].
28. S. V. Amosova, O. A. Tarasova, N. I. Ivanova, L. I. Perzhaꢀ
binskaya, M. V. Sigalov, L. M. Sinegovskaya, Zh. Org. Khim.,
1989, 25, 1638 [J. Org. Chem. USSR (Engl. Transl.), 1989, 25].
29. N. A. Nedolya, V. V. Gerasimova, B. A. Trofimov, Sulfur
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1
67.3 (s and d of the satellites, JP,Se = 741 Hz); 70.2 (s and d of
the satellites, 1JP,Se = 734 Hz). 77Se NMR, : –333.4 (d, 1JP,Se
= 741 Hz); –329.72 (d, JP,Se = 740 Hz); –323.0 (d, JP,Se
= 730 Hz); –317.5 (d, 1JP,Se = 734 Hz).
=
=
1
1
This work was financially supported by the Russian
Foundation for Basic Research (Youth Project "My First
Grant", No. 12ꢀ03ꢀ31631).
30. M.ꢀJ. Jin, J.ꢀA. Jung, S.ꢀH. Kim, Tetrahedron Lett., 1999,
40, 5197.
31. Y. Okuyama, H. Nakano, H. Hongo, Tetrahedron: Asymmeꢀ
try, 2000, 11, 1193.
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Received October 25, 2012