Reactions of diazoalkanes with unsaturated compounds 16. Catalytic reactions of diazomethane with 2-alkenyl-1,3-oxazolidines and 2-alkenyl-1,3-oxathiolanes

Article abstract of DOI:10.1007/s11172-008-0097-5

The influence of 1,3-oxazolidine and 1,3-oxathiolane fragments in substituted alkenes on the direction of their catalytic reaction with diazomethane has been investigated. The olefins bearing an oxazolidine substituent in the α- or γ-position and an oxathiolane substituent in the γ-position relative to the C=C bond react with diazomethane in the presence of Pd(acac)₂ selectively resulting in cyclopropanation products. The use of Cu(OTf)₂ does not result in cyclopropanation; however Cu(OTf)₂ catalyzes the reaction of diazomethane with 2-(alk-1-enyl)-1,3-oxathiolanes yielding 2,3,5,6-tetrahydro-1,4-oxathiocines formed through the [2,3]-sigmatropic rearrangement of the intermediate sulfonium ylides.

Full text of DOI:10.1007/s11172-008-0097-5

Russian Chemical Bulletin, International Edition, Vol. 57, No. 3, pp. 617—621, March, 2008
617
Reactions of diazoalkanes with unsaturated compounds
16.* Catalytic reactions of diazomethane
with 2ꢀalkenylꢀ1,3ꢀoxazolidines and 2ꢀalkenylꢀ1,3ꢀoxathiolanes
M. D. Khanova,a R. M. Sultanova,a R. R. Rafikov,a I. P. Baykova,a R. Z. Biglova,a
V. A. Dokichev,a and Yu. V. Tomilovb
aInstitute of Organic Chemistry, Ufa Research Center of the Russian Academy of Sciences,
71 prosp. Oktyabrya, 450054 Ufa, Russian Federation.
Fax: +7 (347 2) 35 6066. Eꢀmail: dokichev@anrb.ru
bN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (495) 135 6390. Eꢀmail: tom@ioc.ac.ru
The influence of 1,3ꢀoxazolidine and 1,3ꢀoxathiolane fragments in substituted alkenes on
the direction of their catalytic reaction with diazomethane has been investigated. The olefins bearing
an oxazolidine substituent in the αꢀ or γꢀposition and an oxathiolane substituent in the γꢀposition
relative to the C=C bond react with diazomethane in the presence of Pd(acac)2 selectively resulting
in cyclopropanation products. The use of Cu(OTf)2 does not result in cyclopropanation; however
Cu(OTf)2 catalyzes the reaction of diazomethane with 2ꢀ(alkꢀ1ꢀenyl)ꢀ1,3ꢀoxathiolanes yielding
2,3,5,6ꢀtetrahydroꢀ1,4ꢀoxathiocines formed through the [2,3]ꢀsigmatropic rearrangement of
the intermediate sulfonium ylides.
Key words: 1,3ꢀoxazolidines, 1,3ꢀoxathiolanes, diazomethane, cyclopropanation, [2,3]ꢀsigmatꢀ
ropic rearrangement, sulfonium ylides, oxathiocines
The intermolecular rearrangement of oxonium, amꢀ
monium and sulfonium ylides formed in the catalytic
reaction of diazo compounds with 1,3ꢀdiheteracycloꢀ
pentanes is a convinient method for the preparation of
1,3ꢀdioxane, morpholine and oxathiane derivatives,2—7
which are promising as synthons for the preparation
of physiologically active polyfunctional compounds. Reꢀ
cently,1 we have shown, that the yield of catalytic cycloꢀ
propanation products of unsaturated acetals bearing
αꢀ or γꢀpositioned acetal function is higher compared to
the same reaction of parent unprotected alkenes. This
reaction is an efficient approach to cyclopropaneꢀconꢀ
taining carbaldehydes. Also, an example of successꢀ
ful synthesis of optically active 2ꢀphenylcyclopropane
carbaldehyde8 is well known, where the key step is
the reaction of a substituted 2ꢀvinylꢀ1,3ꢀoxazolidine,
obtained from cinnamaldehyde and ephedrine, with
a 10ꢀfold excess of gaseous diazomethane in the presence
of Pd(ОАc)2. However, it has been shown that insertion
of carbenes into C—N or C—S bonds (see Refs 4, 5, 9—
11) rather than cyclopropanation of a double bond occurs
in the reactions of diazo compounds with allylamines and
allyl sulfides in the presence of copper, palladium and
rhodium compounds. This fact provides the evidence of
a possible change in the reaction pathway when the subꢀ
strate bears such bonds.
In this work, we have investigated the behavior of
2ꢀalkenylꢀ1,3ꢀoxazolidines 1а,b and 2ꢀalkenylꢀ1,3ꢀoxꢀ
athiolanes 2aꢀc under conditions of catalytic decomposiꢀ
tion of diazomethane. The reaction has been carried out
in the presence of Pd(acac)2 or Cu(OTf)2, since it is these
catalysts that are the most efficient in catalytic cycloꢀ
propanation of unsaturated compounds, bearing e.g.
1,3ꢀdioxolane fragment.1 Thus the cyclopropanation
of 2ꢀ(transꢀstyryl)ꢀ1,3ꢀdioxolane in the presence of
Pd(acac)2 and Cu(OTf)2 proceeded with 99 and 49%
yield, respectively.
However, the very first experiments showed a distincꢀ
tive feature of heterocycles 1 and 2 in comparison with
earlier studied 2ꢀalkenylꢀ1,3ꢀdioxolanes. If the reaction
was performed using standard procedure1 viz., by addiꢀ
tion of diazomethane to a solution of an olefin and
a catalyst, virtually no products of transformation of
the starting unsaturated compounds 1 and 2 were obꢀ
served, although diazomethane decomposition was rathꢀ
er intensive. Therefore, we have changed the reacꢀ
tion conditions. Ethereal solutions of an unsaturated
compound and CH2N2 were simultaneously added to
* For Part 15 see Ref. 1.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 604—608, March, 2008.
1066ꢀ5285/08/5703ꢀ617 © 2008 Springer Science+Business Media, Inc.

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Khanova et al.
the solution of a catalyst containing some starting unsatꢀ
urated compound in ether or CH2Cl2 at 5ꢀ10 °C (overall
molar ratio olefin:CH2N2:catalyst was 1 : 3 : 0.02). Unꢀ
der these conditions, the reaction of oxazolidine 1a with
diazomethane in the presence of Pd(acac)2 led to a mixꢀ
ture of 2ꢀ(transꢀ2ꢀphenylcyclopropyl)ꢀ3ꢀethylꢀ1,3ꢀoxꢀ
azolidine (3a), the starting oxazolidine 1a and aldehydes
4 and 5 (Scheme 1) according to data from 1H NMR
spectroscopy. Column chromatography on neutral aluꢀ
mina allowed us to isolate oxazolidine 3a in 50—55%
yield, however the use of silica gel for chromatography
considerably increased the yield of 4 and 5, which sugꢀ
gests efficient removal of the oxazolidine protecting group
on this adsorbent.
The cyclopropanation with diazomethane of 2ꢀ(butꢀ3ꢀ
enyl)ꢀ1,3ꢀoxazolidine 1b and (butꢀ3ꢀenyl)ꢀ1,3ꢀoxathiꢀ
olane 2a, which contain monosubstituted C=C bonds, in
the presence of Pd(acac)2 proceeds more effectively than
of oxazolidine 1a, and leads to the formation of cycloproꢀ
panes 3b and 6a in 97 and 53% yields, respectively
(Scheme 2). In contrast to cyclopropanation of 1a,
the obtained results are in good agreement with the fact
that palladium catalysts are most effective in the cycloꢀ
propanation of unsaturated compounds capable of cataꢀ
lyst complexation; first of all, this is true for terminal and
constrained cyclic double bonds.12
Scheme 2
Scheme 1
X = S (a), NEt (b)
As for oxazolidine 1a, attempted use of Cu(OTf)2 as
a catalyst for cyclopropanation of unsaturated compounds
1b and 2a with diazomethane was unsuccessful. In the
case of 1b, the filtration of the reaction mixture through
a pad of silica gel was accompanied by the removal of
the oxazolidine group and the formation of allylacetone
was observed, while in the case of oxathiolane 2a there
was no reaction at all.
The relatively low efficiency of cyclopropanation of
βꢀstyryloxazolidine 1a is probably related to a weak inꢀ
teraction of the C=C bond with a palladium catalyst, and
as a consequence, predominant transformation of diazꢀ
omethane to ethylene.12 It is worth noting that the use of
Cu(OTf)2 as a catalyst in this reaction does not give
cyclopropanation products at all. However, it accelerates
cleavage of the oxazolidine protecting group of the aldeꢀ
hyde, and after column chromatography of the mixture, pure
aldehyde 4 was isolated in virtually quantitative yield.
The structure of cyclopropyloxazolidine 3а isolated by
column chromatography on neutral alumina was estimatꢀ
ed on the basis of mass, 1H, 13C NMR and 1H—1H COSY
и 1H—13C NOESY spectra. The substituents in cycloproꢀ
pane ring have transꢀorientation (3Jtrans ≈ 3.8 Hz). Mass
spectrum (EI) of the obtained compounds have a molecꢀ
ular ion peak and a set of peaks of fragmentation ions,
the most abundant of which are due to the elimination of
CH2О, methyl, ethyl and phenyl groups. The following
fragmentation sequence of oxazolidine 3a was registered,
as proved by the peaks of metastable ions:
In contrast to oxathiolane 2a, the disubstituted double
bond of oxathiolanes 2b,c did not undergo cyclopropanaꢀ
tion with diazomethane in the presence of Pd(acac)2,
probably, due to the coordination of palladium on
the sulfur atom. However, we succeeded to make these oxꢀ
athiolanes react with CH2N2 in the presence of Cu(OTf)2
and obtained 2,3,5,6ꢀtetrahydroꢀ1,4ꢀoxathiocines 7b,c
(1H and 13C NMR spectra), although in low yields (25 and
8% respectively). The latter likely to the reaction of oxꢀ
athiolane 2c with methyl diazoacetate in the presence
of Rh2(OAc)4 (see Ref. 13) are formed as a result of
[2.3]ꢀsigmatropic rearrangement of allylsulfonium ylides
8 (Scheme 3) produced by the reaction of a carbene
complex with heterocycle sulfur atom. In contrast to oxꢀ
athiolane 2a, the reaction of the copper carbene complex
with oxathiolanes 2b,c is likely feasible due to the lower
steric interactions with substituents on the C(2) atom.
The low yield of tetrahydrooxathiocines 7b,c is attributed
to the parallel catalytic reaction of diazomethane decomꢀ
position devoid of substrate participation, which is likely
observed for copperꢀassisted catalysts.12
It is worth noting that the intermediate formation of
ylides 8 could be associated with both the addition of
the carbene complex [CH2=CuX] to the sulfur atom of
oxathiolanes and diazomethane reaction with a preꢀ

Cyclopropanation of alkenyloxazolidines(thiolanes) Russ.Chem.Bull., Int.Ed., Vol. 57, No. 3, March, 2008
619
Scheme 3
internal standard — SiMe4. IR spectra were obtained on a Specord
М82ꢀ63 spectrometer in a thin layer. GC analyses of reaction
mixtures were performed on a Chromꢀ5 chromatograph with a flameꢀ
ionization detector (column, 1200×5 mm with 5% SEꢀ30 on Inerꢀ
ton NꢀAW DMCS (0.125—0.160 mm)), as helium gas carrier. TLC
analyses were performed using Silufol, the separation of comꢀ
pounds was performed by column chromatography on silica gel 60
(0.040—0.063 mm) or neutral Al2O3 (Brockmann, 150 mesh).
Mass spectra were obtained on a Thermo Finnigan MAT 95 XP
spectrometer (EI, 70 eV, temperature of the ionization chamber
250 °C, temperature programming 50—250 °C, heating rate
10 deg•min–1) and MXꢀ1300 (cell temperature — 100 °C, ionizing
potential 12 and 70 eV). The known oxathiolanes 2b,c were
synthesized according to reported procedures,15 oxazolidines
1а,b (see Ref. 16) and oxathiolanes 2a (see Ref.15) were obtained
analogously with other derivatives of corresponding heterocyꢀ
clic structures. Solvents were purified according to standard
techniques.17
R = Me (b), Ph (c)
formed complex of copper(II) triflate with oxathiolanes
2b,c through Cu—S binding. At least, a remarkable shift
of S—O (1120 cm–1) stretching vibration band relative to
that in free Cu(OTf)2 (1032 cm–1) is observed in the IR
spectrum of an equimolar mixture of oxathiolane 2b and
Cu(OTf)2. This shift is characteristic of the coordination
of a metal ion to the sulfur atom of a substrate.14
The structures of eightꢀmembered heterocycles 7b,c
were determined by the IR, 1H, 13C NMR and mass
spectra. In the H NMR spectrum of oxathiocine 7b, the
olefin protons resonate at δ 6.02 (3J = 6.8, J = 1.5 Hz)
2ꢀ(transꢀStyryl)ꢀ3ꢀethylꢀ1,3ꢀoxazolidine (1а) was prepared
analogously to the procedure.16 Yield 65%, yellow liquid, b.p
124—125 °C (1 Torr). Found (%): C, 77.16; H, 8.33; N, 6.35.
C13H17NО. Calculated (%): C, 76.81; H, 8.43; N, 6.89. IR, ν/cm–1
:
696, 752, 968, 1060, 1128, 1200, 1680, 2808, 2888, 2936, 2952,
3
2968. 1H NMR (CDCl3): δ 1.16 (t, 3 H, Ме, J = 7.3 Hz); 2.33
and 2.77 (both dq, each 1 H, CH2Me, 2J = 11.9 Hz, 3J = 7.3 Hz);
2.57 (ddd, 1 H, HaC(4), 2J = 8.4 Hz, 3J = 7.8 Hz, 3J = 7.9 Hz);
3.32 (ddd, 1 H, HbC(4), 2J = 8.4 Hz, 3J = 7.8 Hz, 3J = 7.9 Hz);
1
3
3.99 (m, 2 H, H2C(5)); 4.43 (d, 1 H, HC(2), J = 6.9 Hz); 6.15
(dd, 1 H, HC(1´), 3J = 6.9 Hz, 3J = 15.9 Hz); 6.67 (d, 1 H, HC(2´),
3J = 15.9 Hz); 7.23—7.48 (m, 5 H, Ar). 13C NMR (δ): 13.9
(Ме); 46.0 (CH2Ме); 51.3 (C(4)); 65.0 (C(5)); 96.6 (C(2));
126.7, 127.7, 128.4 (5 CH, Ar); 127.8 (C(1´)); 134.3 (C(2´));
136.1 (C, Ar).
4
and δ 4.84 (3J = 5.5, 3J = 6.8 Hz) and, in contrast to
the starting unsaturated compounds 2b, 7b has cis spinꢀ
spin coupling constants equal to 6.8 Hz. In the 1Hꢀ1H
COSY NMR, the methine signal at δ 2.92 has a correlaꢀ
tion with geminal protons at δ 2.65 and δ 2.40, which,
with account of their chemical shifts, proved the insertion
of a methylene fragment into the C—S bond of heterocyꢀ
cle. The retention of the isolated fragment OCH2CH2S
and aboveꢀmentioned facts point to the presence of
a tetrahydroꢀ1,4ꢀoxathiocine ring.
In conclusion, the product yield and composition of
the catalytic reaction of diazomethane with 2ꢀalkenylꢀ
substituted 1,3ꢀoxazolidines and 1,3ꢀoxathiolanes are
dependent on the nature of both the heterocyclic fragꢀ
ment and the catalyst. It was found that unsaturated comꢀ
pounds bearing an oxazolidine fragment in αꢀ and
γꢀpositions and an oxathiolane substituent in the γꢀposiꢀ
tion relative to the C=C bond react with diazomethane in
the presence of Pd(acac)2 resulting in the formation of
cyclopropanation products. The reaction of 2ꢀ(alkꢀ1ꢀ
enyl)ꢀ1,3ꢀoxathiolanes with diazomethane proceeds
through the intermediate formation of sulfonium ylides
that undergo [2,3]ꢀsigmatropic rearrangement resulting
in 2,3,5,6ꢀtetrahydroꢀ1,4ꢀoxathiocines.
2ꢀ(Butꢀ3ꢀenyl)ꢀ2ꢀmethylꢀ3ꢀethylꢀ1,3ꢀoxazolidine (1b) was
prepared analogously to the procedure.16 Yield 42%, yellow oil,
b.p. 75—77 °C (20 Torr). Found (%): C, 70.03; H, 12.00; N, 8.52.
C10H19NО. Calculated (%): C, 70.96; H, 11.31; N, 8.28. 1H NMR
(CDCl3): δ 1.10 (s, 3 H, Ме); 1.13 (t, 3 H, Ме, 3J = 7.3 Hz); 1.60
(m, 2 H, H2C(2´)); 2.12 (dq, 1 H, CH2Me, 2J = 12.3 Hz,
3J = 7.3 Hz); 2.19 (dq, 1 H, CH2Me, 2J = 12.3 Hz, 3J = 7.3 Hz);
2.39 (ddd, 1 H, HаC(1´), 2J = 10.0 Hz, 3J = 6.6 Hz, 3J = 8.2 Hz);
2.53 (ddd, 1 H, HbC(1´), 2J = 10.0 Hz, 3J = 6.6 Hz, 3J = 8.2 Hz);
2.73 (ddd, 1 H, HaC(4), 2J = 8.0 Hz, 3J = 7.5 Hz, 3J = 7.8 Hz);
3.12 (ddd, 1 H, HаC(5), 2J = 3.5 Hz, 3J = 7.5 Hz, 3J = 7.8 Hz);
3.83 (ddd, 1 H, HbC(4), 2J = 8.0 Hz, 3J = 7.5 Hz, 3J = 7.8 Hz);
3.91 (ddd, 1 H, HbC (5), 2J = 3.5 Hz, 3J = 7.5 Hz, 3J =7.8 Hz);
4.91 (dd, 1 H, HaC (4´), 2J = 2.0 Hz, 3Jcis = 10.2 Hz); 5.00 (dd, 1 H,
HbC (4´), 2J = 2.0 Hz, 3Jtrans = 17.1 Hz); 5.83 (ddt, 1 H, CH (3´),
3J = 6.6 Hz, 3J = 10.2 Hz, 3J = 17.1 Hz). 13C NMR (δ):
14.8 (CH2Me); 19.8 (Me); 28.0 (C(2´)); 36.9 (C(1´)); 42.70
(CH2Me); 49.2 (C(4)); 63.9 (C(5)); 95.5 (C(2)); 113.7 (=CH2);
139.3 (=CH).
2ꢀ(Butꢀ3ꢀenyl)ꢀ2ꢀmethylꢀ1,3ꢀoxathiolane (2а) was prepared
analogously to the procedure.15 Yield 60%, colourless oil, b.p.
130—132 °C (30 Torr). Found (%): C, 61.12; H, 9.02; S, 20.93.
C8H14ОS. Calculated (%): C, 60.71; H, 8.92; S, 20.26. 1H MNR
(CDCl3): δ 1.55 (s, 3 H, Ме); 1.88 (m, 2 H, H2C(2´)); 2.12 (dd, 1 H,
HаC (1´), 2J = 10.0 Hz, 3J = 6.4 Hz, 3J = 8.2 Hz); 2.20 (dd, 1 H,
HbC (1´), 2J = 10.0 Hz, 3J = 6.4 Hz, 3J = 8.2 Hz); 3.02 (m, 2 H,
Experimental
1
H and 13C NMR spectra were recorded on a Bruker AМꢀ300
2
3
H2C (4)); 4.07 (ddd, 1 H, HаC (5), J = 5.6 Hz, J = 6.9 Hz,
spectrometer (300.13 and 75.47 MHz respectively) in CDCl3,
3J = 9.2 Hz); 4.17 (ddd, 1 H, HbC (5), 2J = 5.6 Hz, 3J = 5.1 Hz,

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Khanova et al.
3J = 9.2 Hz); 4.92 (dd, 1 H, HaC(4´), 2J = 1.8 Hz, 3Jcis =10.1 Hz);
5.00 (dd, 1 H, HbC (4´), 2J = 1.8 Hz, 3Jtrans = 17.1 Hz); 5.81 (ddt,
1 H, HC (3´), 3J = 6.4 Hz, 3J =10.1 Hz, 3J = 17.1 Hz). 13C NMR
(δ): 28.9 (Me); 29.6 (C(2´)); 33.9 (C(4)); 42.2 (C(1´)); 70.2
(C(5)); 94.8 (C(2)); 114.4 (=CH2), 138.1 (=CH).
Catalytic reaction of unsaturated compounds 1 and 2 with diazꢀ
omethane (general procedure). To a stirring solution of unsaturated
compounds 1 or 2 (1.0 mmol) and Pd(acac)2 (0.042 g, 0.14 mmol)
in ether (20 mL) (or Cu(OTf)2 in 20 mL CH2Cl2) an ethereal
solution 0.45—0.47 M CH2N2 (45 mL, ~21 mmol) and the correꢀ
sponding 2ꢀalkenylꢀ1,3ꢀoxazolidine 1 (6.0 mmol) or 1,3ꢀoxathiꢀ
olane 2 were added at 5—10 °C. The mixture was stirred for
30—40 min and then filtered through a thin layer of Al2O3,
the solvent was evaporated in vacuo distillation and the residue was
chromatographed on Al2O3 or SiO2.
6ꢀMethylꢀ2,3,5,6ꢀtetrahydroꢀ1,4ꢀoxathiocine (7b). The prodꢀ
uct was isolated by vacuum distillation, yield 25%, yellowish liqiud,
b.p. 95—97 °C (10 Torr). Mass spectrum (EI) m/z (Irel (%)): 144
[М]+ (54); 129 (8); 116 (22); 99 (43); 83 (13); 71 (100). Found (%):
C, 58.79; H, 8.84; S, 22.14. C7H12SО. Calculated (%): C, 58.29; H,
8.39; S, 22.23. IR, ν/cm–1: 760, 976, 1056, 1064, 1088, 1208, 1248,
1304, 1360, 1512, 1656, 2872, 2920, 2960. 1H NMR (CDCl3): δ
1.07 (d, 3 H, Ме, 3J = 7.1 Hz); 2.40 (dd, 1 H, HaC(5), 2J = 14.1 Hz,
3J = 10.0 Hz); 2.69 (dd, 1 H, HbC(5), 2J = 14.1 Hz, 3J = 2.0 Hz);
2.72 (dt, 1 H, HaC(3), 2J = 12.0 Hz, 3J = 3.7 Hz); 2.90 (dddd, 1 H,
HC(6), 3J = 7.1 Hz, 3J = 2.0 Hz, 3J = 10.0 Hz, 4J = 1.5 Hz); 2.92
(dt, 1 H, HbC(3), 2J = 12.0 Hz, 3J = 7.1 Hz); 3.88 (dd, 2 H, H2C(2),
3J = 7.1 Hz, 3J = 3.7 Hz); 4.84 (dd, 1 H, HC(7), 3J = 5.5 Hz, 3J = 6.8
Hz); 6.02 (dd, 1 H, HC(8), 3J = 5.5 Hz, 4J = 1.5 Hz). 13C NMR (δ):
21.0 (Ме); 31.4 (C(3)); 33.6 (C(6)); 39.5 (C(5)); 71.7 (C(2)); 124.3
(C(7)); 142.4 (C(8)).
2ꢀ(transꢀ2ꢀPhenylcyclopropyl)ꢀ3ꢀethylꢀ1,3ꢀoxazolidine (3a).
The product was isolated using column chromatography on neutral
Al2O3, Rf 0.72 (eluent was petroleum ether—AcOEt, 20 : 1), yield
50—55%. Found (%): C, 76.93; H, 8.90; N, 6.92. C14H19NО.
Calculated (%): C, 77.38; H, 8.81; N, 6.45. IR, ν/cm–1: 696, 752, 968,
1060, 1128, 1200, 1680, 2808, 2888, 2936, 2952, 2968. 1H NMR
(CDCl3): δ 1.09 (t, 3 H, Ме, 3J = 7.1 Hz); 1.32 (m, 1 H, HC (1´),
of cyclopropane); 1.38 (m, 1 H, HаC (3´), of cyclopropane); 1.59
(m, 1 H, HbC (3´), of cyclopropane); 2.06 (м, 1 H, HC(2´), of
cyclopropane); 2.66 (q, 2 H, CH2Ме, 3J = 7.1 Hz); 2.74 (t, 2 H,
6ꢀPhenylꢀ2,3,5,6ꢀtetrahydroꢀ1,4ꢀoxathiocine (7c). The prodꢀ
uct was isolated by vacuum distillation, yield 8%, yellow oil, b.p.
144—146 °C (1 Torr). Mass spectrum (EI), m/z (Iотн (%)): 206 [М]+
(5); 146 (7); 131 (23); 115 (20); 102 (100); 89 (10). Found (%):
C, 70.16; H, 7.04; S, 16.13. C12H14SО. Calculated (%): C, 69.86;
1
H, 6.84; S, 15.54. H NMR (CDCl3): δ 2.45 and 2.52 (both dt,
each 1 H, H2C(3), 2J = 13.2 Hz, 3J = 6.8 Hz); 2.60 and
3
2.62 (both d, each 1 H, H2C(5), J = 7.1 Hz); 3.50 (m, 1 H,
HC(6)); 3.70 and 3.87 (both m, each 1 H, H2C(2)); 4.95 (dd, 1 H,
HC(7), 3J = 6.8 Hz, 3J = 5.6 Hz); 5.90 (dd, 1 H, HC(8),
3J = 5.6 Hz, 4J = 1.5 Hz); 7.00—7.19 (m, 5 H, Ph). 13C NMR (δ):
31.7 (C(3)); 39.8 (C(5)); 46.3 (C(6)); 72.0 (C(2)); 122.1
(C(7)); 143.0 (C(8)), 126.5; 126.7 and 128.8 (5 CH, Ph);
135.7 (C, Ph).
3
3
H2C(4), J = 6.2 Hz); 3.56 (t, 2 H, H2C(5), J = 6.2 Hz); 5.10
(d, 1 H, CH(2), 3J= 11.3 Hz); 7.23—7.48 (m, 5 H, Ph). 13C NMR (δ):
4.3 (CH2 of cyclopropane); 11.8 and 15.2 (2 CH of cyclopropane);
12.5 (Me); 48.1 (CH2Me); 58.5 (C(4)); 69.3 (C(5)); 98.4 (C(2));
126.7, 127.7, 128.4 (5 CH, Ph); 137.1 (C, Ph).
2ꢀ(2ꢀCyclopropylethyl)ꢀ3ꢀethylꢀ2ꢀmethylꢀ1,3ꢀoxazolidine (3b).
The product was obtained as an yellow oil after the solvent evaporaꢀ
tion, yield 97%. Analytically pure sample was obtained upon
column chromatography on SiO2, Rf 0.81 (eluent was petroꢀ
leum ether—AcOEt, 20 : 1). Found (%): C, 71.63; H, 11.88; N, 7.83.
The work was supported by the Presidium of Russian
Academy of Sciences (program of fundamental investigaꢀ
tions Pꢀ08 "The Development of Methodology of Orꢀ
ganic Synthesis with Valuable Application Properties")
and by Division of Chemistry and Materials Science of
Russian Academy of Sciences (program of fundamental
investigations OHꢀ01 "Theoretical and Experimental
Studies of the Nature of Chemical Bonds and Mechaꢀ
nisms of Important Chemical Reactions and Processes").
C11H21NО. Calculated (%): C, 72.08; H, 11.55; N, 7.64. IR, ν/cm–1
:
736, 756, 916, 960, 1060, 1152, 1192, 1304, 1380, 1456, 1552,
1
1632, 1712, 2856, 2936, 2952, 3080. H NMR (CDCl3): δ 0.02
and 0.37 (both m, each 2 H, CH2CH2 of cyclopropane); 0.62 (m, 1 H,
CH of cyclopropane); 1.06 (bs, 3 H, Ме); 1.10 (t, 3 H, Ме, 3J= 7.3 Hz);
1.27 (m, 2 H, H2C(1´), 2J = 10.0 Hz, 3J = 8.2 Hz); 1.60 (m, 2 H,
H2C(2´)); 2.39 and 2.52 (both dq, each 1 H, CH2Me, 2J = 12.0 Hz,
3J = 7.3 Hz); 2.72 (dt, 1 H, HaC(4), 2J = 8.2 Hz, 3J = 7.5 Hz); 3.08
(ddd, 1 H, HbC(4), 2J = 8.2 Hz, 3J = 7.0 Hz, 3J = 3.7 Hz); 3.80
(ddd, 1 H, HaC(5), 2J = 7.7 Hz, 3J = 7.0 Hz, 3J = 7.5 Hz); 3.88
References
2
3
3
(ddd, 1 H, HbC(5), J = 7.7 Hz, J = 7.5 Hz, J = 3.7 Hz).
13C NMR (δ): 4.3 (CH2CH2 of cyclopropane)); 11.1 (Me); 14.7
(CH); 19.6 (Me); 28.8 и 37.5 (H2CCH2); 42.7 (NCH2); 49.2
(C(4)); 63.7 (C(5)); 95.5 (C(2)).
1. M. D. Khanova, R. M. Sultanova, S. S. Zlotsky, V. A. Dokꢀ
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2ꢀ(2ꢀCyclopropylethyl)ꢀ2ꢀmethylꢀ1,3ꢀoxathiolane (6a). The
product was isolated using column chromatography SiO2, Rf 0.88
(eluent was petroleum ether—AcOEt, 20 : 1), yield 53%, yellow oil.
Found (%): C, 63.01; H, 9.21; S, 18.93. C9H16SО. Calculated (%):
C, 62.74; H, 9.36; S, 18.61. IR, ν/cm–1: 760, 832, 1016, 1064,
1
1224, 1268, 1376, 1444, 2856, 2928, 3080. H NMR (CDCl3):
δ 0.20 and 0.39 (both m, each 2 H, CH2CH2 of cyclopropane);
0.66 (m, 1 H, CH); 1.79 (m, 2 H, CH2); 1.55 (s, 3 H, Ме); 2.02
(m, 2 H, CH2); 2.96—3.11 (m, 2 H, H2C(4)); 4.10—4.22 (m, 2 H,
H2C(5)). 13C NMR (δ): 4.2 (CH2CH2 of cyclopropane); 10.9
(CH); 28.9 (Ме); 30.5 and 33.7 (H2CCH2); 43.1 (C(4)); 70.1 (C(5));
95.1 (C(2)).
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23, 503.

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Recieved May, 15 2007;
In revised September, 10 2007