Asymmetric synthesis of new optically active sulfinamides of menthane series and their derivatives

Article abstract of DOI:10.1134/S1070428012020066

Asymmetric syntheses were performed of neomenthanesulfi namide in the yield of 60% and de 74%, of neomenthanesulfi naldimines and N-substituted neomenthanesulfi namides in 22-80 and 40-90% yields respectively. Pleiades Publishing, Ltd., 2012.

Full text of DOI:10.1134/S1070428012020066

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 2, pp. 184−192. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © E.S. Izmest’ev, D.V. Sudarikov, S.A. Rubtsova, P.A. Slepukhin, A.V. Kuchin, 2012, published in Zhurnal Organicheskoi Khimii, 2012,
Vol. 48, No. 2, pp. 197−205.
Asymmetric Synthesis of New Optically Active Sulfinamides
of Menthane Series and Their Derivatives
E. S. Izmest’eva, D. V. Sudarikova, S. A. Rubtsovaa, P. A. Slepukhinb, and A. V. Kuchina
aInstitute of Chemistry, Komi Scientific Center, Ural Branch, Russian Academy of Sciences,
Syktyvkar, 167982 Russia
e-mail: izmestev-es@chemi.komisc.ru
bPostovskii Institute of Organic Synthesis, Ural Division, Russian Academy of Sciences,
Yekaterinburg, Russia
Received July 20, 2011
Abstract—Asymmetric syntheses were performed of neomenthanesulfinamide in the yield of 60% and de 74%, of
neomenthanesulfinaldimines and N-substituted neomenthanesulfinamides in 22–80 and 40–90% yields respectively.
DOI: 10.1134/S1070428012020066
Sulfinamides and their derivatives are known to ex-
hibit a pronounced antisclerosis effect, potential antineu-
rotic and antimetastasis action [1], they are widely used
in the organic synthesis of chiral amines [2], as reagents
for amino group introduction in the preparation of α- and
β-amino acids [2, 3], they are employed in the synthesis
of drugs, e.g., of sibutramine [4]. Besides, sulfinimines
are good ligands in the reactions of asymmetric synthesis
[2], and N-substituted amides are used as catalysts in the
enantioselective reduction of chiral Schiff bases [5].
Initial neomenthanethiol (III) was synthesized by the
reaction of L- menthol p-toluenesulfonate (I) and thiourea
followed by alkaline hydrolysis of the formed isothiou-
ronium salt II in 60% yield calculated on compound I.
In the oxidative dimerization of thiol III with iodine di-
neomenthyl disulfide IV was obtained that was oxidized
in the system tert-butyl hydroperoxide (TBHP)–vanadyl
acetylacetonate [VO(acac)2] to give diastereomeric thio-
sulfinates (V, VI) in 67% yield with respect to compound
IV with de 45% (Scheme 1).
It was shown in [2, 6–9] that chiral inducers were
catalysts based on ligands of salen type used in the oxida-
tion of prochiral disulfides to enantiomerically enriched
thiosulfinates which at the amidation and subsequent crys-
tallization provided finally optically pure sulfinamides.
Thiol III, disulfide IV, and thiosulfinates V, VI we
have described in [10]. Disulfide IV was oxidized with
m-CPBA to obtain diastereomeric thiosulfinates V, VI
(de 28%). It was presumed that in the course of the reac-
tion formed a sterically less hindered thiosulfinate, where
the oxygen of the sulfinyl group and the isopropyl group
are oriented in the opposite directions [10].
Although the sulfinamides and their derivatives are
extensively utilized, the terpene nitrogen-containing sul-
finyl derivatives have not been described in the literature
up till now, yet natural optically pure monoterpenoids are
commercially available. They are labile in the chemical
transformations. In this approach the chiral inducer of the
sulfinyl group is the substrate molecule itself. Therefore
the studies in the chemistry of terpene sulfinamides and
their derivatives are now timely.
In this study the diastereomeric mixture V, VI of
de 45% was subjected to amidation. In [2, 8, 9] the amida-
tion of tert-butyl-containing thiosulfinates was performed
using lithium in liquid ammonia, but with dineomenthyl
thiosulfinates this system was inactive. Yet in the reac-
tion of compounds V, VI with potassium in liquid am-
monia we succeeded in obtaining diastereomeric mixture
of neomenthanesulfinamides VIIа, VIIb with de 74%
(Scheme 2). At the amidation for 2 h only the prevailing
isomer V entered the reaction. The prevailing sulfinamide
In this study we synthesized a number of sulfinyl de-
rivatives proceeding from neomenthanethiol: sulfinamide,
sulfinaldimines, and N-substituted sulfinamides.
184

ASYMMETRIC SYNTHESIS OF NEW OPTICALLY ACTIVE SULFINAMIDES
185
Scheme 1.
_
+
(1) NaOH
(2) HCl
OTs
NH2
(NH2)2CS
[EtOH]
C
NH2
OTs
S
SH
II
I
III
I2
TBHP, VO(acac)2
CHCl3
S
S
S
+
S
O_
V, VI
IV
Scheme 2.
H
O
R1
C
R1
7
HO
R1
4'
HO
HO
3'
5'
5
H
R2
LiAlH4
6'
1
2'
3
N
N
R2
R2
_48°C
S
S
7'
1'
8
9 O
O
CuSO4
THF
10
K/NH3
_78°С
H
O
NH2
VIII_XI, XIIа, XIIb
XV_XIX
V, VI
C
S
O
R3
R3
H
VIIа, VIIb
R3
LiAlH4
_48°C
N
S
N
S
O
O
XX, XXI
XIII, XIV
R1 = R2 = H (VIII, XV), t-Bu (X, XVII), Br (XI, XVIII), I (XII, XIX); R1 = H, R2 = Cl (IX, XVI); R3 = NO2 (XIII, XX),
N(СH3)2 (XIV, XXI).
VIIа we succeeded to isolate in the individual state by
crystallization from methanol and to characterize it. The
second diastereomer VIIb we failed to isolate in the pure
state. The 1H NMR spectrum of compound VIIа contains
all characteristic signals of the neomenthane fragment
and a broadened singlet of the NH2 group at 4.12 ppm.
In the 13С NMR spectrum the characteristic signal of the
atom С1 of the neomenthane fragment adjacent to the
sulfinyl group appears at 65.45 ppm. In the IR spectrum
absorption bands of the sulfinyl (1034 cm–1) and amino
(3233 cm–1) groups are observed.
derivatives: 5-chlorosalicylic, 3,5-di-tert-butylsalicylic,
3,5-dibromo- and 3,5-diiodosalicylic aldehydes, and also
para-nitro and para-dimethylamino derivatives of benzal-
dehyde. The condensation was carried out in the presence
of dehydrating agent CuSO4 and acid catalysts. Individual
diastereomer VIIа was not used in the pure state for the
condensation with aldehydes because of its low yield.
The reaction of aldehydes with the diastereomerically
enriched mixture VIIа, VIIb afforded sulfinylaldimines
VIII–XIV (Scheme 2). In all cases save compound XII
it was possible to separate by column chromatography
on silica gel in individual state and to characterize only
one of the stereoisomeric sulfinimines. At the use of the
As carbonyl compounds for the condensation with dia-
stereomers VIIа, VIIb we selected salicylaldehyde and its
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 2 2012

IZMEST’EV et al.
186
rounding, therewith the atoms S1 and О1 lie virtually in
the plane of the nitrophenyl ring. Molecular packing is by
layers, the layers are oriented parallel to the [0 1 0] plane.
No shortened intermolecular contacts between the layers
are observed, inside the layers several shortened contacts
are present, the most pronounced between them is the
contact between the oxygen of the sulfoxide fragment and
the proton in the ortho-position to the nitro group of the
phenyl ring O1⋯H5A [–1 + x, y, z] ~2.32 Å, the distance
comparable to that of an intermolecular hydrogen bond.
3,5-diiodosalicylaldehyde we isolated both sulfinimines
(S)-(XIIa) and (R)-(XIIb) in the individual state.
In the 1H NMR spectra of sulfinimines the signal of
the NH2 group of the initial sulfinamide is absent, and
the characteristic signals of the methine group C1'H at the
double bond appear in the region 8.5–8.8 ppm, and also
the proton signals of the aromatic ring are observed. The
13С NMR spectra contain the signals of the carbon atom
of the methine group C1'H in the region 159.6–165.4 ppm.
In the IR spectra absorption bands characteristic of the
С=N bond are observed in the region 1610–1650 cm–1,
and also the bands of the sulfinyl group appear. The
difference in the absolute configuration of the diiodo-
substituted diastereomers (S)-(XIIа) and (R)-(XIIb) is
observed in the dissimilar location of the corresponding
signals of the atoms of neomenthane fragment in the 1H
and 13С NMR spectra, but no displacement of the signals
of the aromatic atoms occurs for the benzene ring and the
sulfinyl group are at a large distance.
It was shown in [2] that the amidation of thiosul-
finates proceeded by the mechanism of bimolecular
nucleophilic substitution with a complete configuration
reversion at the sulfur atom. Consequently, the prevail-
ing in the mixture (S)-sulfinamide (VIIa) forms from
the predominant (S)-thiosulfinate (V) whose oxygen atom
is directed oppositely to the isopropyl group as has been
presumed in [10].
Compounds VIII–XIV, except for compound XIIb,
were reduced with LiAlH4 to the corresponding N-substi-
tuted sulfinamides (XV–XXI) obtained in 40–90% yields.
All obtained compounds XV–XXI were characterized
by NMR and IR spectra and by elemental analyses. In
the 1Н NMR spectra of the reaction products the signals
of the methine protons of sulfinimines disappear, and the
overlapping multiplets arise of protons Н1а', Н1b' and NH
in the region 4.35–5.70 ppm. In the 13С NMR spectra
an additional signal of a methylene group is observed
at 40.02–46.24 ppm. In the IR spectra a characteristic
absorption band of NH group appears in the region
3200–3400 cm–1.
The majority of the obtained sulfinimines are liquid or
amorphous substances. We succeeded in growing a single
crystal of sulfinimine XIII suitable for XRD analysis. The
sulfur atom of the sulfinyl group has the S-configuration
where the oxygen atom is oriented in the same direction
as the isopropyl group (see the figure). It was described in
[2] that sulfinimines with bulky substituents possessed the
E-configuration of the –N=CH–C group. The XRD data
of compound XIII agree with this statement. Compounds
VIII–XIV did not form Z-isomers.
Structure XIII is characterized by bond lengths and
bond angles close to the standard values (see the table).
The sulfur atom is located in the trigonal-pyramidal sur-
Hence we synthesized sulfinyl derivatives of menthane
series where the sulfinyl group is linked directly to the
nitrogen atom. Previously such compounds based on the
natural terpenoids were not known. By the XRD analy-
sis of compound XIII the absolute configuration of all
Selected bond lengths and bond distances of compound XIII
Bond
S1–O1
S1–N2
S1–C8
N2–C7
N1–O2
N1–O3
N1–C4
Å
Angle
O1S1N2
O1S1C8
N2S1C8
C7N2S1
C9C8S1
C13C8S1
N2C7C1
deg
1.4789(18)
1.695(2)
1.841(2)
1.269(3)
1.202(3)
1.216(3)
1.476(4)
110.07(12)
108.81(12)
93.27(12)
116.5(2)
112.36(17)
108.48(18)
120.6(3)
Spatial arrangement of (S,1S,2S,5R,E)-2-isopropyl-5-methyl-
N-(4-nitrobenzylidene)cyclohexanesulfinamide (XIII) by
XRD data.
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ASYMMETRIC SYNTHESIS OF NEW OPTICALLY ACTIVE SULFINAMIDES
187
sulfinyl-containing substances obtained in this study was
established, and also that of dineomenthylthiosulfinates
described in [10].
wR2 0.0828 for reflections with I > 2σ(I), R1 0.0982, wR2
0.0875 for all reflections, S 1.000. Maximal and minimal
peaks of the residual density are 0.133 и –0.129 ē Å–3.
The results of the XRD analysis are deposited in the
Cambridge Christallographic Data Center (CCDC no.
851810). These data are in free access at the address
www.ccdc.cam.ac.uk/data_request/cif.
EXPERIMENTAL
IR spectra were recorded on an IR Fourier spectro-
photometer Shimadzu IR Prestige 21 from thin films or
pellets with KBr. Melting points were measured on an
instrument Gallencamp-Sanyo. 1H and 13C NMR spectra
were registered on a spectrometer Bruker Avance-300
at operating frequencies 300.17 and 75.48 MHz respec-
tively) in CDCl3, as internal reference chloroform signals
were used. Complete assignment of the signals in the 1Н
and 13С NMR spectra was carried out with the help of
L-Menthol para-toluenesulfonate (I) was prepared
by procedure [13] from the commercial L-menthol (Alfa
Aesar), [α]D20 –50° (с 10, EtOH).
Neomenthanethiol (III). A solution of 0.31 g
(1 mmol) of menthol tosylate (I) and 0.33 g (4.3 mmol)
of thiourea in 5 ml of EtOH was boiled over 4 days. The
obtained isothiouronium salt was used without isolation.
To the solution of the isothiouronium salt containing the
residue of thiourea was added dropwise at cooling under
argon 40% NaOH solution till the complete dissolution
of the white precipitate of isothiouronium salt. At the
repeated precipitation of the isothiouronium salt new
portions of NaOH were added till complete dissolution.
The mixture was stirred under the inert atmosphere over
3–4 days, then thereto was slowly added dropwise at
vigorous stirring 10% solution of HCl. On the acid ad-
dition the reaction mixture lost the transparency and got
green-brown color. The addition of the acid was stopped
when the solution became again transparent and colorless,
or the pH of the medium should be controlled: The acid
addition was finished at pH 5–6. The solution was stirred
for another 5 min, extracted with petroleum ether (3 ×
10 ml), dried with Na2SO4, the solvent was removed in
a vacuum, the residue was subjected to chromatography
on silica gel (eluent petroleum ether, developer KMnO4).
Yield 60%. Characteristics of thiol III are given in [10].
1
2D homo- (1H–1H COSY, H–1H NOESY) and hetero-
nuclear experiments (1H–13C HSQC, HMBC). The values
of the diastereomeric excess was calculated by the ratios
of the integral intensities in the 1Н NMR spectra of the
signals of protons at the С1 atom, linked to the sulfinyl
group. The angle of the optical rotation was measured on
an automated digital polarimeter P3002RS Kruss. TLC
was performed on Sorbfil plates. Elemental analysis was
carried out on an automatic analyzer ЕА 1110 CHNS-O.
The column chromatography was performed on silica gel
Alfa Aesar (0.06–0.2 mm).
The XRD analysis of compound XIII was performed
on a fraction of a light yellow crystal of dimensions 0.25 ×
0.20 × 0.15 mm. C17H24N2O3S. Crystal rhombic, space
group Р212121, a 8.4679(7), b 14.0746(18), c 15.3817(13)
Е, V 1833.2(3)5.6(5) Е3, M 336.44, dcalc 1.219 g cm–3,
Z 4. Parameters of the unit cell and the measurement of
experimental reflections at 295(2) K was carried out on
an automatic four-circle diffractometer Xcalibur 3 (OX-
FORD DIFFRACTION) equipped with a CCD-detector
along the standard procedure [11] of ω-2θ-scanning on
the monochromated MоKα-radiation in the angles range
2.75 < θ < 28.29. Overall number of measured reflections
8351, among them 4031 independent (Rint 0.031), 1882
with I > 2σ(I). The completeness of the experiment was
96.5% for the angle θ 26.00°. No correction for extinction
was done (μ 0.192 mm–1). The structure was solved by
the direct statistical method and refined by the full-matrix
least-squares procedure with respect to F2 in the anisotro-
pic approximation for all nonhydrogen atoms. Hydrogen
atoms were placed in the geometrically calculated posi-
tions and were refined in the isotropic approximation.All
calculations were carried out using SHELX 97 software
[12]. The final results of refining are as follows: R1 0.0364,
Dineomenthyl disulfide (IV). To a solution of 0.172 g
(1 mmol) of neomenthanethiol (III) in 4 ml of ethanol
was very slowly added dropwise at vigorous stirring a
solution of 0.127 g (0.5 mmol) of I2 in 6 ml of ethanol.
The mixture was stirred for 5 h, and thereafter a double
excess of I2 was added, and the stirring was continued
for 48 h. Water (5 ml) was added, the product was ex-
tracted into petroleum ether (3 × 10 ml). The extract was
washed with 10% Na2S2O3 solution till the discoloration
of the organic phase. The upper layer was separated on
a separation funnel, dried with anhydrous Na2SO4, the
solvent was distilled off in a vacuum, the residue was
separated by column chromatography (eluent petroleum
ether, developer KMnO4). Yield 98%. Characteristics of
disulfide IV are given in [10].
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IZMEST’EV et al.
188
Оxidation of disulfides in the system TBHP–
N 6.90; S 16.01.
VO(acac)2. General procedure. In 5 ml of chloroform was
dissolved 1 mmol (0.342 g) of disulfide and 0.01 mmol
(2.7 mg) of VO(acac)2. At stirring the solution in chloro-
form of 1 mmol of TBHPwas added.After stirring for 1 h
at room temperature 10 ml of water solution containing
0.5 g of FeSO4 and 0.1 g of citric acid was added to the
reaction mixture. The reaction product was extracted
into ethyl ether (3 × 15 ml). The exract was washed with
saturated solutions of NaHCO3 and NaCl, dried with
Na2SO4. On distilling off the solvent the reaction prod-
ucts were isolated by column chromatography on silica
gel (eluent chloroform, developer KMnO4). Yield 67%,
de 45%. The characteristics of individual thiosulfinates
V, VI are given in [10].
Sulfinimines VIII–XIV. General procedure. To
1 mmol (0.20 g) of a mixture of compounds VIIа, VIIb
in 20 ml of anhydrous THF was added 1.1 mmol of alde-
hyde and 0.3 g (2 mmol) of calcined CuSO4 and 5 mol%
of p-toluenesulfonic acid as catalyst. The mixture was
stirred at room temperature over 24–48 h, afterwards the
solid residue was filtered off, the filtrate was evaporated
in a vacuum, the residue was subjected to column chro-
matography on silica gel (eluents ethyl acetate, benzene,
or CCl4–EtOAc, 2 : 1). Yields of all obtained sulfinimines
are calculated with respect to the mixture of initial sul-
finamides VIIa, VIIb.
(S,1S,2S,5R,E)-N-(2-Hydroxybenzylidene)-2-
isopropyl-5-methylcyclohexanesulfinamide (VIII).
Yellowish oily fluid, [α]D20 –6.5° (с 0.50, CHCl3). Yield
0.11 g (38%), Rf 0.19 (ethyl acetate). IR spectrum, ν,
cm–1: 3136 (OH), 2953, 2922, 1643 (C=N), 1620, 1597,
1562, 1458, 1354, 1273, 1200, 1089 (S=O), 897 (S–N),
(S,1S,2S,5R)-2-Isopropyl-5-methylcyclohexanesul-
finamide (VIIа). Into 3 ml of liquid ammonia cooled to
–78°С was slowly charged 93 mg (2.32 mmol) of metal
potassium, several crystals of FeCl3 was added, and the
mixture was stirred for 15–20 min. To this mixture was
added slowly dropwise 0.36 g (1 mmol) of the mixture
of thiosulfinates V, VI in 5 ml of anhydrous THF. The
reaction mixture was stirred for 1.5 h, then 0.4 g of NH4Cl
was added, and the stirring was continued for 15 min. The
mixture was slowly warmed to room temperature, after
evaporation of ammonia the residue was washed with
water and extracted with ethyl acetate (3 × 10 ml), the
combined organic solutions were dried with Na2SO4. The
solvent was removed in a vacuum, the reaction products
were isolated by column chromatography on silica gel
(eluents chloroform, next ethyl acetate). Yield of the
diastereomers VIIа, VIIb mixture 0.12 g (60% calculated
on the mixture V, VI). On recrystallization from methanol
yield of VIIа 0.05 g (24% calculated on the mixture V,
VI), Rf 0.25 (ethyl acetate). White amorphous powder,
[α]D20 –6.4° (с 0.40, CHCl3). IR spectrum, ν, cm–1: 3233
(NH2), 2953, 2914, 1449, 1381, 1034 (S=O), 903 (S–N),
716. 1Н NMR spectrum, δ, ppm: 0.88 d (3H, С7H3,
J 6.2 Hz), 0.94 d (3H, С10H3, J 6.7 Hz), 0.94–1.07 m
(1H, H4a), 1.06 d (3H, С9H3, J 6.2 Hz), 1.18–1.28 m
(1H, H6a), 1.29–1.41 m (1H, H2), 1.60 q.d (1H, Н3a,
J 13.2, J 3.5 Hz), 1.65–1.79 m (1H, H5), 1.84–1.99 m
(2H, H3e,4e), 2.08 d.d.t (1H, H8, J 12.9, J 10.3, J 6.5 Hz),
2.31 d.d.t (1H, H6e, J 14.4, J 3.2, J 2.5 Hz), 3.09–3.15 m
(1H, H1), 4.12 br.s (2H, NH2). 13C NMR spectrum, δ,
ppm: 21.88 (C9), 21.96 (C10), 22.57 (C7), 26.03 (C3),
27.79 (C5), 29.00 (C8), 35.53 (C4), 37.66 (C6), 49.11
(C2), 65.45 (C1). Found, %: С 59.07; H 10.41; N 6.89;
S 15.77. C10H21NOS. Calculated, %: С 58.96; H 10.38;
1
758. Н NMR spectrum, δ, ppm: 0.95 d (3H, С7H3,
J 6.4 Hz), 0.98–1.11 m (1H, H4a), 1.02 d (3H, С10H3,
J 6.6 Hz), 1.08 d (3H, С9H3, J 6.4 Hz), 1.30 d.d.d (1H,
H6a, J 14.4, J 12.7, J 3.6 Hz), 1.42–1.51 m (1H, H2),
1.74 q.d (1H, H3a, J 12.9, J 3.3 Hz), 1.73–1.87 m (1H,
H5), 1.90–2.22 m (3H, H3e,4e,8), 2.39 d.d.t (1H, H6e, J 14.4,
J 3.1, J 2.7 Hz), 3.21–3.24 m (1H, H1), 7.00–7.08 m (2H,
H4',6'), 7.45–7.52 m (2H, H5',7'), 8.80 s (1H, H1'), 11.18 s
(1H, OH). 13C NMR spectrum, δ, ppm: 21.73 (C9), 21.73
(C10), 22.53 (C7), 26.52 (C3), 28.37 (C5), 29.52 (C8),
35.41 (C4), 36.98 (C6), 49.16 (C2), 68.21 (C1), 117.31
(C4'), 118.58 (C2'), 119.85 (C6'), 133.20 (C7'), 134.63 (C5'),
160.15 (C3'), 164.59 (C1'). Found, %: С 66.44; H 8.15; N
4.59; S 10.39. C17H25NO2S. Calculated, %: С 66.41; H
8.20; N 4.56; S 10.43.
(S,1S,2S,5R,E)-N-(5-Chloro-2-hydroxybenzylid-
ene)-2-isopropyl-5-methylcyclohexanesulfinamide
(IX). Yellowish oily fluid, [α]D22 +3.8° (с 0.32, CHCl3).
Yield 0.13 g (38%), Rf 0.13 (benzene). IR spectrum, ν,
cm–1: 3115 (OH), 2953, 1618 (C=N), 1599, 1560, 1476,
1
1482, 1344, 1271, 1180 (S=O), 1091, 825, 768. Н NMR
spectrum, δ, ppm: 0.94 d (3H, С7H3, J 6.5 Hz), 0.97–
1.11 m (1H, H4a), 1.01 d (3H, С10H3, J 6.5 Hz), 1.06 d
(3H, С9H3, J 6.4 Hz), 1.30 d.d.d (1H, H6a, J 14.4, J 12.6,
J 3.9 Hz), 1.46 d.d.t (1H, H2, J 12.7, J 10.1, J 3.0 Hz),
1.71 q.d (1H, H3a, J 13.0, J 3.3 Hz), 1.71–1.83 m (1H,
H5), 1.88–2.17 m (3H, H3e,4e,8), 2.35 d.d.t (1H, H6e,
J 14.4, J 3.0, J 2.7 Hz), 3.21–3.25 m (1H, H1), 7.00 d
(1H, H4', J 8.8 Hz), 7.40 d.d (1H, H5', J 8.8, J 2.5 Hz),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 2 2012

ASYMMETRIC SYNTHESIS OF NEW OPTICALLY ACTIVE SULFINAMIDES
189
7.46 d (1H, H7', J 2.5 Hz), 8.72 s (1H, H1'), 11.16 s (1H,
OH). 13C NMR spectrum, δ, ppm: 21.71 (C9), 21.74 (C10),
22.51 (C7), 26.52 (C3), 28.40 (C5), 29.51 (C8), 35.35 (C4),
37.00 (C6), 49.15 (C2), 68.30 (C1), 118.91 (C4'), 119.26
(C2'), 124.56 (C6'), 132.01 (C7'), 134.37 (C5'), 158.65
(C3'), 163.57 (C1'). Found, %: С 59.78; H 7.00; N 3.96;
S 9.60. C17H24ClNO2S. Calculated, %: С 59.72; H 7.08;
N 4.10; S 9.38.
(C1), 111.41 (C6'), 112.09 (C4'), 120.19 (C2'), 134.34
(C7'), 139.51 (C5'), 155.85 (C3'), 162.99 (C1'). Found, %:
С 44.01; H 4.95; N 3.08; S 6.73. C17H23Br2NO2S. Calcu-
lated, %: С 43.89; H 4.98; N 3.01; S 6.89.
(S,1S,2S,5R,E)-N-(2-Hydroxy-3,5-diiodobenzylid-
ene)-2-isopropyl-5-methylcyclohexanesulfinamide
(XIIа). Yellowish oily fluid, [α]D20 +4.0° (с 0.70, CHCl3).
Yield 0.21 g (38%), Rf 0.25 (benzene). IR spectrum, ν,
cm–1: 3072 (OH), 2916, 1670 (C=N), 1586, 1546, 1458,
1430, 1344, 1306, 1276, 1226, 1154, 1086 (S=O), 900
(S,1S,2S,5R,E)-N-(3,5-Di-tert-butyl-2-hydroxy-
benzylidene)-2-isopropyl-5-methylcyclohexane-sul-
finamide (X). Colorless oily fluid, [α]D22 –9.6° (с 0.32,
CHCl3). Yield 0.09 g (22%), Rf 0.28 (benzene). IR
spectrum, ν, cm–1: 2964, 2932, 2880, 1614 (C=N), 1578,
1460, 1366, 1252, 1174, 1084 (S=O), 836 (S–N), 762.
1Н NMR spectrum, δ, ppm: 0.98 d (3H, С7H3, J 6.4 Hz),
1.00–1.14 m (1H, H4a), 1.04 d (3H, С10H3, J 6.5 Hz),
1.09 d (3H, С9H3, J 6.5 Hz), 1.20–1.32 m (1H, H6a), 1.36 s
(9H, C13'H3, C14'H3, C15'H3), 1.38–1.50 m (1H, H2), 1.50 s
(9H, С9'H3, С10'H3, С11'H3), 1.76 q.d (1H, H3a, J 12.9,
J 3.4 Hz), 1.80–1.92 m (1H, H5), 1.90–2.11 m (2H, H3e,4e),
2.20 d.d.t (1H, H8, J 12.9, J 10.3, J 6.5 Hz), 2.41 d.d.t
(1H, H6e, J 14.4, J 2.5, J 2.3 Hz), 3.18–3.24 m (1H, H1),
7.36 d (1H, H7', J 2.4 Hz), 7.56 d (1H, H5', J 2.3 Hz),
8.80 s (1H, H1'), 11.58 s (1H, OH). 13C NMR spectrum,
δ, ppm: 21.76 (C9), 21.80 (C10), 22.56 (C7), 26.60 (C3),
28.43 (C5), 29.43 (С9',10',11'), 29.48 (C8), 29.72 (C12'),
31.40 (С13',14',15'), 34.25 (C8'), 35.44 (C4), 37.19 (C6),
49.29 (C2), 68.54 (C1), 117.98 (C2'), 127.88 (C7'), 129.56
(C5'), 137.14 (C4'), 141.46 (C6'), 157.28 (C3'), 165.40 (C1').
Found, %: С 71.50; H 9.89; N 3.42; S 7.61. C25H41NO2S.
Calculated, %: С 71.55; H 9.85; N 3.34; S 7.64.
1
(S–N), 760, 700, 666, 622, 478. Н NMR spectrum, δ,
ppm: 0.97 d (3H, С7H3, J 6.4 Hz), 0.98–1.15 m (1H,
H4a), 1.01 d (3H, С10H3, J 6.6 Hz), 1.04 d (3H, С9H3,
J 6.5 Hz), 1.33 d.d.d (1H, H6a, J 14.4, J 12.7, J 3.8 Hz),
1.41–1.51 m (1H, H2), 1.71 q.d (1H, H3a, J 12.9, J 3.3
Hz), 1.71–1.89 m (1H, H5), 1.95–2.22 m (3H, H3e,4e,8),
2.34 d.d.t (1H, H6e, J 14.6, J 2.6, J 2.3 Hz), 3.23–3.27 m
(1H, H1), 7.78 d (1H, H7', J 2.0 Hz), 8.19 d (1H, H5',
J 2.0 Hz), 8.63 s (1H, H1'), 12.07 с (1H, OH). 13C NMR
spectrum, δ, ppm: 21.76 (C9), 21.81 (C10), 22.57 (C7),
26.50 (C3), 28.39 (C5), 29.43 (C8), 35.39 (C4), 36.89 (C6),
49.39 (C2), 68.11 (C1), 81.14 (C4'), 86.74 (C6'), 120.06
(C2'), 141.40 (C7'), 150.59 (C5'), 158.76 (C3'), 162.74 (C1').
Found, %: С 36.48; H 4.20; N 2.61; S 5.70. C17H23I2NO2S.
Calculated, %: С 36.51; H 4.15; N 2.50; S 5.73.
(R,1S,2S,5R,E)-N-(2-Hydroxy-3,5-diiodobenzylid-
ene)-2-isopropyl-5-methylcyclohexanesulfinamide
22
(XIIб). Yellowish oily liquid, [α]D +65.0° (с 0.12,
CHCl3). Yield 0.033 г (6%), Rf 0.26 (benzene). IR spec-
trum, ν, cm–1: 3072 (OH), 2932, 1668 (C=N), 1590, 1546,
1444, 1424, 1346, 1300, 1276, 1218, 1158, 1084 (S=O),
904 (S–N), 760, 700, 666, 622, 478. 1Н NMR spectrum,
δ, ppm: 0.84 d (3H, С7H3, J 6.2 Hz), 0.88–0.98 m (1H,
H4a), 0.84 d (3H, С10H3, J 6.4 Hz), 1.10 d (3H, С9H3,
J 6.4 Hz), 1.05–1.21 m (1H, H6a), 1.45–1.55 m (1H,
H2), 1.71 d.q (1H, H3a, J 12.3, J 3.4 Hz), 1.95–2.22 m
(5H, H3e,4e,5,8,6e), 3.27–3.32 m (1H, H1), 7.80 d (1H, H7',
J 2.0 Hz), 8.20 d (1H, H5', J 2.0 Hz), 8.57 s (1H, H1'),
12.02 s (1H, OH). 13C NMR spectrum, δ, ppm: 21.41
(C9), 21.54 (C10), 22.75 (C7), 26.21 (C3), 27.84 (C5), 29.97
(C8), 33.06 (C6), 34.94 (C4), 47.12 (C2), 62.42 (C1), 81.13
(C4'), 86.78 (C6'), 119.85 (C2'), 141.31 (C7'), 150.52 (C5'),
158.77 (C3'), 162.80 (C1'). Found, %: С 36.50; H 4.13;
N 2.64; S 5.72. C17H23I2NO2S. Calculated, %: С 36.51;
H 4.15; N 2.50; S 5.73.
(S,1S,2S,5R,E)-N-(3,5-Dibromo-2-hydroxy-
benzylidene)-2-isopropyl-5-methylcyclohexanesul-
finamide (XI). Yellowish oily fluid, [α]D22 +3.7° (с 0.87,
CHCl3). Yield 0.23 g (50%), Rf 0.23 (benzene). IR spec-
trum, ν, cm–1: 3428 (OH), 2964, 1612 (C=N), 1592, 1556,
1444, 1370, 1344, 1276, 1220, 1170, 1094 (S=O), 903
1
(S–N), 764, 744, 692, 624, 564. Н NMR spectrum, δ,
ppm: 0.96 d (3H, С7H3, J 6.4 Hz), 0.97–1.14 m (1H, H4a),
1.01 d (3H, С10H3, J 6.5 Hz), 1.04 d (3H, С9H3, J 6.4 Hz),
1.33 d.d.d (1H, H6a, J 14.4, J 12.7, J 3.6 Hz), 1.42–1.51 m
(1H, H2), 1.71 q.d (1H, H3a, J 12.9, J 3.3 Hz), 1.74–1.87 m
(1H, H5), 1.90–2.19 m (3H, H3e,4e,8), 2.50 d.d.t (1H, H6e,
J14.4, J 2.5, J 2.3 Hz), 3.23–3.29 m (1H, H1), 7.59 d (1H,
H7', J 2.2 Hz), 7.84 d (1H, H5', J 2.2 Hz), 8.70 s (1H, H1'),
11.87 s (1H, OH). 13C NMR spectrum, δ, ppm: 21.74
(C9), 21.80 (C10), 22.57 (C7), 26.50 (C3), 28.40 (C5),
29.46 (C8), 35.37 (C4), 36.87 (C6), 49.33 (C2), 68.13
(S,1S,2S,5R,E)-2-Isopropyl-5-methyl-N-(4-nitro-
benzylidene)cyclohexanesulfinamide (XIII). Yellow
crystals, mp 107.5°С, [α]D22 +28° (с 0.53, CHCl3). Yield
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 2 2012

IZMEST’EV et al.
190
0.26 g (80%), Rf 0.24 (benzene). IR spectrum, ν, cm–1:
3420, 3120, 3084, 2952, 1618 (C=N), 1590, 1522 (NO2),
1484, 1453, 1346 (NO2), 1300, 1088 (S=O), 865 (S–N),
chromatography on silica gel (eluent ethyl acetate).
(S,1S,2S,5R)-N-(2-Hydroxybenzyl)-2-isopropyl-5-
methylcyclohexanesulfinamide (XV). Colorless oily
fluid, [α]D22 +55° (с 0.30, EtOH). Yield 0.28 g (90%), Rf
0.56 (EtOAc–hexane, 5 : 1). IR spectrum, ν, cm–1: 3256
(OH), 3145 (NH), 2951, 1600, 1454, 1373, 1265, 1032
(S=O), 854 (S–N), 746, 677. 1Н NMR spectrum, δ, ppm:
0.90 d (3H, С7H3, J 6.5 Hz), 0.97–1.10 m (1H, H4a),
0.97 d (3H, С10H3, J 6.6 Hz), 1.09 d (3H, С9H3, J 6.5 Hz),
1.22–1.32 m (1H, H6a), 1.39 d.d.t (1H, H2, J 12.6, J 10.2,
J 2.8 Hz), 1.60 q.d (1H, H3a, J 12.9, J 3.3 Hz), 1.60–
1.72 m (1H, H5), 1.68–1.89 m (2H, H3e,4e), 2.08 d.d.t (1H,
H8, J 2.9, J 10.3, J 6.5 Hz), 2.19 d.d.t (1H, H6e, J 14.3,
J 3.0, J 2.2 Hz), 3.40–3.44 m (1H, H1), 4.11 d.d (1H,
H1a', J 13.1, J 2.7 Hz), 4.18 d.d (1H, NH, J 7.0, J 2.7 Hz),
4.48 d.d (1H, H1b', J 13.1, J 7.0 Hz), 6.87 d.d.d (1H, H6',
J 7.8, J 7.4, J 1.3 Hz), 6.95 d.d (1H, H4', J 7.8, J 1.3 Hz),
7.17 d (1H, H7', J 7.4, J 1.6 Hz), 7.26 t.d (1H, H5', J 7.8,
J 1.6 Hz), 8.64 s (1H, OH). 13C NMR spectrum, δ, ppm:
21.87 (C9), 21.97 (C10), 22.57 (C7), 26.15 (C3), 27.89 (C5),
29.30 (C8), 35.57 (C4), 38.45 (C6), 41.20 (C1'), 48.85 (C2),
62.47 (C1), 118.24 (C4'), 120.05 (C6'), 124.03 (C2'), 130.17
(C5'), 130.37 (C7'), 155.72 (C3'). Found, %: С 66.02;
H 8.82; N 4.49; S 10.30. C19H30NO2S. Calculated, %: С
65.98; H 8.79; N 4.53; S 10.36.
1
838, 756, 692, 660. Н NMR spectrum, δ, ppm: 0.89 d
(3H, С7H3, J 6.4 Hz), 0.96–1.09 m (1H, H4a), 1.02 d (3H,
С10H3, J 6.5 Hz), 1.08 d (3H, С9H3, J 6.5 Hz), 1.16–
1.29 m (1H, H6a), 1.42–1.51 m (1H, H2), 1.68–1.84 m
(2H, Н3a,5), 1.85–2.04 m (2H, H3e,4e), 2.14 d.d.t (1H,
H8, J 12.9, J 10.3, J 6.5 Hz), 2.49 d.d.t (1H, H6e, J 14.4,
J 3.2, J 2.5 Hz), 3.32–3.38 m (1H, H1), 8.05 d (2H, H3',7'
,
J 8.7 Hz), 8.38 d (2H, H4',6', J 8.7 Hz), 8.76 s (1H, H1').
13C NMR spectrum, δ, ppm: 21.73 (C9), 21.76 (C10),
22.62 (C7), 26.28 (C3), 28.06 (C5), 29.41 (C8), 35.36 (C4),
35.59 (C6), 48.92 (C2), 67.25 (C1), 124.27 (C4',6'), 129.99
(C3',7'), 139.06 (C5'), 149.79 (C2'), 159.59 (C1'). Found,
%: С 60.65; H 7.20; N 7.92; S 10.01. C17H24N2O3S.
Calculated, %: С 60.69; H 7.19; N 8.33; S 9.53.
(S, 1S, 2S, 5R, E)-N-[4-(Dimethylamino)
benzylidene]-2-isopropyl-5-menthylcyclohexane-
sulfinamide (XIV). Yellow powder, mp 103.7°С,
22
[α]D +16° (с 0.26, CHCl3). Yield 0.12 g (35%),
Rf 0.30 (CCl4–EtOAc, 1:1). IR spectrum, ν, cm–1:
3424 [(NCH3)2], 2949, 2845, 1611 (C=N), 1584, 1530,
1450, 1373, 1179, 1086 (S=O), 945 (S–N), 818, 708.
1Н NMR spectrum, δ, ppm: 0.89 d (3H, С7H3, J 6.5 Hz),
0.94–1.05 m (1H, H4a), 0.95 d (3H, С10H3, J 6.6 Hz),
1.10 d (3H, С9H3, J 6.5 Hz), 1.21 t.d (1H, H6a, J 13.5,
J 3.6 Hz), 1.32 d.d.t (1H, H2, J 12.8, J 9.8, J 2.9 Hz),
1.71–1.98 m (4H, Н3a,3e,4e,5), 2.17 d.d.t (1H, H8, J 12.9,
J 10.3, J 6.5 Hz), 2.50 d.d.t (1H, H6e, J 14.2, J 2.5,
J 2.2 Hz), 3.09 s (6H, H8',9'), 3.18–3.23 m (1H, H1), 6.74 d
(2H, H4',6', J 8.8 Hz), 7.34 d (2H, H3',7', J 8.8 Hz), 8.50 s
(1H, H1'). 13C NMR spectrum, δ, ppm: 21.82 (C9), 21.82
(C10), 22.78 (C7), 26.19 (C3), 27.79 (C5), 29.37 (C8),
34.96 (C6), 35.55 (C4), 40.10 (С8',9'), 48.67 (C2), 66.50
(C1), 111.44 (C4',6'), 122.85 (C2'), 131.17 (C3',7'), 152.95
(C5'), 160.52 (C1'). Found, %: С 68.30; H 8.56; N 8.82;
S 9.62. C19H30NO2S. Calculated, %: С 68.22; H 9.04;
N 8.37; S 9.59.
(S,1S,2S,5R)-N-(5-Chloro-2-hydroxybenzyl)-2-iso-
propyl-5-methylcyclohexanesulfinamide (XVI). Color-
less oily fluid, [α]D22 +40.0° (с 0.17, CHCl3). Yield 0.30 g
(86%), Rf 0.28 (EtOAc). IR spectrum, ν, cm–1: 3258 (OH),
3135 (NH), 2930, 1621, 1445, 1371, 1271, 1034 (S=O),
1
856 (S–N), 733, 684. Н NMR spectrum, δ, ppm: 0.90 d
(3H, С7H3, J 6.4 Hz), 0.95–1.09 m (1H, H4a), 0.96 d (3H,
С10H3, J 6.5 Hz), 1.07 d (3H, С9H3, J 6.4 Hz), 1.27 t.d (1H,
H6a, J 13.1, J 3.5 Hz), 1.39 d.d.t (1H, H2, J 12.5, J 10.2,
J 2.6 Hz), 1.59 q.d (1H, H3a, J 12.8, J 3.2 Hz), 1.58–1.70 m
(1H, H5), 1.98–2.10 m (3H, H3e,4e,8), 1.18 d.t.d (1H, H6e,
J 14.1, J 2.8, J 2.3 Hz), 3.37–3.41 m (1H, H1), 4.07 d.d
(1H, H1a', J 12.2, J 1.8 Hz), 4.35 br.d (1H, NH,
J 7.0 Hz), 4.40 d.d (1H, H1b', J 12.2, J 7.0 Hz), 6.83 d
(1H, H4', J 9.3 Hz), 7.15 d (1H, H7', J 2.6 Hz), 7.6 d.d
(1H, H5', J 9.3, J 2.6 Hz), 8.97 s (1H, OH). 13C NMR
spectrum, δ, ppm: 21.86 (C9), 21.92 (C10), 22.58 (C7),
26.12 (C3), 27.91 (C5), 29.30 (C8), 35.51 (C4), 38.33
(C6), 41.49 (C1'), 48.79 (C2), 62.73 (C1), 119.19 (C4'),
124.31 (C6'), 125.73 (C2'), 129.68 (C7'), 129.75 (C5'),
154.31 (C3'). Found, %: С 59.35; H 7.65; N 4.26;
S 9.25. C17H25ClNO2S. Calculated, %: С 59.37; H 7.62;
N 4.07; S 9.32.
N-Substituted sulfinamides XV–XXI. General
procedure. To a solution of 1 mmol of an appropriate
sulfinimine VIII–XIV in 20 ml of anhydrous THF cooled
to –48°С was slowly added 0.11 g (3 mmol) of LiAlH4.
The mixture was stirred for 10–20 min, then it was filtered
under a reduced pressure, the filtrate was washed with 5
ml of water and extracted with ethyl acetate (3 × 10 ml).
The extract was dried with Na2SO4, the solvent was re-
moved in a vacuum, the residue was subjected to column
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ASYMMETRIC SYNTHESIS OF NEW OPTICALLY ACTIVE SULFINAMIDES
191
(S,1S,2S,5R)-N-(3,5-Di-tert-butyl-2-hydroxy-
benzyl)-2-isopropyl-5-methylcyclohexanesulfinamide
(XVII). Colorless oily fluid, [α]D22 +46.0° (с 0.20, CHCl3).
Yield 0.31 g (75%), Rf 0.53 (EtOAc–petroleum ether,
1:6). IR spectrum, ν, cm–1: 3280 (NH, OH), 2928, 1740,
1486, 1460, 1366, 1204, 1128, 1038 (S=O), 884 (S–N).
1Н NMR spectrum (CDCl3), δ, ppm: 0.93 d (3H, С7H3,
J 6.4 Hz), 0.97–1.12 m (1H, H4a), 0.98 d (3H, С10H3,
J 6.6 Hz), 1.11 d (3H, С9H3, J 6.4 Hz), 1.21–1.33 m (1H,
H6a), 1.33 s (9H, C13'H3, C14'H3, C15'H3), 1.32–1.43 m
(1H, H2), 1.46 s (9H, С9'H3, С10'H3, С11'H3), 1.61 q.d
(1H, H3a, J 12.9, J 3.4 Hz), 1.62–1.73 m (1H, H5), 1.89–
2.15 m (3H, H3e,4e,8), 2.19 d.d.t (1H, H6e, J 14.0, J 2.3,
J 1.9 Hz), 3.40–3.44 m (1H, H1), 3.99 br.d (1H, NH,
J 7.7 Hz), 4.12 d.d (1H, H1a', J 13.2, J 1.9 Hz), 4.52 d.d
(1H, H1b', J 13.2, J 7.7 Hz), 7.06 (1H, H7', J 2.3 Hz), 7.36 d
(1H, H5', J 2.3 Hz), 8.13 s (1H, OH). 13C NMR spectrum,
δ, ppm: 21.83 (C9), 22.03 (C10), 22.56 (C7), 26.23 (C3),
27.95 (C5), 29.37 (C8), 29.79 (С9',10',11'), 31.62 (С13',14',15'),
34.23 (C12'), 35.22 (C8'), 35.56 (C4), 38.62 (C6), 41.75
(C1'), 48.88 (C2), 62.79 (C1), 123.40 (C2'), 124.68 (C7'),
124.97 (C5'), 138.01 (C4'), 141.85 (C6'), 152.17 (C3').
Found, %: С 71.19; H 10.25; N 3.39; S 7.54. C25H43NO2S.
Calculated, %: С 71.21; H 10.28; N 3.32; S 7.60.
isopropyl-5-methylcyclohexanesulfinamide (XIX).
Yellowish powder, mp 101.3°С, [α]D +72.6° (с 0.22,
22
CHCl3). Yield 0.22 g (40%), Rf 0.34 (EtOAc–hexane,
1:2). IR spectrum, ν, cm–1: 3246 (NH, OH), 2949,
1440, 1357, 1286, 1224, 1034 (S=O), 997, 864 (S–N).
1Н NMR spectrum, δ, ppm: 0.71 d (3H, С7H3, J 6.4 Hz),
0.76–0.89 m (1H, H4a), 0.78 d (3H, С10H3, J 6.6 Hz),
0.90 d (3H, С9H3, J 6.5 Hz), 1.08 t.d (1H, H6a, J 12.9,
J 3.3 Hz), 1.21 d.d.t (1H, H2, J 12.5, J 10.2, J 2.5 Hz),
1.40 q.d (1H, H3a, J 12.9, J 3.3 Hz), 1.38–1.52 m (1H,
H5), 1.68–1.89 m (3H, H3e,4e,8), 1.93 d.d.t (1H, H6e,
J 14.6, J 2.6, J 2.3 Hz), 3.21–3.26 m (1H, H1), 3.87 d.d
(1H, H1a', J 14.2, J 1.8 Hz), 4.21 d.d (1H, H1b', J 14.2,
J 7.6 Hz), 5.69 br.d (1H, NH, J 7.6 Hz), 7.32 d (1H, H7',
J 2.1 Hz), 7.82 (1H, H5', J 2.1 Hz), 9.83 s (1H, OH).
13C NMR spectrum, δ, ppm: 21.74 (C9), 21.91 (C10),
22.52 (C7), 26.05 (C3), 27.61 (C5), 29.27 (C8), 35.39
(C4), 38.53 (C6), 40.02 (C1'), 48.40 (C2), 61.85 (C1),
81.68 (C4'), 89.23 (C6'), 127.43 (C2'), 139.54 (C7'), 146.24
(C5'), 158.80 (C3'). Found, %: С 36.35; H 4.41; N 2.67;
S 5.73. C17H25I2NO2S. Calculated, %: С 36.38; H 4.49;
N 2.50; S 5.71.
(S,1S,2S,5R)-N-(4-Nitrobenzyl)-2-isopropyl-5-
methylcyclohexanesulfinamide (XX). Yellow powder,
mp 92.7°С, [α]D22 +34.4° (с 0.45, CHCl3). Yield 0.32 g
(94%), Rf 0.45 (EtOAc). IR spectrum, ν, cm–1: 3177 (NH),
2949, 1603, 1517 (NO2), 1344 (NO2), 1036 (S=O), 853
(S–N). 1Н NMR spectrum, δ, ppm: 0.87 d (3H, С7H3,
J 6.5 Hz), 0.91–1.02 m (1H, H4a), 0.92 d (3H, С10H3,
J 6.6 Hz), 1.04 d (3H, С9H3, J 6.4 Hz), 1.19–1.29 m
(1H, H6a), 1.35 d.d.t (1H, H2, J 12.5, J 9.8, J 2.7 Hz),
1.56 q.d (1H, H3a, J 13.0, J 3.5 Hz), 1.56–1.66 m (1H,
H5), 1.79–2.07 m (3H, H3e,4e,8), 2.23 d.d.t (1H, H6e, J 13.8,
J 2.5, J 2.2 Hz), 3.26–3.30 m (1H, H1), 4.35–4.45 m (3H,
H1a',1b', NH), 7.55 d (2H, H3',7', J 8.5 Hz), 8.21 d (2H,
H4',6', J 8.5 Hz). 13C NMR spectrum, δ, ppm: 21.88 (C9),
21.96 (C10), 22.56 (C7), 26.13 (C3), 27.96 (C5), 29.10 (C8),
35.47 (C4), 38.13 (C6), 46.24 (C1'), 49.11 (C2), 63.49 (C1),
123.84 (C4',6'), 128.82 (C3',7'), 146.16 (C2'), 147.50 (C5').
Found, %: С 60.29; H 7.77; N 8.33; S 9.51. C17H26N2O3S.
Calculated, %: С 60.33; H 7.74; N 8.28; S 9.47.
(S,1S,2S,5R)-N-(3,5-Dibromo-2-hydroxybenzyl)-2-
isopropyl-5-methylcyclohexanesulfinamide (XVIII).
22
Yellowish powder, mp 98.4°С, [α]D +67.3° (с 0.30,
CHCl3). Yield 0.33 g (72%), Rf 0.33 (ССl4–EtOAc,
2:1). IR spectrum, ν, cm–1: 3280 (NH, OH), 2929, 1742,
1490, 1455, 1334, 1206, 1132, 1038 (S=O), 854 (S–N).
1Н NMR spectrum, δ, ppm: 0.90 d (3H, С7H3, J 6.4 Hz),
0.95–1.08 m (1H, H4a), 0.96 d (3H, С10H3, J 6.6 Hz),
1.07 d (3H, С9H3, J 6.3 Hz), 1.28 t.d (1H, H6a, J 13.2,
J 3.5 Hz), 1.39 d.d.t (1H, H2, J 12.7, J 10.1, J 3.0 Hz),
1.57 q.d (1H, H3a, J 12.9, J 3.3 Hz), 1.55–1.68 m (1H, H5),
1.83–2.06m (3H, H3e,4e,8), 2.13 d.d.t (1H, H6e, J 14.7, J 2.7,
J 2.3 Hz), 3.37–3.41 m (1H, H1), 4.11 d.d (1H, H1a', J 14.0,
J 1.9 Hz), 4.25 br.d (1H, NH, J 7.4 Hz), 4.44 d.d (1H,
H1b', J 14.0, J 7.4 Hz), 7.29 d (1H, H7', J 2.4 Hz), 7.64 d
(1H, H5', J 2.4 Hz), 8.91s (1H, OH). 13C NMR spec-
trum, δ, ppm: 21.84 (C9), 21.97 (C10), 22.57 (C7), 26.18
(C3), 27.90 (C5), 29.32 (C8), 35.53 (C4), 38.54 (C6),
40.65 (C1'), 48.77 (C2), 62.65 (C1), 111.14 (C4'), 113.54
(C6'), 127.27 (C2'), 132.19 (C7'), 135.25 (C5'), 151.42
(C3'). Found, %: С 44.01; H 5.36; N 2.82; S 6.83.
C17H25Br2NO2S. Calculated, %: С 43.70; H 5.39; N 3.00;
S 6.86.
(S,1S,2S,5R)-N-[4-(Dimethylamino)benzyl]-2-
isopropyl-5-methylcyclohexanesulfinamide (XXI). Yel-
22
lowish powder, mp 84.3°С, [α]D +49.1° (с 0.27, CHCl3).
Yield 0.30 g (88%), Rf 0.48 (EtOAc). IR spectrum, ν, cm–
1: 3184 (NH), 2951, 1614, 1524, 1450, 1348, 1049 (S=O),
1
947 (S–N), 810, 754. Н NMR spectrum, δ, ppm: 0.90 d
(S,1S,2S,5R)-N-(2-Hydroxy-3,5-diiodobenzyl)-2-
(3H, С7H3, J 6.4 Hz), 0.95–1.08 m (1H, H4a), 0.96 d (3H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 2 2012

IZMEST’EV et al.
192
С10H3, J 6.6 Hz), 1.07 d (3H, С9H3, J 6.3 Hz), 1.28 t.d (1H,
H6a, J 13.2, J 3.5 Hz), 1.39 d.d.t (1H, H2, J 12.7, J 10.1,
J 3.0 Hz), 1.57 q.d (1H, H3a, J 13.0, J 3.5 Hz), 1.62–1.75 m
(1H, H5), 1.82–1.98 m (2H, H3e,4e), 2.13 d.d.t (1H, H8,
J 12.9, J 10.4, J 6.5 Hz), 2.28 d.d.t (1H, H6e, J 14.0,
J 2.8, J 2.5 Hz), 2.97 s (6H, H8',9'), 3.26–3.30 m (1H, H1),
4.25 t (1H, NH, J 6.0 Hz), 4.22 t (2H, H1a',1b', J 6.0 Hz),
6.74 d (2H, H4',6', J 8.6 Hz), 7.24 d (2H, H3',7', J 8.6 Hz).
13C NMR spectrum, δ, ppm: 21.92 (C9), 22.03 (C10),
22.63 (C7), 26.08 (C3), 27.90 (C5), 29.09 (C8), 35.63
(C4), 38.09 (C6), 40.63 (С8',9'), 46.07 (C1'), 49.15 (C2),
62.87 (C1), 112.65 (C4',6'), 126.00 (C2'), 129.30 (C3',7'),
150.20 (C5'). Found, %: С 67.84; H 9.50; N 8.38;
S 9.49. C19H32N2OS. Calculated, %: С 67.81; H 9.58;
N 8.32; S 9.53.
E.N. Zainullina, S.P. Kuznetsov, and A.N. Alekseev for
registering NMR spectra sand to E.U. Ipatova for regis-
tering IR spectra.
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of the Russian Foundation for Basic Research (grant
no.10-03-00969) and of the Federal Agency for Science
and Innovations in the framework of the Federal Targeted
program “Scientific and Pedagogical Staff of Innovation
Russia” (State Contract no. 02.740.11.0081).
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