Synthesis and reduction of new sulfinimines with isobornane structure

Article abstract of DOI:10.1134/S1070428012110024

Synthesis of sulfenimines proceeding from isobornanethiol with yields up to 78% was performed. They were oxidized to diastereomeric isobornylsulfinimines and the latter were reduced to N-substituted isobornylsulfinamides in high yields.

Full text of DOI:10.1134/S1070428012110024

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 11, pp. 1407−1418. © Pleiades Publishing, Ltd., 2012.
Original English 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. 11, pp. 1412−1421.
Synthesis and Reduction of New Sulfinimines
with Isobornane Structure
E. S. Izmest’eva, D. V. Sudarikova, S. A. Rubtsovaa, P. A. Slepukhinb, and A. V. Kuchina
aInstitute of Chemistry, Komi Scientific Center, Ural Division, 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 ,
Ekaterinburg, Russia
Received May 13, 2012
Abstract—Synthesis of sulfenimines proceeding from isobornanethiol with yields up to 78% was performed.
They were oxidized to diastereomeric isobornylsulfinimines and the latter were reduced to N-substituted
isobornylsulfinamides in high yields.
DOI: 10.1134/S1070428012110024
The synthetic opportunities provided by sulfinimines
are known to be wider than those of imines due to the
higher reactivity originating from the presence of the
sulfinyl group that increases the electrophilicity of imines
and thus facilitates the nucleophilic attack on the C=N
bond [1].
the substrate the research in the field of the chemistry of
terpene sulfinamides and their derivatives is important
today.
Sulfinyl derivatives of neomenthane series were
described in [6]. In the present study a series of sulfen-
imines, sulfinimines and N-substituted sulfinamides was
synthesized proceeding from the isobornanethiol.
The sulfinyl group is a good chiral directing group
for the synthesis of enantiomerically pure amino acids,
α-branched amines, structural fragments of biologically
active substances: antibiotics (nikkomycin, ciomycin,
bottromycin) and pesticides [2, 3].
Initial isobornanethiol (I) was synthesized in 85%
yield from L-bornyl p-toluenesulfonate (II) and thiourea
followed by an alkaline hydrolysis of isothiuronium salt
III without its isolation (Scheme 1). The formation of
the isothiuronium salt occurs along the mechanism of
the bimolecular nucleophilic substitution with a complete
reversal of the configuration at the atom C2 [7].
Ligands based on chelate type sulfinimines are used
in complex formation [4], and metal complexes prepared
therefrom are utilized in the asymmetrical synthesis of
cyclic compounds along Diels-Alder reaction [5].
The reaction of thiols with N-chlorosuccinimide
(NCS) in liquid ammonia or in the presence of primary
or secondary amines leads to the formation of the corre-
sponding sulfenamides [8]. Thiol I was treated with NCS
in liquid ammonia to obtain isobornylsulfenamide (IV).
Compound IV is unstable, we failed to isolate it in pure
state and to characterize it, therefore it was used without
Though the sulfinimines and their derivatives are
widely used, terpene nitrogen-containing sulfinyl deriva-
tives are insufficiently studied, although natural optically
pure monoterpenoids are commercially available and
labile in chemical transformations. Inasmuch as the chiral
inductor of the sulfinyl group is the proper molecule of
Scheme 1.
NH2OTs (1) NaOH
(2) HCl
OTs
S
SH
S
(NH2)2CS
[EtOH]
NCS
NH3
C
NH2
NH2
I
II
III
IV
1407

IZMEST’EV et al.
1408
separation from the reaction mixture in condensation
with aldehydes at room temperature in the mixture THF–
CH2Cl2. The aldehyde was added to the reaction mixture
after the evaporation of the most part of ammonia. The
following carbonyl compounds were used in the conden-
sation with sulfenamide IV: salicylaldehyde, its 5-chloro-,
5-bromo-, 3,5-di-tert-butyl-, 3,5-dibromo-, 3,5-diiodo
derivatives and p-nitro- and p-dimethylaminobenzoic
aldehydes. This choice of aldehydes was governed,
firstly, by the presence of fungicidal and antimicrobial
activity of salicylaldehyde and its derivatives, secondly,
by their application to the synthesis of pharmaceuticals
(chelating agents), and, thirdly, by the presence of OH
group in the ortho-position to CH=O and imino group
that may result in the increase of the chelating ability of
the salicylimines compared with the salicylaldehyde and
provide a possibility to use the compounds as ligands
in complexing with d-transition metals. The derivatives
of benzoic aldehyde are well crystallizable, and this is
important for establishing the absolute configuration of
compounds by XRD analysis.
target sulfenimines. The low yields of compounds VII,
XI, XII are likely to result from the longer duration of
the condensation leading to the decomposition of the
unstable intermediate sulfenamide IV.
The composition and structure of the sulfenimines
were established from NMR and IR spectra and elemental
13
analysis. The C NMR spectra of sulfenimines V–XII
contain the characteristic signals of atoms C1' at the
1
double bond (151–161 ppm). In the H NMR spectra
the signals of protons attached to these carbon atoms
appear in the region 8.3–8.6 ppm. In the IR spectra of all
sulfenimines the absorption bands characteristic of the
stretching vibrations of the C=N bond were observed in
the range 1570–1613 cm–1.
All synthesized sulfenimines were solid substances,
we succeeded to grow crystals from compounds V, IX
suitable for XRD analysis (Fig. 1). The sulfenimines have
the (E)-configuration of the N=CH–C group in agreement
with the published data on the compounds with bulky
substituents [2]. Besides the (E)-configuration was con-
firmed by the NOE-interaction between the proton of the
OH group and the H2 of the terpene fragment.
Thus a series of sulfenimines V–XII containing the
isobornyl fragment was prepared (Scheme 2).
The synthesized sulfenimines were oxidized with
m-chloroperoxybenzoic acid and with the system tert-
butylhydroperoxide–vanadyl acetylacetonate VO(acac)2
to sulfinyl derivatives XIII–XX in quantitative yields.
The choice of the oxidant does not affect the de value.
The oxidation with m-chloroperoxybenzoic acid at room
temperature proceeds quantitatively, de 52–54%. The
reaction carried out at –78°C led to insignificant enhance-
ment of the diastereoselectivity to 58–61%. The system
tert-butylhydroperoxide–VO(acac)2 also quantitatively
oxidized compounds V–XII to sulfinimines, de 52–55%.
Sulfenimines V–XII were obtained in 36–78% yields
except for compound VIII that was isolated in 11%
yield. The low yield of sulfenimine VIII was due to
the formation of a large amount of 2,4-di-tert-butyl-6-
(iminomethyl)phenol, the by-product of the condensa-
tion of 3,5-di-tert-butyl-salicylaldehyde with residual
ammonia that was difficultly separated from the target
sulfenimine. We did not observe any regularity in the
effects of electronic and steric factors of the substituents
in the benzene ring of the aldehyde on the yield of the
Scheme 2.
O
10
OH
R1
O
S
O
S
S
R2
2'
2
R2
R2
6
1'
[O]
[O]
N
N
LiAlH4
R2
N
7
9
8
H
3
O
HO
HO
HO
4'
R1
R1
R1
XIII_XVIII
O
S
XXI_XXVI
V_X
IV
O
S
3'
S
R3
1'
N
N
LiAlH4
N
H
R3
R3
R3
XI, XII
XIX, XX
XXVII, XXVIII
R1 = R2 = H (V, XIII, XXI), Br (VI, XIV, XXII), I (VII, XV, XXIII), t-Bu (VIII, XVI, XXIV); R1 = H, R2 = Cl (IX, XVII, XXV), Br
(X, XVIII, XXVI); R3 = NO2 (XI, XIX, XXVII), N(CH3)2 (XII, XX, XXVIII).
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SYNTHESIS AND REDUCTION OF NEW SULFINIMINES
1409
We did not observe any regular trends in the influence of
the electronic and steric factors of the substituents in the
benzene ring of the aldehyde on the diastereoselectivity of
the oxidation and on the yields of the target sulfinimines.
Sulfinimines XIII–XX were obtained as mixtures of
diastereomers which we failed to separate by column
chromatography. The structure of compounds XIII–XX
was confirmed by NMR and IR spectra.
V
In the IR spectra of all sulfinimines as compared with
the corresponding sulfenimines appear the characteristic
absorption band of the stretching vibrations of S=O bond
(1010–1090 cm–1), and the absorption bands of the C=N
bond in the range 1570–1613 cm–1 are retained.
In the 13C NMR spectra of compounds XIII–XX the
signals of the carbon atom of the CH=N group in the
region 159–165 ppm are conserved. The signal of the
proton at atom C1' in the 1H NMR spectra is observed in
the range 8.4–8.8 ppm. The signals of atoms C2 of the
terpene fragment in the 13C NMR spectra compared with
the corresponding sulfenyl derivatives (59.49–60.93 ppm)
are shifted downfield (75.13–77.64 ppm), and the signals
of protons H2 in the 1H NMR spectra are shifted upfield
from 3.53–3.64 to 2.46–2.84 ppm.
IX
Fig. 1. General view of the molecules (1S,2S,4S,E)-N-
(2-hydroxybenzylidene)-1,7,7-trimethylbicyclo[2.2.1]
heptane-2-sulfenamide (V) and (1S,2S,4S,E)-N-(2-hydroxy-
5-chlorobenzylidene)-1,7,7-trimethylbicyclo[2.2.1]heptane-
2-sulfenamide (IX) according to the data of XRD analysis.
the S=O group into shielding the nucleus of this proton
from the external magnetic field.
From the diastereomeric mixture of sulfinimines XIX
the prevailing isomer (RS)-XIX was isolated by crystal-
lization, and its structure was proved by XRD analysis
(Fig. 2).
Compounds XIII–XX as diastereomeric mixtures
were reduced with LiAlH4 to the corresponding N-
substituted sulfinamides XXI–XXVIII in 80–98%
yields.All N-substituted sulfinamides except for XXVII,
XXVIII were separated by column chromatography into
individual diastereomers, and each of them were charac-
terized by IR and NMR spectroscopy and by elemental
analysis. In the 1H NMR spectra the signals of methine
protons of sulfinimines disappeared and superimposed
multiplets arose of protons H1'A, H1'C, and NH in the
region 3.8–5.2 ppm. In the 13C NMR spectrum an ad-
ditional signal appeared belonging to the methylene
group in the region 40.23–43.65 ppm. In the IR spectra
appeared a characteristic absorption band of NH group
in the region 3200–3400 cm–1. The reduction of imines
proceeds without changes in the configuration of the
chiral centers of the sulfinyl group and isobornane frag-
ment, therefore the prevailing isomers of N-substituted
sulfinamides have the (R)-configuration, like the initial
sulfinimines. It was proved by NMR spectroscopy. In the
spectra 1H–1H NOESY of compounds XXI–XXVIII the
correlations of the protons of the terpene fragment are
the same as in the initial sulfinimines.
Notwithstanding the presence of sufficiently heavy
atoms and the expected appearance of the anomalous light
scattering in the diffraction experiment the error in the
measurement of this parameter prevented the unambiguous
establishing the absolute configuration of compounds under
investigation. The absolute configuration of molecules V,
IX, (RS)-XIX was established out basing on the isobornane
fragment whose configuration was preliminary known [7].
In the molecule (RS)-XIX the oxygen atom of the sulfinyl
group is directed to the opposite side from the group C10H3.
Consequently it was sterically more favorable to form the
less hindered (RS)-diastereomer.
The absolute configuration of the sulfinyl group of
sulfinimines XIII–XVIII, XX we succeeded to establish
by the correlation of 1H NMR spectra and the XRD data.
The signals of the endo-proton at C3 in the prevailing (RS)-
diastereomer are shifted upfield (~1.50 ppm) compared to
the signals of the analogous protons of (SS)-isomer (~1.70
ppm). The upfield shift of the signal of the endo-proton at
C3 diastereomer with R-configuration of the sulfinyl group
may be attributed to the involvement of the electrons of
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IZMEST’EV et al.
1410
fraction) along a stsndard procedure [9] by the method of
ω-2θ-scanning with a step of 1° with the monochromated
MoKα-radiation.
The structures were solved by the direct statistical
method and refined using full-matrix least-squares proce-
dure with respect to F2 in the anisotropic approximation
for all nonhydrogen atoms. Hydrogen atoms were placed
in the geometrically calculated positions and were refined
in the isotropic approximation. All calculations were
performed with SHELX 97 software [10].
Fig. 2. General view of the molecule (RS,1S,2S,4S,E)-N-(4-
nitrobenzylidene)-1,7,7-trimethylbicyclo[2.2.1]heptane-2-
sulfinamide RS-(XIX) according to the data of XRD analysis.
The XRD experiment on compound V, C17H23NOS,
was performed using a fragment of colorless crystal of
the size 0.25 × 0.20 × 0.12 mm. The crystal is rhom-
bic, space group P212121, a 10.2194(9), b 20.0748(9),
c 23.6648(9) Å, V 4854.9(5) Å3, dcalc 1.188 g/cm3, Z 12.
In the range of angles 2.66 < θ < 28.29° 29538 reflec-
tions were measured, among them 11953 independent
(Rint 0.0527), 4350 with I > 2σ(I). The completeness
of experiment at the angle θ 28.29° was 99.7%. The
correction for extinction was not done (μ 0.196 mm–1).
Final results of the refining are as follows: R1 0.0353,
wR2 0.0828 for reflections with I > 2σ(I); R1 0.1388,
wR2 0.0795 for all reflections, GOOF 0.999. The
maximal and minimal peaks of the residual electron
density are 0.200 and –0.172 ēÅ–3. The absolute structural
parameter is –0.03(5).
Thus new sulfenyl and sulfinyl derivatives were
synthesized containing an isobornyl fragment. In these
substances the sulfinyl group is directly bound to the nitro-
gen atom. Proceeding from NMR, XRD of compounds V,
IX, XIX, and published data we established the absolute
configuration of all compounds obtained in this study.
EXPERIMENTAL
IR spectra were recorded on IR Fourier spectrometer
Shimadzu IR Prestige 21 from thin films or pellets with
KBr. Melting points were measured on an instrument Gal-
lencamp-Sanyo. NMR spectra were registered on a spec-
trometer Bruker Avance-300 [300.17 (1H), 75.48 MHz
(13C)] from solutions in CDCl3, if not indicated otherwise,
residual signals of undeuterated chloroform served as
internal reference. The complete assignment of signals
The XRD experiment on compound IX, C17H22Cl-
NOS, was performed using a fragment of colorless
crystal of the size 0.25 × 0.20 × 0.15 mm. The crystal is
monoclinic, space group P21, a 14.5018(11), b 6.8357(3),
c 17.1670(14) Å, β 101.757(7)°, V 1666.1(2) Å3,
dcalc 1.291 g/cm3, Z 4. In the range of angles 2.87 < θ <
28.29° 10740 reflections were measured, among them
6007 independent (Rint 0.0249), 3622 with I > 2σ(I).
The completeness of experiment at the angle θ 26.00°
was 98.5%. The correction for extinction was not done
(μ 0.353 mm–1). Final results of the refining are as fol-
lows: R1 0.0321, wR2 0.0542 for reflections with I > 2σ(I);
R1 0.0682, wR2 0.0574 for all reflections, GOOF 1.000.
The maximal and minimal peaks of the residual electron
density are 0.163 and –0.150 ēÅ–3. The absolute structural
parameter is 0.00(4).
1
in H and 13C NMR spectra was performed using 2D
homo- (1H–1H COSY, 1H–1H NOESY) and heteronuclear
experiments (1H–13C HSQC, HMBC). The values of
diastereomer exess (de) were calculated from the data of
1H NMR spectra from the intensity ratio of the protons
linked to atom C2 bound to the sulfinyl group. The angle of
the optical rotation was measured on an automatic digital
polarimeter P3002RS Kruss. Thin layer chromatography
was carried out on Sorbfil plates eluting with the mixed
solvents CHCl3–EtOAc (or Et2O), petroleum ether–EtO-
Ac, C6H6–Et2O, C6H6, CHCl3, development with etanol
solution of phosphomolibdic acid or KMnO4. Elemental
analysis was performed on an automatic analyzer EA1110
CHNS-O. All reactions were carried out using freshly
distilled solvents. For the column chromatography silica
gel Alfa Aesar (0.06–0.2 mm) was utilized, elution with
the same solvent systems as in the TLC.
The XRD experiment on compound XIX,
C17H22N2O3S, was performed using a fragment of yel-
low crystal of the dimensions 0.25 × 0.20 × 0.15 mm.
The crystal is rhombic, space group P212121, a 6.7902(5),
b 12.0189(11), c 20.7455(19) Å, β 101.757(7)°,
V 1693.1(3) Å3, dcalc 1.312 g/cm3, Z 4. In the range of
The unit cell parameters and the set of experimental
reflections in the XRD experiments were measured at
295(2) K on an automatic four-circle diffractometer
equipped with a CCD detector Xcalibur 3 (Oxford Dif-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 11 2012

SYNTHESIS AND REDUCTION OF NEW SULFINIMINES
1411
angles 3.16 < θ < 28.30° 8588 reflections were measured,
among them 4092 independent (Rint 0.0296), 1722 with
I > 2σ(I). The completeness of experiment at the angle
θ 28.30° was 99.7%. The correction for extinction was
not done (μ 0.207 mm–1). Final results of the refining are
as follows: R1 0.0311, wR2 0.0361 for reflections with I >
2σ(I); R1 0.0917, wR2 0.0373 for all reflections, GOOF
0.999. The maximal and minimal peaks of the residual
electron density are 0.119 and –0.138 ēA–3. The absolute
structural parameter is –0.03(5).
(C2), 116.89 (C4'), 119.17 (C6'), 120.25 (C2'), 130.16
(C7'), 131.36 (C5'), 158.88 (C3'), 159.43 (C1'). Found, %:
C 70.63; H 8.06; N 4.79; S 11.00. C17H23NOS. Calculated,
%: C 70.54; H 8.01; N 4.84; S 11.08.
(1S,2S,4S,E)-N-(2-Hydroxy-3,5-dibromo-
benzylidene)-1,7,7-trimethylbicyclo[2.2.1]heptane-
2-sulfenamide (VI). Yield 78%, yellow powder, mp
22
92–93°C, [α]D +48.0° (C 0.20, acetone), Rf 0.54 (pe-
troleum ether–Et2O, 10:1). IR spectrum, ν, cm–1: 1578
1
(C=N), 1280 (Carom–OH), 1165 (C–Br). H NMR
spectrum, δ, ppm: 0.91 s (6H, C9H3, C8H3), 1.06 s (3H,
C10H3), 1.24–1.40 m (2H, H5-endo,6-endo), 1.73–1.93 m (4H,
H3-exo,4,5-exo,6-exo), 2.05 d.d (1H, H3-endo, J 13.0, 9.6 Hz),
3.54 d.d (1H, H2, J 9.4, 5.9 Hz), 7.23 d (1H, H7', J 2.2 Hz),
7.65 d (1H, H5', J 2.2 Hz), 8.38 s (1H, H1'), 12.44 br.s (1H,
OH). 13C NMR spectrum, δ, ppm: 13.69 (C10), 19.97 (C9),
20.03 (C8), 27.29 (C5), 37.47 (C3), 38.02 (C6), 45.46 (C4),
47.30 (C7), 50.04 (C1), 60.63 (C2), 110.73 (C6'), 111.57
(C4'), 121.89 (C2'), 131.36 (C7'), 136.30 (C5'), 154.65
(C3'), 156.52 (C1'). Found, %: C 45.61; H 4.69; N 3.16;
S 7.15. C17H21Br2NOS. Calculated, %: C 45.66; H 4.73;
N 3.13; S 7.17.
The results of the XRD experiments were deposited
in the Cambridge Crystallographic Data Center (CCDC
nos. 904102–904104. These data are free to obtain at the
address: www.ccdc.cam.ac.uk/data_request/cif.
L-Bornyl p-toluenesulfonate (II) was obtained by
procedure [6] from crude L-borneol purified by fractional
crystallization from hexane. [α]D20 –38.0°(C 10, EtOH).
Isobornanethiol [(1S-exo)-2-bornanethiol] (I) was
20
synthesized by the method [11]. Yield up to 85%, [α]D
20
+47.0° (C 1.0, EtOH) {[α]D +48.3° (C 11.8, MeOH)
[8]}. Characteristics of thiol I were reported in [8].
Isobornylsulfenimines V–XII. To 15–20 ml of liquid
ammonia at–(35–40°C) was carefully added 2 mmol
(0.266 g) of NCS, the mixture was stirred for 5 min, a
solution of 1 mmol (0.170 g) of isobornanethiol in 3 ml
of anhydrous THF, was added, the reaction mixture
was stirred for 4 h, 3 ml of CH2Cl2 was added, and the
mixture was warmed to room temperature. After the am-
monia evaporation 2 mmol of aldehyde was added, and
the reaction mixture was stirred for 12 h. The reaction
mixture was filtered in a vacuum, and the solvent was
removed. The reaction product was isolated by column
chromatography on silica gel, elution with CH2Cl2 or
CHCl3 containing a little Et2O.
(1S,2S,4S,E)-N-(2-Hydroxy-3,5-diiodobenzylid-
ene)-1,7,7-trimethylbicyclo[2.2.1]heptane-2-sulfen-
amide (VII). Yield 36%, yellow powder, mp 81–82°C
(decomp), [α]D22 +34.3° (C 0.18, acetone), Rf 0.33 (pe-
troleum ether–Et2O, 10:1). IR spectrum, ν, cm–1: 1573
(C=N), 1275 (Carom–OH), 739 (C–I), 658 (C–I). 1H NMR
spectrum, δ, ppm: 0.90 s (6H, C9H3, C8H3), 1.05 s (3H,
C10H3), 1.23–1.41 m (2H, H5-endo,6-endo), 1.73–1.92 m
(4H, H3-exo,4,5-exo,6-exo), 2.05 d.d (1H, H3-endo, J 13.0,
9.6 Hz), 3.53 d.d (1H, H2, J 9.4, 5.9 Hz), 7.41 d (1H, H7',
J 1.8 Hz), 8.00 d (1H, H5', J 1.8 Hz), 8.30 s (1H, H1'),
12.63 br.s (1H, OH). 13C NMR spectrum, δ, ppm: 13.77
(C10), 19.98 (C9), 20.07 (C8), 27.30 (C5), 37.60 (C3), 37.98
(C6), 45.42 (C4), 47.31 (C7), 50.04 (C1), 60.60 (C2), 80.57
(C6'), 86.49 (C4'), 121.76 (C2'), 138.39 (C7'), 137.30 (C5'),
156.27 (C1'), 157.58 (C3'). Found, %: C 37.75; H 3.94;
N 2.56; S 5.97. C17H21I2NOS. Calculated, %: C 37.73,
H 3.91; N 2.59; S 5.92.
(1S,2S,4S,E)-N-(2-Hydroxybenzylidene)-1,7,7-
trimethylbicyclo[2.2.1]heptane-2-sulfenamide (V).
Yield 71%, yellow crystals, mp 79–80°C, [α]D22 +63.2°
(C 0.19, acetone), Rf 0.40 (petroleum ether–Et2O, 10:1).
IR spectrum, ν, cm–1: 1593 (C=N), 1273 (Carom–OH).
1H NMR spectrum, δ, ppm: 0.90 s (3H, C8H), 0.92 s (3H,
C9H3), 1.08 s (3H, C10H3), 1.21–1.39 m (2H, H5-endo,6-
endo), 1.72–1.90 m (4H, H3-exo,4,5-exo,6-exo), 2.04 d.d (1H,
H3-endo, J 13.0, 9.6 Hz), 3.55 d.d (1H, H2, J 9.6, 6.0 Hz),
6.85–6.99 m (2H, H6',4'), 7.16 d.d (1H, H7', J 7.6, 1.4 Hz),
2.29 d.d.d (1H, H5', J 8.0, 7.6, 1.4 Hz), 8.25 s (1H, H1'),
11.67 br.s (1H, OH). 13C NMR spectrum, δ, ppm: 13.68
(C10), 20.01 (C9), 20.10 (C8), 27.34 (C5), 37.24 (C3),
38.06 (C6), 45.43 (C4), 47.30 (C7), 49.91 (C1), 60.08
(1S,2S,4S,E)-N-(2-Hydroxy-3,5-di-tert-
butylbenzylidene)-1,7,7-trimethylbicyclo[2.2.1]-
heptane-2-sulfenamide (VIII). Yield 11%, yellow oily
fluid, [α]D22 +44.0° (C 0.45, acetone), Rf 0.56 (petroleum
ether–Et2O, 10:1). IR spectrum, ν, cm–1: 1564 (C=N),
1271 (Carom–OH). 1H NMR spectrum, δ, ppm: 0.92 s (3H,
C8H3), 0.95 s (3H, C9H3), 1.10 s (3H, C10H3), 1.28–1.56 m
(2H, H5-endo,6-endo), 1.35 s (9H, C13',14',15'H3), 1.51 s (9H,
C9',10',11'H3), 1.72–1.93 m (4H, H3-exo,4,5-exo,6-exo), 2.07 d.d
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IZMEST’EV et al.
1412
(1H, H3-endo, J 13.0, 9.6 Hz), 3.60 d.d (1H, H2, J 9.6,
6.0 Hz), 7.02 d (1H, H7', J 2.2 Hz), 7.39 d (1H, H5',
J 2.2 Hz), 8.57 c (1H, H1'), 11.99 br.s (1H, OH). 13C NMR
spectrum, δ, ppm: 13.70 (C10), 20.04 (C9,8), 27.34 (C5),
29.46 (C9',10',11'), 31.49 (C13',14',15'), 34.13 (C12'), 35.02
(C8'), 37.49 (C3), 38.02 (C6), 45.44 (C4), 47.27 (C7), 49.89
(C1), 59.78 (C2), 119.47 (C2'), 125.07 (C5'), 126.17 (C7'),
136.54 (C4'), 140.55 (C6'), 155.86 (C3'), 160.88 (C1').
Found, %: C 74.70; H 9.84; N 3.48; S 8.00. C25H39NOS.
Calculated, %: C 74.76; H 9.79; N 3.49; S 7.98.
2.03 d.d (1H, H3-endo, J 13.0, J 9.6 Hz), 3.53 d.d (1H, H2,
J 9.5, 5.9 Hz), 6.85 d (1H, H4', J 8.7 Hz), 7.26 d (1H, H7',
J 2.4 Hz), 7.35 d.d (1H, H5', J 8.7, 2.4 Hz), 8.42 s (1H,
13
H1'), 11.65 br.s (1H, OH). C NMR spectrum, δ, ppm:
13.67 (C10), 20.01 (C9), 20.05 (C8), 27.31 (C5), 37.23
(C3), 38.06 (C6), 45.41 (C4), 47.32 (C7), 49.96 (C1), 60.17
(C2), 110.75 (C2'), 118.83 (C4'), 121.59 (C6'), 132.19
(C7'), 133.87 (C5'), 157.59 (C1'), 157.85 (C3'). Found, %:
C 55.46; H 5.99; N 3.76; S 8.75. C17H22BrNOS. Calcu-
lated, %: C 55.43; H 6.02; N 3.80; S 8.71.
2,4-Di-tert-butyl-6-(iminomethyl)phenol. Yield
50%, yellow powder, mp 209–210°C, Rf 0.54 (petroleum
ether–Et2O, 10:1). IR spectrum, ν, cm–1: 1622 (C=N),
(1S,2S,4S,E)-N-(4-Nitrobenzylidene)-1,7,7-tri-
methylbicyclo[2.2.1]heptane-2-sulfenamide (XI). Yield
48%, yellow powder, mp 83–84°C, [α]D22 +117.5°(C 0.14,
acetone), Rf 0.48 (petroleum ether–EtOAc, 10:1). IR
spectrum, ν, cm–1: 1597 (C=N), 1516 (NO2), 1339 (NO2).
1H NMR spectrum, δ, ppm: 0.90 s (6H, C8,9H3), 1.05 s
(3H, C10H3), 1.20–1.33 m (1H, H5-endo), 1.34–1.46 m (1H,
H6-endo), 1.69–1.93 m (4H, H3-exo,4,5-exo,6-exo), 1.95–2.11 m
(1H, H3-endo), 3.64 d.d (1H, H2, J 9.5, 6.1 Hz), 7.76 d (2H,
H3',7', J 8.7 Hz), 8.25 d (2H, 4',6', J 8.7 Hz), 8.48 s (1H,
H1'). 13C NMR spectrum, δ, ppm: 13.78 (C10), 19.99 (C9),
20.06 (C8), 27.41 (C5), 37.43 (C3), 38.05 (C6), 45.49 (C4),
47.22 (C7), 49.93 (C1), 60.62 (C2), 124.00 (C4',6'), 127.16
(C3',7'), 141.77 (C2'), 147.97 (C5'), 151.22 (C1'). Found,
%: C 64.14; H 6.95; N 8.84; S 10.07. C17H22N2O2S.
Calculated, %: C 64.12; H 6.96; N 8.80; S 10.07.
1
1253 (Carom–OH). H NMR spectrum, δ, ppm: 1.37 s
(9H, t-Bu), 1.52 s (9H, t-Bu), 7.21 d (1Harom, J 2.4 Hz),
7.50 d (1Harom, J 2.4 Hz), 8.81 c (1H, CH=N), 11.95 br.s
(1H, OH). 13C NMR spectrum, δ, ppm: 29.47 (3CH3),
31.46 (3CH3), 34.21 [C(CH3)3], 35.16 [C(CH3)3], 116.71
(C–CH=N), 126.98 (CH), 128.24 (CH), 136.91 [C–
C(CH3)3], 141.30 [C–C(CH3)3], 156.88 (C–OH), 165.29
(CH=N). Found, %: C 77.21; H 9.94; N 6.02. C15H23NO.
Calculated, %: C 77.21; H 9.93; N 6.00.
(1S,2S,4S,E)-N-(2-Hydroxy-5-chlorobenzylidene)-
1,7,7-trimethylbicyclo[2.2.1]heptane-2-sulfen-amide
22
(IX). Yield 75%, yellow crystals, mp 80–81°C, [α]D
+87.2° (C 0.14, acetone), Rf 0.41 (petroleum ether–Et2O,
10:1). IR spectrum, ν, cm–1: 1085 (C–Cl), 1273 (Carom
–
(1S,2S,4S,E)-N-(4-Dimethylaminobenzylidene)-
OH), 1591 (C=N). 1H NMR spectrum, δ, ppm: 0.90 s (3H,
C8H3), 0.91 s (3H, C9H3), 1.06 s (3H, C10H3), 1.24–1.40 m
(2H, H5-endo,6-endo), 1.73–1.91 m (4H, H3-exo,4,5-exo,6-exo),
2.03 d.d (1H, H3-endo, J 13.0, 9.6 Hz), 3.53 d.d (1H, H2,
J 9.6, 5.9 Hz), 6.90 d (1H, H4', J 8.7 Hz), 7.12 d (1H, H7',
J 2.6 Hz), 7.22 d.d (1H, H5', J 8.7, 2.6 Hz), 8.43 s (1H,
1,7,7-trimethylbicyclo[2.2.1]heptane-2-sulfenamide
(XII). Yield 39%, yellow powder, mp 79–80°C, [α]D
22
+83.4 (C 0.28, acetone), Rf 0.26 (petroleum ether–Et2O,
10:1). IR spectrum, ν, cm–1: 1579 (C=N), 1177 (C-N).
1H NMR spectrum, δ, ppm: 0.89 s (3H, C8H3), 0.92 s (3H,
C9H3), 1.06 s (3H, C10H3), 1.20–1.49 m (2H, H5-endo,6-
endo), 1.71–1.90 m (4H, H3-exo,4,5-exo,6-exo), 2.04 d.d (1H,
H3-endo, J 13.0, 9.6 Hz), 3.03 s [6H, N(CH3)2], 3.59 d.d
(1H, H2, J 9.5, 6.2 Hz), 6.71 d (2H, H4',6', J 8.7 Hz),
7.52 d (2H, H3',7', J 8.7 Hz), 8.35 s (1H, H1'). 13C NMR
spectrum, δ, ppm: 13.77 (C10), 20.11 (C9,8), 27.47 (C5),
37.7 (C3), 38.08 (C6), 40.27 [N(CH3)2], 45.57 (C4), 47.18
(C7), 49.74 (C1), 59.49 (C2), 111.74 (C4',6'), 125.65 (C5'),
128.25 (C3',7'), 151.40 (C2'), 155.23 (C1'). Found, %:
C 72.15; H 8.87; N 8.90; S 10.08. C19H28N2S. Calculated,
%: C 72.10; H 8.92; N 8.85; S 10.13.
13
H1'), 11.63 br.s (1H, OH). C NMR spectrum, δ, ppm:
13.68 (C10), 20.01 (C9), 20.06 (C8), 27.32 (C5), 37.22
(C3), 38.05 (C6), 45.41 (C4), 47.32 (C7), 49.96 (C1), 60.18
(C2), 118.38 (C4'), 120.98 (C2'), 123.83 (C6'), 129.22
(C7'), 131.04 (C5'), 157.37 (C3'), 157.71 (C1'). Found, %:
C 63.05; H 6.80; N 4.35; S 9.86. C17H22ClNOS. Calcu-
lated, %: C 63.04; H 6.85; N 4.32; S 9.90.
(1S,2S,4S,E)-N-(2-Hydroxy-5-bromobenzylidene)-
1,7,7-trimethylbicyclo[2.2.1]heptane-2-sulfenamide
22
(X). Yield 50%, yellow powder, mp 78–79°C, [α]D
+76.5° (C 0.20, acetone), Rf 0.60 (petroleum ether–Et2O,
Sulfenimines oxidation with tert-butylhydroper-
oxide–VO(acac)2. In a flask equipped with a stirrer
was charged 1 mmol of sulfenimine in 5 ml of CHCl3
and 0.01 mmol (2.7 mg) of VO(acac)2. The mixture
was stirred for 5 min, and a solution of 1 mmol of tert-
10:1). IR spectrum, ν, cm–1: 1587 (C=N), 1273 (Carom
–
OH), 1076 (C–Br). 1H NMR spectrum, δ, ppm: 0.90 s (3H,
C8H3), 0.91 s (3H, C9H3), 1.06 s (3H, C10H3), 1.24–1.43 m
(2H, H5-endo,6-endo), 1.73–1.90 m (4H, H3-exo,4,5-exo,6-exo),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 11 2012

SYNTHESIS AND REDUCTION OF NEW SULFINIMINES
1413
13
butylhydroperoxide in chloroform was slowly added. The
stirring continued for 3–4 h at room temperature. After
the removal of the solvent the reaction products were
isolated by column chromatography on silica gel (eluent
benzene–EtOAc, petroleum ether–EtOAc, CCl4–EtOAc
in various ratios, developer KMnO4).
OHR), 11.94 s (1H, OHS). C NMR spectrum, δ, ppm:
13.86 (C10R,S), 19.77 (C9S,8S), 20.01 (C9R,8R), 26.97 (C5S),
27.24 (C5R), 29.74 (C3R), 31.89 (C3S), 38.86 (C6R), 39.00
(C6S), 44.72 (C4S), 45.02 (C4R), 47.80 (C7S), 47.90 (C7R),
49.91 (C1S,R), 75.13 (C2R), 77.13 (C2S), 111.40 (C6'R,S),
112.04 (C4R,S), 119.94 (C2'R), 120.18 (C2'S), 134.28 (C7'S),
134.34 (C7'R), 139.46 (C5'R,S), 155.89 (C3'R,S), 161.79
(C1'R), 162.60 (C1'S). Found, %: C 44.12; H 4.61; N 2.98;
S 6.90. C17H21Br2NO2S. Calculated, %: C 44.08; H 4.57;
N 3.02; S 6.92.
(R,S)-N-(E)-(2-Hydroxybenzylidene)-{(1S,2S,4S)-
1,7,7-trimethylbicyclo[2.2.1]heptane}-2-sulfin-
amide (XIII), diastereomers mixture.1 Yield 99%
(de 52%), yellow fluid, Rf 0.40 (petroleum ether–
Et2O, 10:1). IR spectrum, ν, cm–1: 1599 (C=N), 1275
(R,S)-N-(E)-(2-Hydroxy-3,5-diiodobenzylidene)-
{(1S,2S,4S)-1,7,7-trimethylbicyclo[2.2.1]heptane}-2-
sulfinamide (XV), diastereomers mixture. Yield 92%
(de 53%), yellow powder, Rf 0.24 (CHCl3). IR spectrum,
ν, cm–1: 3055 (NH), 1585 (C=N), 1088 (S=O), 758 (C-I).
1H NMR spectrum, δ, ppm: 0.95 s (3H, C9RH3), 0.97 s
(3H, C9SH3), 1.08 s (3H, C8RH3), 1.11 s (3H, C8SH3),
1.26 s (6H, C10R,SH3), 1.15–1.40 m (4H, H5R,S-endo;6R,S-endo),
1.49 d.d (1H, H3R-exo, J 13.9, 9.6 Hz), 1.58–1.86 m
(5H, H6R,S-exo;3S-exo;5R,S-exo), 1.86–1.95 m (2H, H4R,S),
2.16–2.25 m (1H, H3S-endo), 2.21–2.34 m (1H, H3R-endo),
2.47 d.d (1H, H2S, J 9.2, 6.5 Hz), 2.84 d.d (1H, H2R, J 9.5,
1
(Carom–OH), 1084 (S=O). H NMR spectrum, δ, ppm:
0.93 c (3H, C9RH3), 0.95 c (3H, C9SH3), 1.09 c (3H,
C8RH3), 1.12 c (3H, C8SH3), 1.25 c (3H, C10RH3), 1.27 s
(3H, C10SH3), 1.10–1.26 m (2H, H5R,S-endo), 1.17–
1.35 m (2H, H6R,S-endo), 1.52 d.d (1H, H3R-exo, J 13.9,
J 9.7 Hz), 1.61–1.87 m (5H, H6R,S-exo;3S-exo;5R,S-exo),
1.79–1.96 m (2H, H4R,S), 2.15–2.28 m (1H, H3S-endo),
2.23–2.38 m (1H, H3R-endo), 2.45 d.d (1H, H2S, J 9.2,
6.4 Hz), 2.81 d.d (1H, H2R, J 9.6, 6.0 Hz), 6.95–7.07 m
(4H, H4'R,S;6'R,S), 7.40–7.52 m (4H, H5'R,S;7'R,S), 8.73 C (2H,
H1'R,S), 11.12 C (1H, OHS), 11.14 C (1H, OHR). 13C NMR
spectrum, δ, ppm: 13.18 (C10R,S), 19.83 (C9S,8S), 20.07
(C9R,8R), 27.02 (C5S), 27.28 (C5R), 29.90 (C3R), 31.88
(C3S), 38.89 (C6R), 39.03 (C6S), 44.75 (C4S), 45.02 (C4R),
47.76 (C7S), 47.87 (C7R), 49.75 (C1S), 49.80 (C1R), 75.26
(C2R), 77.12 (C2S), 117.24 (C4'R,S), 118.26 (C2'R), 118.52
(C2'S), 119.79 (C6'S), 119.84 (C6'R), 133.22 (C5'S,R), 134.54
(C7'S), 134.59 (C7'R), 160.16 (C3'R,S), 163.27 (C1'R), 164.10
(C1'S). Found, %: C 66.83; H 7.61; N 4.53; S 10.47. C17H-
23NO2S. Calculated, %: C 66.85; H 7.59; N 4.59; S 10.50.
6.1 Hz), 7.75 d (2H, H7'R,S, J 1.83 Hz), 8.19 d (2H, H5'R,S
,
J 1.7 Hz), 8.57 s (2H, H1'R,S), 12.09 s (1H, OHR), 12.14 s
(1H, OHS). 13C NMR spectrum, δ, ppm: 13.86 (C10R,S),
19.77 (C9S,8S), 20.04 (C9R,8R), 26.97 (C5S), 27.24 (C5R),
29.58 (C3R), 31.91 (C3S), 38.88 (C6R), 39.00 (C6S), 44.73
(C4S), 45.02 (C4R), 47.89 (C7R,S), 49.93 (C1S,R), 75.05
(C2R), 77.17 (C2S), 81.11 (C4'R,S), 88.70 (C6'R,S), 119.80
(C2'R,S), 141.40 (C7'R,S), 150.55 (C5'R,S), 158.80 (C3'R,S),
161.58 (C1'R), 162.35 (C1'S). Found, %: C 36.69; H 3.78;
N 2.47; S 5.74. C17H21I2NO2S. Calculated, %: C 36.64;
H 3.80; N 2.51; S 5.75.
(R,S)-N-(E)-(2-Hydroxy-3,5-dibromobenzylidene)
{(1S,2S,4S)-1,7,7-trimethylbicyclo[2.2.1]-heptane}-
2-sulfinamide (XIV), diastereomers mixture. Yield
95% (de 52%), yellow powder, Rf 0.47 (CHCl3). IR
spectrum, ν, cm–1: 3067 (NH), 1591 (C=N), 1165 (C-
(R,S)-N-(E)-(2-Hydroxy-3,5-di-tert-butylbenzyl-
id-ene)-{(1S,2S,4S)-1,7,7-trimethylbicyclo-[2.2.1]
heptane}-2-sulfinamide (XVI), diastereomers mixture.
Yield 97% (de 54%), colorless fluid, Rf 0.60 (CHCl3). IR
1
Br), 1088 (S=O). H NMR spectrum, δ, ppm: 0.94 s
(3H, C9RH3), 0.96 s (3H, C9SH3), 1.08 s (3H, C8RH3),
1.11 s (3H, C8SH3), 1.25 s (6H, C10R,SH3), 1.14–1.37 m
(4H, H5R,S-endo;6R,S-endo), 1.50 d.d (1H, H3R-exo, J 13.8,
9.8 Hz), 1.60–1.88 m (5H, H6R,S-exo;3S-exo;5R,S-exo),
1.86–1.95 m (2H, H4R,S), 2.14–2.25 m (1H, H3S-endo),
2.21–2.37 m (1H, H3R-endo), 2.47 d.d (1H, H2S, J 8.9,
6.6 Hz), 2.84 d.d (1H, H2R, J 9.2, 6.2 Hz), 7.56 s (2H,
spectrum, ν, cm–1: 1572 (C=N), 1086 (S=O). H NMR
1
spectrum, δ, ppm: 0.95 s (3H, C9RH3), 0.97 s (3H, C9SH3),
1.11 s (3H, C8RH3), 1.14 s (3H, C8SH3), 1.28 s (3H,
C10RH3), 1.30 s (3H, C10SH3), 1.16–1.36 m (4H, H5R,S-
endo;6R,S-endo), 1.35 s (18H, C13'R,SH3, C14'R,SH3, C15'R,SH3),
1.50 s (18H, C9'R,SH3, C10'R,SH3, C11'R,SH3), 1.46–1.58 m
(1H, H3R-exo), 1.63–1.85 m (5H, H6R,S-exo;3S-exo;5R,S-exo),
1.89 q (2H, H4R,S, J 4.35 Hz), 2.21–2.31 m (1H, H3S-endo),
2.26–2.39 m (1H, H3R-endo), 2.45 d.d (1H, H2S, J 9.2,
6.5 Hz), 2.83 d.d (1H, H2R, J 9.5, 6.1 Hz), 7.33 d (2H,
H7'R,S, J 2.4 Hz), 7.55 d (2H, H5'R,S, J 2.1 Hz), 8.75 s (1H,
H7'R,S), 7.82 s (2H, H5'R,S), 8.64 s (2H, H1'R,S), 11.89 s (1H,
___________
1 Here and hereinafter in the upper index the signals are indicated of
the corresponding atoms of (RS)-diastereomer or (SS)-diastereomer,
or of their mixture.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 11 2012

IZMEST’EV et al.
1414
H1'R), 8.76 s (1H, H1'S), 11.50 s (1H, OHR), 11.54 s (1H,
OHS). 13C NMR spectrum, δ, ppm: 13.94 (C10R,S), 19.86
(C9S,8S), 20.09 (C9R,8R), 27.06 (C5S), 27.33 (C5R), 29.45
(C9'S,R,10'S,R,11'S,R), 29.80 (C3R), 31.41 (C13'S,R,14'S,R,15'S,R),
31.95 (C3S), 34.22 (C8'R,S), 35.16 (C12'R,S), 38.95 (C6R),
39.08 (C6S), 44.78 (C4S), 45.05 (C4R), 47.77 (C7S), 47.83
(C7R), 49.78 (C1S), 49.84 (C1R), 75.35 (C2R), 77.32 (C2S),
117.64 (C2'R), 117.92 (C2'S), 127.93 (C7'R,S), 129.45 (C5'S),
129.51 (C5'R), 137.05 (C4'R,S), 141.47 (C6'R,S), 157.19
(C3'S), 157.27 (C3'R), 164.24 (C1'R), 164.98 (C1'S). Found,
%: C 71.91; H 9.45; N 3.31; S 7.63. C25H39NO2S. Cal-
culated, %: C 71.89; H 9.41; N 3.35; S 7.68.
J 13.9, 9.7 Hz), 1.62–1.89 m (5H, H6R,S-exo;3S-exo;5R,S-exo),
1.81–1.94 m (2H, H4R,S), 2.16–2.26 m (1H, H3S-endo),
2.23–2.37 m (1H, H3R-endo), 2.46 d.d (1H, H2S, J 9.3,
6.4 Hz), 2.83 d.d (1H, H2R, J 9.5, 6.1 Hz), 6.94 d (1H,
H4'S, J 8.8 Hz), 6.95 d (1H, H4'R, J 8.8 Hz), 7.54 d.d
(2H, H5'R,S, J 8.8, 2.2 Hz), 7.58 d (2H, H7'R,S, J 2.0 Hz),
8.67 s (2H, H1'R,S), 11.16 s (1H, OHS), 11.18 s (1H,
OHR). 13C NMR spectrum, δ, ppm: 13.84 (C10R,S), 19.80
(C9S,8S), 20.04 (C9R,8R), 27.00 (C5S), 27.26 (C5R), 29.82
(C3R), 31.86 (C3S), 38.89 (C6R), 39.01 (C6S), 44.75 (C4S),
45.02 (C4R), 47.79 (C7S), 47.88 (C7R), 49.87 (C1S,R), 75.18
(C2R), 77.11 (C2S), 111.38 (C2'S,R), 119.26 (C4'R,S), 119.61
(C6'R,S), 135.06 (C7'S,R), 137.15 (C5'S,R), 159.16 (C3'R,S),
162.22 (C1'R), 163.04 (C1'S). Found, %: C 53.15; H 5.73;
N 3.65; S 8.36. C17H22BrNO2S. Calculated, %: C 53.13;
H 5.77; N 3.64; S 8.34.
(R,S)-N-(E)-(2-Hydroxy-5-chlorobenzylidene)-
{(1S,2S,4S)-1,7,7-trimethylbicyclo[2.2.1]heptane}-
2-sulfinamide (XVII), diastereomers mixture.
Yield 99% (de 55%), white powder, Rf 0.42 (petro-
leum ether–Et2O, 10:1). IR spectrum, ν, cm–1: 1599
(C=N), 1273 (Carom–OH), 1182 (C–Cl), 1084 (S=O).
1H NMR spectrum, δ, ppm: 0.95 s (3H, C9RH3), 0.97 s
(3H, C9SH3), 1.09 s (3H, C8RH3), 1.12 s (3H, C8SH3),
1.25 s (3H, C10RH3), 1.28 s (3H, C10SH3), 1.16–1.36 m
(4H, H5R,S-endo;6R,S-endo), 1.52 d.d (1H, H3R-exo, J 13.9,
9.6 Hz), 1.64–1.88 m (5H, H6R,S-эq;3S-exo;5R,S-exo),
1.87–1.94 m (2H, H4R,S), 2.16–2.27 m (1H, H3S-endo),
2.22–2.36 m (1H, H3R-endo), 2.46 d.d (1H, H2S, J 9.2,
6.5 Hz), 2.83 d.d (1H, H2R, J 9.5, 6.1 Hz), 6.99 d (1H, H4'S,
(R,1S,2S,4S,E)-N-(4-Nitrobenzylidene)-1,7,7-
trimethylbicyclo[2.2.1]heptane-2-sulfinamide,
22
(
RS)-XIX. Yellow crystals, mp 132–133°C, [α]D
+77.8° (C 0.26, acetone), Rf 0.45 (CHCl3–EtOAc, 5:1).
IR spectrum, ν, cm–1: 1589 (C=N), 1522 (NO2), 1346
(NO2), 1078 (S=O). 1H NMR spectrum, δ, ppm: 0.94 s
(3H, C9H3), 1.09 s (3H, C8H3), 1.12–1.26 m (1H, H5-
endo), 1.19–1.36 m (1H, H6-endo), 1.28 s (3H, C10H3),
1.48 d.d (1H, H3-exo, J 13.8, 9.7 Hz), 1.64–1.79 m (1H,
H6-exo), 1.71–1.84 m (1H, H5-exo), 1.83–1.93 m (1H,
H4), 2.23–2.36 m (1H, H3-endo), 2.86 d.d (1H, H2, J 9.5,
J 8.7 Hz), 7.00 d (1H, H4'R, J 8.7 Hz), 7.40 d.d (2H, H5'R,S
,
6.1 Hz), 8.04 d (2H, H3',7', J 8.7 Hz), 8.35 d (2H, H4',6'
,
J 8.8, 2.4 Hz), 7.44 d (2H, H7'R,S, J 2.3 Hz), 8.67 s (2H,
H1'R,S), 11.14 s (1H, OHS), 11.15 s (1H, OHR). 13C NMR
spectrum, δ, ppm: 13.84 (C10R,S), 19.80 (C9S,8S), 20.03
(C9R,8R), 27.00 (C5S), 27.25 (C5R), 29.84 (C3R), 31.85
(C3S), 38.89 (C6R), 39.00 (C6S), 44.75 (C4S), 45.02 (C4R),
47.79 (C7S), 47.88 (C7R), 49.86 (C1S,R), 75.18 (C2R), 77.09
(C2S), 118.86 (C4'R,S), 118.98 (C2'S,R), 124.57 (C6'R,S),
132.04 (C7'S,R), 134.35 (C5'S,R), 158.69 (C3'R,S), 162.30
(C1'R), 163.13 (C1'S). Found, %: C 60.10; H 6.49; N 3.10;
S 9.45. C17H22ClNO2S. Calculated, %: C 60.07; H 6.52;
N 4.12; S 9.43.
J 8.7 Hz), 8.70 s (1H, H1'). 13C NMR spectrum, δ, ppm:
14.07 (C10), 20.02 (C9), 20.06 (C8), 27.32 (C5), 29.84
(C3), 38.93 (C6), 45.15 (C4), 47.81 (C7), 49.84 (C1), 74.34
(C2), 124.18 (C4',6'), 130.07 (C3',7'), 139.04 (C5'), 149.79
(C2'), 158.40 (C1'). Found, %: C 61.07; H 6.61; N 8.42;
S 9.54. C17H22N2O3S. Calculated, %: C 61.05; H 6.63;
N 8.38; S 9.59.
(R,S)-(1S,2S,4S,E)-N-(4-Nitrobenzylidene)-1,7,7-
trimethylbicyclo[2.2.1]heptane-2-sulfinamide (XIX),
diastereomers mixture. Yield 85% (de 53%), yellow
crystals, Rf 0.45 (CHCl3–EtOAc, 5:1). IR spectrum, ν,
cm–1: 1589 (C=N), 1522 (NO2), 1345 (NO2), 1079 (S=O).
1H NMR spectrum, δ, ppm: 0.94 s (3H, C9RH3), 0.97 s
(3H, C9SH3), 1.09 s (3H, C8RH3), 1.15 s (3H, C8SH3),
1.12–1.26 m (2H, H5R,S-endo), 1.19–1.36 m (2H, H6R,S-endo),
(R,S)-N-(E)-(2-Hydroxy-5-dibromobenzylidene)-
{(1S,2S,4S)-1,7,7-trimethylbicyclo[2.2.1]heptane}-
2-sulfinamide (XVIII), diastereomers mixture.
Yield 98% (de 52%), white powder, Rf 0.40 (petro-
leum ether–Et2O, 10:1). IR spectrum, ν, cm–1: 1597
(C=N), 1273 (Carom–OH), 1180 (C–Br), 1084 (S=O).
1H NMR spectrum, δ, ppm: 0.95 s (3H, C9RH3), 0.97 s
(3H, C9SH3), 1.10 s (3H, C8RH3), 1.13 s (3H, C8SH3),
1.25 s (3H, C10RH3), 1.28 s (3H, C10SH3), 1.16–
1.28 s (6H, C10R,SH3), 1.48 d.d (1H, H3R-exo
, J 13.8, 9.6 Hz),
1.65–1.88 m (5H, H6R,S-exo;3S-exo;5R,S-exo), 1.82–1.93 m
(2H, H4S,R), 2.23–2.51 m (3H, H2S;3R,S-endo), 2.86 d.d (1H,
H2R, J 9.5, 6.1 Hz), 8.04 d (2H, H3'S,7'S, J 8.8 Hz), 8.05 d
(2H, H4'R,6R', J 8.8 Hz), 8.71 s (1H, H1'R), 8.73 s (1H,
1.36 m (4H, H5R,S-endo;6R,S-endo), 1.52 d.d (1H, H3R-exo
,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 11 2012

SYNTHESIS AND REDUCTION OF NEW SULFINIMINES
1415
H1'S). 13C NMR spectrum, δ, ppm, S-isomer: 13.97 (C10),
19.81 (C9,8), 27.11 (C5), 32.55 (C3), 38.98 (C6), 44.81 (C4),
47.83 (C7), 49.85 (C1), 77.33 (C2), 124.19 (C4',6'), 130.05
(C3',7'), 139.04 (C5'), 149.79 (C2'), 159.39 (C1'). Found, %:
C 61.10; H 6.62; N 8.40; S 9.56. C17H22N2O3S. Calculated,
%: C 61.05; H 6.63; N 8.38; S 9.59.
(3H, C10H3), 1.16–1.26 m (1H, H5-endo), 1.27–1.41 m (1H,
H6-endo), 1.60–1.70 (1H, H3-endo), 1.64–1.75 (1H, H6-exo),
1.72–1.84 m (2H, H4,5-exo), 1.86–1.97 m (1H, H3-exo),
2.78 d.d (1H, H2, J 9.1, 6.4 Hz), 4.01 d.d (1H, H1A', J 13.4,
2.9 Hz), 4.10 br.d (1H, NH, J 6.5 Hz), 4.44 d.d (1H, H1C',
J 13.3, 6.9 Hz), 6.86 t (1H, H6', J 7.3 Hz), 6.95 d (1H,
H4', J 8.1 Hz), 7.15 d (1H, H7', J 7.4 Hz), 7.25 t (1H, H5',
J 7.7 Hz), 8.55 br.s (1H, OH). 13C NMR spectrum, δ, ppm:
13.84 (C10), 19.89 (C8,9), 27.21 (C5), 33.29 (C3), 39.02
(C6), 40.81 (C1'), 44.86 (C4), 47.69 (C7), 49.08 (C1), 73.64
(C2), 118.07 (C4'), 120.02 (C6'), 123.92 (C2'), 120.10 (C5'),
130.31 (C7'), 155.70 (C3'). Found, %: C 66.43; H 8.19;
N 4.59; S 10.42. C17H25NO2S. Calculated, %: C 66.41;
H 8.20; N 4.56; S 10.43.
(R,S)-(1S,2S,4S,E)-N-(4-Dimethylaminobenzyl-
idene)-1,7,7-trimethylbicyclo[2.2.1]heptane-2-sul-
finamide (XX), diastereomers mixture. Yield 94%
(de 54%), yellow oily fluid, Rf 0.48 (CHCl3–EtOAc,
5 : 1). IR spectrum, ν, cm–1: 1581 (C=N), 1074 (S=O).
1H NMR spectrum, δ, ppm: 0.93 s (3H, C9RH3), 0.95 s (3H,
C9SH3), 1.10 s (3H, C8RH3), 1.13 s (3H, C8SH3), 1.26 s (3H,
C10RH3), 1.28 s (3H, C10SH3), 1.14–1.25 m (2H, H5R,S-endo),
1.19–1.35 m (2H, H6R,S-endo), 1.50 d.d (1H, H3R-exo
,
(R)-N-(2-Hydroxybenzyl){(1S,2S,4S)-1,7,7-
trimethylbicyclo[2.2.1]heptane}-2-sulfinamide,
(RS)-XXI. Yield 61% calculated on stereoisomers mixture
J 13.8, 9.7 Hz), 1.66 t.d (2H, H6R,S-exo, J 11.6, 4.1 Hz),
1.64–1.73 m (1H, H3S-exo), 1.69–1.78 m (2H, H5R,S-exo),
1,86 d.d (2H, H4R,S, J 9.0, 4.6 Hz), 2.23–2.41 m (3H,
H3S,R-endo;2S), 2.75 d.d (1H, H2R, J 9.7, 6.1 Hz), 3.09 s (12H,
C8'S,RH3, C9'S,RH3), 6.72 d (2H, H4'S,6'S, J 9.7 Hz), 6.73 d.d
(2H, H4'R,6'R, J 9.7 Hz), 7.70–7.79 m (4H, H3'R,S;7'R,S),
8.48 s (1H, H1'R), 8.50 s (1H, H1'S). 13C NMR spectrum,
δ, ppm: 13.94 (C10S), 14.21 (C10R), 19.93 (C9S,8S), 20.11
(C9R), 20.14 (C8R), 27.21 (C5S), 27.41 (C5R), 29.91 (C3R),
32.55 (C3S), 39.06 (C6R,S), 40.11 (C8'R,S;9'R,S), 44.91 (C4S),
45.18 (C4R), 47.69 (C7S), 49.65 (C7R), 49.65 (C1S,R), 75.05
(C2R), 77.64 (C2S), 111.42 (C4'R,S;6'R,S), 122.52 (C2'R),
122.74 (C2'S), 131.22 (C3'R,S;7'R,S), 153.02 (C5'S,R), 159.51
(C1'R), 160.49 (C1'S). Found, %: C 68.64; H 8.52; N 8.39;
S 9.63. C19H28ClNO2S. Calculated, %: C 68.63; H 8.49;
N 8.42; S 9.64.
22
XIII, colorless powder, mp 157–158°C, [α]D +145.2°
(C 0.12, acetone), Rf 0.32 (EtOAc–CHCl3, 5:3). IR
spectrum, ν, cm–1: 3150 (NH), 1275 (Carom–OH), 1015
(S=O). 1H NMR spectrum, δ, ppm: 0.90 s (3H, C9H3),
0.98 s (3H, C8H3), 1.02 s (3H, C10H3), 1.13–1.31 m (2H,
H5-endo,6-endo), 1.53–1.69 (2H, H3-endo,6-exo), 1.73–1.83 m
(1H, H5-exo), 1.79–1.90 m (1H, H4), 2.29 d.d.d (1H, H3-
exo, J 13.8, 3.9, 3.8 Hz), 2.81 d.d (1H, H2, J 9.7, 5.7 Hz),
4.25–4.46 m (3H, H1A',1C', NH), 6.85 t (1H, H6', J 7.4 Hz),
6.91 d (1H, H4', J 7.9 Hz), 7.25 t (2H, H5',7', J 7.7 Hz),
13
8.66 br.s (1H, OH). C NMR spectrum, δ, ppm: 13.53
(C10), 19.83 (C9), 20.01 (C8), 27.38 (C5), 31.69 (C3), 38.86
(C6), 43.65 (C1'), 45.00 (C4), 47.81 (C7), 49.35 (C1), 71.97
(C2), 116.86 (C4'), 119.88 (C6'), 124.17 (C2'), 129.63 (C5'),
130.12 (C7'), 155.63 (C3'). Found, %: C 66.42; H 8.23;
N 4.58; S 10.39. C17H25NO2S. Calculated, %: C 66.41;
H 8.20; N 4.56; S 10.43.
N-Substituted sulfinamides XXI–XXVIII. To a so-
lution of 1 mmol of an appropriate sulfinimine in 20 ml
of anhydrous THF cooled to –48°C was carefully added
3 mmol (0.11 g) of LiAlH4. The mixture was stirred for
10–20 min, the solution was filtered in a vacuum, the
filtrate was washed with 5 ml of water, the product was
extracted into EtOAc (3 × 10 ml), the combined extract
was dried with Na2SO4, the solvent was removed in a
vacuum, the reaction products were isolated by column
chromatography on silica gel (eluent EtOAc).
(S)-N-(2-Hydroxy-3,5-dibromobenzyl){(1S,2S,4S)-
1,7,7-trimethylbicyclo[2.2.1]heptane}-2-sulfinamide,
(SS)-XXII. Yield 14% calculated on diastereomers mix-
ture XIV, yellow powder, mp 174–175°C, [α]D22 +85.6°
(C 0.15, acetone), Rf 0.45 (EtOAc–CHCl3, 1:1). IR spec-
trum, ν, cm–1: 3271 (NH), 1305 (Carom–OH), 1147 (C–Br),
1
1053 (S=O). H NMR spectrum, δ, ppm: 0.91 s (3H,
C9H3), 0.92 s (3H, C8H3), 1.17 s (3H, C10H3), 1.17–1.27 m
(1H, H5-endo), 1.29–1.41 m (1H, H6-endo), 1.59–1.68 (1H,
H3-endo), 1.65–1.74 m (1H, H6-exo), 1.75–1.85 m (1H,
H5-exo), 1.74–1.83 m (1H, H4), 1.82–1.95 m (1H, H3-exo),
2.76 d.d (1H, H2, J 9.3, 6.1 Hz), 4.00 d.d (1H, H1A', J 14.0,
2.6 Hz), 4.08 br.d (1H, NH, J 7.0 Hz), 4.38 d.d (1H, H1C',
J 13.9, 7.1 Hz), 7.27 d (1H, H7', J 2.4 Hz), 7.64 d (1H,
(S)-N-(2-Hydroxybenzyl){(1S,2S,4S)-1,7,7-
trimethylbicyclo[2.2.1]heptane}-2-sulfinamide,
(SS)-XXI. Yield 18% calculated on diastereomers mixture
22
XIII, colorless powder, mp 167–168°C, [α]D +133.6°
(C 0.12, acetone), Rf 0.41 (EtOAc–CHCl3, 5:3). IR spec-
trum, ν, cm–1: 3275 (NH), 1261 (Carom–OH), 1040 (S=O).
1H NMR spectrum, δ, ppm: 0.92 s (6H, C8,9H3), 1.20 s
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 11 2012

IZMEST’EV et al.
1416
H5', J 2.4 Hz), 8.73 br.s (1H, OH). 13C NMR spectrum, C 36.51; H 4.15; N 2.50; S 5.73.
δ, ppm: 13.79 (C10), 19.88 (C9,8), 27.20 (C5), 33.19 (C3),
(R)-N-(2-Hydroxy-3,5-diiodobenzyl){(1S,2S,4S)-
39.06 (C6), 40.51 (C1'), 44.85 (C4), 47.69 (C7), 49.16 (C1),
73.66 (C2), 111.85 (C4'), 113.43 (C6'), 127.27 (C2'), 132.12
(C7'), 135.18 (C5'), 151.40 (C3'). Found, %: C 43.92;
H 4.97; N 2.98; S 6.90. C17H23Br2NO2S. Calculated, %:
C 43.89; H 4.98; N 3.01; S 6.89.
1,7,7-trimethylbicyclo[2.2.1]heptane}-2-sulfin-amide,
(RS)-XXIII. Yield 53% calculated on diastereo-
mers mixture XV, colorless powder, mp 137–138°C
22
(decomp), [α]D +13.0° (C 0.20, acetone), Rf 0.45
(CHCl3–EtOAc, 1:1). IR spectrum, ν, cm–1: 3207
(R)-N-(2-Hydroxy-3,5-dibromobenzyl){(1S,2S,4S)-
1,7,7-trimethylbicyclo[2.2.1]heptane}-2-sulfinamide,
(RS)-XXII. Yield 51% calculated on diastereomers mix-
ture XIV, yellow powder, mp 177–178°C, [α]D22 +18.0°
(C 0.18, acetone), Rf 0.38 (EtOAc–CHCl3, 1:1). IR spec-
trum, ν, cm–1: 3197 (NH), 1298 (Carom–OH), 1142 (C–Br),
(NH), 1288 (Carom–OH), 1038 (S=O), 760 (C–I), 662
1
(C–I). H NMR spectrum, δ, ppm: 0.90 s (3H, C9H3),
0.96 s (3H, C8H3), 1.05 s (3H, C10H3), 1.16–1.40 m
(2H, H5-endo,6-endo), 1.55–1.63 (1H, H3-endo), 1.59–1.72
(1H, H6-exo), 1.72–1.86 m (1H, H5-exo), 1.83–1.91 m
(1H, H4), 2.21–2.34 m (1H, H3-exo), 2.81 d.d (1H, H2,
J 9.7, 5.7 Hz), 4.01 br.d (1H, NH, J 2.7 Hz), 4.12 d.d
(1H, H1A', J 14.1, 3.2 Hz), 4.32 d.d (1H, H1C', J 14.1,
6.8 Hz), 7.47 d (1H, H7', J 7.5 Hz), 8.01 d (1H, H5',
J 1.8 Hz), 8.71 s (1H, OH). 13C NMR spectrum, δ, ppm:
13.49 (C10), 19.79 (C9), 19.92 (C8), 27.37 (C5), 31.43 (C3),
38.97 (C6), 42.01 (C1') 45.02 (C4), 47.82 (C7), 49.47 (C1),
71.50 (C2), 82.34 (C4'), 89.22 (C6'), 126.67 (C2'), 139.13
(C7'), 146.57 (C5'), 154.51 (C3'). Found, %: C 36.50;
H 4.13; N 2.53; S 5.69. C17H23I2NO2S. Calculated, %:
C 36.51; H 4.15; N 2.50; S 5.73.
1
1020 (S=O). H NMR spectrum (CDCl3 + DMSO), δ,
ppm: 0.69 c (3H, C9H3), 0.76 c (3H, C8H3), 0.82 c (3H,
C10H3), 0.94–1.18 m (2H, H5-endo,6-endo), 1.31–1.47 (1H,
H3-endo), 1.38–1.52 m (1H, H6-exo), 1.53–1.68 m (1H,
H5-exo), 1.59–1.72 m (1H, H4), 1.96–2.14 m (1H, H3-exo),
2.68 d.d (1H, H2, J 9.6, 5.8 Hz), 3.99 d.d (1H, H1A', J 14.6,
4.9 Hz), 4.09 d.d (1H, H1C', J 13.9, 6.9 Hz), 5.16 t (1H,
NH, J 5.5 Hz), 7.17 d (1H, H7', J 4.9 Hz), 7.64 d (1H,
H5', J 2.5 Hz), 8.92 br.s (1H, OH). 13C NMR spectrum,
δ, ppm: 13.34 (C10), 19.68 (C9), 19.84 (C8), 27.26 (C5),
31.45 (C3), 38.69 (C6), 41.92 (C1'), 44.87 (C4), 47.58 (C7),
49.13 (C1), 0.83 (C2), 111.46 (C4'), 112.77 (C6'), 128.76
(C2'), 131.92 (C7'), 134.22 (C5'), 151.31 (C3'). Found, %:
C 43.91; H 5.02; N 2.97; S 6.92. C17H23Br2NO2S. Cal-
culated, %: C 43.89; H 4.98; N 3.01; S 6.89.
(S)-N-(2-Hydroxy-3,5-di-tert-butylbenzyl)-
{(1S,2S,4S)-1,7,7-trimethylbicyclo[2.2.1]heptane}-2-
sulfinamide, (SS)-XXIV. Yield 12% calculated on dia-
stereomers mixture XVI, colorless glass-like substance,
22
mp 42–43°C, [α]D +83.5° (C 0.37, acetone), Rf 0.50
(C6H6–CHCl3–Et2O, 3:3:1). IR spectrum, ν, cm–1: 3219
(NH), 1229 (Carom–OH), 1036 (S=O). 1H NMR spectrum
(CDCl3), δ, ppm: 0.92 s (3H, C9H3), 0.93 s (3H, C8H3),
1.20 s (3H, C10H3), 1.17–1.25 m (1H, H5-endo), 1.33 s
(9H, C13',14',15'H3), 1.30–1.41 m (1H, H6-endo), 1.46 s (9H,
C9',10',11'H3), 1.62–1.72 (2H, H3-endo), 1.66–1.76 m (1H,
H6-exo), 1.76–1.87 m (2H, H5-exo,4), 1.88–2.00 m (1H, H3-
exo), 2.80 d.d (1H, H2, J 9.4, 6.2 Hz), 3.88 br.d (1H, NH,
J 6.9 Hz), 3.99 d.d (1H, H1A', J 13.4, 2.1 Hz), 4.46 d.d (1H,
H1C', J 13.4, 7.6 Hz), 7.04 d (1H, H7', J 2.4 Hz), 7.36 d
(1H, H5', J 2.3 Hz), 8.17 br.s (1H, OH). 13C NMR spec-
trum, δ, ppm: 13.80 (C10), 19.90 (C9,8), 27.20 (C5), 29.79
(C9',10',11'), 31.62 (C13',14',15'), 33.21 (C3), 34.23 (C12'),
35.23 (C8'), 39.01 (C6), 40.98 (C1'), 44.89 (C4), 47.69 (C7),
49.08 (C1), 73.54 (C2), 123.62 (C2'), 124.66 (C5'), 124.95
(C7'), 138.14 (C4'), 141.92 (C6'), 152.09 (C3'). Found, %:
C 71.59; H 9.79; N 3.37; S 7.60. C25H41NO2S. Calculated,
%: C 71.55; H 9.85; N 3.34; S 7.64.
(S)-N-(2-Hydroxy-3,5-diiodobenzyl){(1S,2S,4S)-
1,7,7-trimethylbicyclo[2.2.1]heptane}-2-sulfin-amide,
(SS)-XXIII. Yield 10% calculated on diastereomers
mixture XV, colorless powder, mp 119–120°C (decomp),
[α]D22 +77.8° (C 0.26, acetone), Rf 0.48 (CHCl3–EtOAc,
1:1). IR spectrum, ν, cm–1: 3319 (NH), 1284 (Carom–OH),
1
1035 (S=O), 728 (C–I), 660 (C–I). H NMR spectrum,
δ, ppm: 0.90 s (3H, C9H3), 0.92 s (3H, C8H3), 1.16 s
(3H, C10H3), 1.16–1.26 m (1H, H5-endo), 1.27–1.40 m
(1H, H6-endo), 1.59–1.68 (1H, H3-endo), 1.64–1.74 (1H,
H6-exo), 1.73–1.86 m (1H, H5-exo), 1.74–1.85 m (1H, H4),
1.82–1.94 m (1H, H3-exo), 2.76 d.d (1H, H2, J 9.2, 6.1 Hz),
3.93 d (1H, H1A', J 13.9 Hz), 4.17 br.d (1H, NH, J 5.5 Hz),
4.36 d.d (1H, H1C', J 13.9, 7.0 Hz), 7.42 s (1H, H7'), 8.01 s
(1H, H5'), 9.35 br.s (1H, OH). 13C NMR spectrum, δ, ppm:
13.78 (C10), 19.87 (C9), 19.93 (C8), 27.19 (C5), 33.17 (C3),
39.03 (C6), 40.30 (C1'), 44.85 (C4), 47.72 (C7), 49.14 (C1),
73.52 (C2), 82.10 (C4'), 89.47 (C6'), 126.59 (C2'), 139.12
(C7'), 146.78 (C5'), 154.76 (C3'). Found, %: C 36.53;
H 4.18; N 2.47; S 5.76. C17H23I2NO2S. Calculated, %:
(R)-N-(2-Hydroxy-3,5-di-tert-butylbenzyl)-
{(1S,2S,4S)-1,7,7-trimethylbicyclo[2.2.1]heptane}-2-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 11 2012

SYNTHESIS AND REDUCTION OF NEW SULFINIMINES
1417
sulfinamide, (RS)-XXIV. Yield 48% calculated on dia-
stereomers mixture XVI, colorless glass-like substance,
mp 63–64°C, [α]D +17.5° (C 0.12, acetone), Rf 0.35
ν, cm–1: 3144 (NH), 1277 (Carom–OH), 1072 (C–Cl), 1010
1
(S=O). H NMR spectrum, δ, ppm: 0.90 c (3H, C9H3),
22
0.97 s (3H, C8H3), 1.03 s (3H, C10H3), 1.16–1.33 m
(2H, H5-endo,6-endo), 1.54–1.64 (1H, H3-endo), 1.64–1.73
(1H, H6-exo), 1.74–1.83 m (1H, H5-exo), 1.87 t (1H, H4,
J 4.0 Hz), 2.20–2.33 m (1H, H3-exo), 2.80 d.d (1H, H2,
J 9.8, 5.7 Hz), 4.13–4.32 m (2H, H1A', NH), 4.36 t (1H,
H1C', J 5.7 Hz), 6.79 d (1H, H4', J 8.6 Hz), 7.11 d.d (1H,
H7', J 8.5, 2.5 Hz), 7.15 d (1H, H5', J 2.4 Hz), 8.96 br.s
(1H, OH). 13C NMR spectrum, δ, ppm: 13.57 (C10), 19.79
(C9), 19.98 (C8), 27.37 (C5), 31.74 (C3), 38.87 (C6), 43.51
(C1'), 44.96 (C4), 47.83 (C7), 49.40 (C1), 72.27 (C2),
118.31 (C4'), 124.22 (C6'), 125.79 (C2'), 129.32 (C7'),
129.60 (C5'), 154.25 (C3'). Found, %: C 59.74; H 7.03;
N 4.12; S 9.41. C17H24ClNO2S. Calculated, %: C 59.72;
H 7.08; N 4.10; S 9.38.
(C6H6–CHCl3–Et2O, 3:3:1). IR spectrum, ν, cm–1: 3194
(NH), 1227 (Carom–OH), 1036 (S=O). 1H NMR spectrum,
δ, ppm: 0.91 s (3H, C9H3), 0.98 s (3H, C8H3), 1.09 s
(3H, C10H3), 1.12–1.28 m (2H, H5-endo,6-endo), 1.33 s (9H,
C13',14',15'H3), 1.46 s (9H, C9',10',11'H3), 1.54–1.73 (2H, H3-
endo,6-exo), 1.81 d.d.d (1H, H5-exo, J 15.7, 8.1, 3.8 Hz), 1.88 t
(1H, H4, J 4.2 Hz), 2.22–2.38 m (1H, H3-exo), 2.85 d.d
(1H, H2, J 9.7, 5.7 Hz), 3.91 br.d (1H, NH, J 4.9 Hz),
4.20 d.d (1H, H1A', J 13.3, 2.2 Hz), 4.39 d.d (1H, H1C',
J 13.3, 7.2 Hz), 7.06 d (1H, H7', J 2.2 Hz), 7.36 d (1H,
H5', J 2.2 Hz), 7.85 s (1H, OH). 13C NMR spectrum, δ,
ppm: 13.56 (C10), 19.82 (C9), 19.95 (C8), 27.39 (C5),
29.81 (C9',10',11'), 31.42 (C3), 31.62 (C13',14',15'), 34.26
(C12'), 35.19 (C8'), 38.95 (C6), 42.91 (C1'), 45.04 (C4),
47.79 (C7), 49.38 (C1), 71.26 (C2), 123.49 (C2'), 124.96
(C7'), 124.55 (C5'), 138.00 (C4'), 142.14 (C6'), 152.14 (C3').
Found, %: C 71.53; H 9.81; N 3.31; S 7.62. C25H41NO2S.
Calculated, %: C 71.55; H 9.85; N 3.34; S 7.64.
(S)-N-(2-Hydroxy-5-bromobenzyl){(1S,2S,4S)-
1,7,7-trimethylbicyclo[2.2.1]heptane}-2-sulfinamide,
(SS)-XXVI. Yield 16% calculated on diastereomers
22
mixture XVIII, white powder, mp 172–173°C, [α]D
+99.8° (C 0.14, acetone), Rf 0.40 (EtOAc–CCl4, 5 : 1).
IR spectrum, ν, cm–1: 3296 (NH), 1279 (Carom–OH),
(S)-N-(2-Hydroxy-5-chlorobenzyl){(1S,2S,4S)-
1,7,7-trimethylbicyclo[2.2.1]heptane}-2-sulfinamide,
(SS)-XXV. Yield 17% calculated on diastereomers
1
1098 (S=O). H NMR spectrum (CDCl3 + CD3OD),
δ, ppm: 0.86 s (3H, C9H3), 0.87 s (3H, C8H3), 1.12 s
(3H, C10H3), 1.10–1.21 m (1H, H5-endo), 1.23–1.36 m
(1H, H6-endo), 1.53–1.65 (1H, H3-endo), 1.60–1.71 m (1H,
H6-exo), 1.70–1.83 m (2H, H4,5-exo), 1.79–1.91 m (1H,
H3-exo), 2.72 d.d (H, H2, J 9.5, 6.2 Hz), 2.75–2.84 br.s
(1H, NH), 3.98 d (1H, H1A', J 13.8 Hz), 4.25 d (1H, H1C',
J 13.9 Hz), 6.74 d (1H, H4', J 8.3 Hz), 7.19–7.32 m (2H,
H5',7'), 8.97 br.s (1H, OH). 13C NMR spectrum, δ, ppm:
13.76 (C10), 19.78 (C9), 19.82 (C8), 27.14 (C5), 33.26 (C3),
39.00 (C6), 40.82 (C1'), 44.79 (C4), 47.63 (C7), 48.99 (C1),
73.45 (C2), 111.53 (C6'), 118.73 (C4'), 126.44 (C2'), 132.15
(C7'), 132.46 (C5'), 154.48 (C3'). Found, %: C 52.83;
H 6.29; N 3.61; S 8.32. C17H24BrNO2S. Calculated, %:
C 52.85; H 6.26; N 3.63; S 8.30.
22
mixture XVII, colorless fluid, [α]D +61.6° (C 0.10,
acetone), Rf 0.23 (C6H6–Et2O, 1:1). IR spectrum, ν,
cm–1: 3178 (NH), 1275 (Carom–OH), 1072 (C–Cl), 1035
1
(S=O). H NMR spectrum, δ, ppm: 0.91 s (3H, C9H3),
0.93 s (3H, C8H3), 1.19 s (3H, C10H3), 1.16–1.25 m
(1H, H5-endo), 1.29–1.42 m (1H, H6-endo), 1.60–1.71
(1H, H3-endo), 1.66–1.77 (1H, H6-exo), 1.75–1.86 m
(1H, H5-exo), 1.76–1.85 m (1H, H4), 1.85–1.98 m (1H,
H3-exo), 2.78 d.d (1H, H2, J 9.4, 6.2 Hz), 3.93 d.d (1H,
H1A', J 13.6, 2.4 Hz), 4.03 br.d (1H, NH, J 5.9 Hz),
4.36 d.d (1H, H1C', J 13.6, 7.0 Hz), 6.89 d (1H, H4',
J 8.6 Hz), 7.13 d (1H, H7', J 2.6 Hz), 7.20 d.d (1H, H5',
J 8.6, 2.6 Hz), 8.74 br.s (1H, OH). 13C NMR spectrum,
δ, ppm: 13.81 (C10), 19.88 (C8,9), 27.20 (C5), 33.28 (C3),
39.02 (C6), 40.23 (C1'), 44.85 (C4), 47.70 (C7), 49.13 (C1),
72.76 (C2), 119.79 (C4'), 124.48 (C6'), 125.52 (C2'), 129.88
(C7'), 129.96 (C5'), 154.33 (C3'). Found, %: C 59.76;
H 6.99; N 4.13; S 9.36. C17H24NO2SCl. Calculated, %:
C 59.72; H 7.08; N 4.10; S 9.38.
(R)-N-(2-Hydroxy-5-bromobenzyl){(1S,2S,4S)-
1,7,7-trimethylbicyclo[2.2.1]heptane}-2-sulfinamide,
(RS)-XXVI. Yield 54% calculated on diastereomers mix-
22
ture XVIII, colorless powder, mp 157–158°C, [α]D
+
57.7° (C 0.12, acetone), Rf 0.31 (EtOAc–CCl4, 5:1). IR
spectrum, ν, cm–1: 3140 (NH), 1277 (Carom–OH), 1013
1
(S=O). H NMR spectrum, δ, ppm: 0.91 s (3H, C9H3),
(R)-N-(2-Hydroxy-5-chlorobenzyl){(1S,2S,4S)-
1,7,7-trimethylbicyclo[2.2.1]heptane}-2-sulfinamide,
(RS)-XXV. Yield 59% calculated on diastereomers mix-
ture XVII, white powder, mp 153–154°C, [α]D22 +35.5°
(C 0.20, acetone), Rf 0.18 (C6H6–Et2O, 1:1). IR spectrum,
0.98 s (3H, C8H3), 1.03 s (3H, C10H3), 1.15–1.33 m (2H,
H5-endo,6-endo), 1.54–1.64 (1H, H3-endo), 1.59–1.71 m (1H,
H6-exo), 1.74–1.85 m (1H, H5-exo), 1.79–1.92 m (1H, H4),
2.20–2.34 m (1H, H3-exo), 2.80 d.d (1H, H2, J 9.8, 5.7 Hz),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 11 2012

IZMEST’EV et al.
1418
4.11–4.34 m (3H, H1A',1C', NH), 6.75 d (1H, H4', J 8.4 Hz),
7.25 d (1H, H7', J 2.4 Hz), 7.28 t (1H, H5', J 2.0 Hz),
8.93 br.s (1H, OH). C NMR spectrum, δ, ppm: 13.55
(C10), 19.79 (C9), 19.97 (C8), 27.37 (C5), 31.69 (C3), 38.90
(C6), 43.17 (C1'), 44.97 (C4), 47.83 (C7), 49.42 (C1), 72.19
(C2), 111.48 (C6'), 119.09 (C4'), 126.27 (C2'), 132.41 (C7'),
132.54 (C5'), 154.81 (C3'). Found, %: C 52.86; H 6.28;
N 3.65; S 8.33. C17H24BrNO2S. Calculated, %: C 52.85;
H 6.26; N 3.63; S 8.30.
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ACKNOWLEDGMENTS
The study was carried out under the financial support
of the Russian Foundation for Basic Research (grant
nos. 10-03-00969 and 12-03-31338 mol.-a) and of Ural
Division of RussianAcademy of Sciences (12-U-3-1015).
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 11 2012