New N-substituted sulfinamides of neomenthane series

Article abstract of DOI:10.1007/s11172-013-0343-3

A reaction of neomenthanethiol with ammonia and N-chlorosuccinimide with subsequent addition of aromatic aldehydes leads to chiral N- arylideneneomenthylsulfenimines, whose oxidation at the sulfur atom gives N-arylideneneomenthylsulfinimines. The reactions of N- arylideneneomenthylsulfinimines with lithium aluminum hydride or Grignard reagents proceed at the imine fragment and lead to the corresponding N-benzylneomenthylsulfinamides.

Full text of DOI:10.1007/s11172-013-0343-3

Russian Chemical Bulletin, International Edition, Vol. 62, No. 11, pp. 2367—2376, November, 2013
2367
New Nꢀsubstituted sulfinamides of neomenthane series*
E. S. Izmest´ev,a D. V. Sudarikov,a S. A. Rubtsova,a P. A. Slepukhin,b and A. V. Kutchina
aInstitute of Chemistry, Komi Scientific Center of the Ural Branch of the Russian Academy of Sciences,
48 ul. Pervomaiskaya, 167982 Syktyvkar, Russian Federation.
Fax: +7 (821 2) 21 84 77. Eꢀmail: izmestevꢀes@chemi.komisc.ru
bI. Ya. Postovsky Institute of Organic Synthesis, Ural Branch of the Russian Academy of Sciences,
22 ul. S. Kovalevskoi, 620041 Ekaterinburg, Russian Federation
A reaction of neomenthanethiol with ammonia and Nꢀchlorosuccinimide with subsequent
addition of aromatic aldehydes leads to chiral Nꢀarylideneneomenthylsulfenimines, whose
oxidation at the sulfur atom gives Nꢀarylideneneomenthylsulfinimines. The reactions of
Nꢀarylideneneomenthylsulfinimines with lithium aluminum hydride or Grignard reagents proꢀ
ceed at the imine fragment and lead to the corresponding Nꢀbenzylneomenthylsulfinamides.
Key words: (+)ꢀneomenthanethiol, sulfenimines, sulfinimines, sulfinamides, Grignard
reaction.
Application of terpene substrates in the asymmetric
synthesis of chiral nitrogenꢀcontaining compounds is studꢀ
ied first of all due to the practical importance of target
compounds. Analysis of the market of modern pharmaꢀ
ceutical agents shows that majority of such compounds
are amines, frequently of synthetic origin, which are used
in medicine for treatment of the Alzheimer´s disease
(Rivastigmin),1 tuberculosis (Etambutol),2 diabetes (Reꢀ
paglinid),3 etc. Compounds containing, besides amino
group, a sulfoxide fragment exhibit good antibacterial acꢀ
tivity (Sparzomicin, Sparoxomicin).4,5 The use of terpeꢀ
nes as the source of chirality allows one to develop
new directed methods for the preparation of chiral
sulfinylꢀcontaining amines with a desired configuraꢀ
tion of stereocenters. One of such approaches is based
on chemical transformation of terpene sulfinimines,
which possess high stability to moisture and light
due to the presence of additional resonance stabilization
of the double bond by the sulfinyl group, that also increasꢀ
es their reactivity.6 In addition, the sulfinyl group itself
is a good chiral inductor, allowing one to accomplish
asymmetric transformations of the nearby prochiral
centers of the substrate. That is why development of conꢀ
venient methods for the synthesis of chiral sulfinimines, as
well as their chemical transformations for the preparation
of aminoꢀcontaining compounds deserves attention of reꢀ
searchers.
derived sulfinimines using neomenthylsulfinamide as a preꢀ
cursor was also described.8
In the present work, we suggest to use chiral neomenꢀ
thanethiol as a starting compound for the preparation of
a series of diastereomerically pure Sꢀ and Nꢀcontaining comꢀ
pounds, viz., sulfenimines, sulfinimines, and Nꢀsubstitutꢀ
ed sulfinamides.
In the first step of our work, we accomplished the
synthesis of a series of sulfenimines by the reaction of
neomenthanethiol 1 with aromatic aldehydes in liquid
ammonia in the presence of Nꢀchlorosuccinimide (NCS).
An unstable neomenthylsulfenamide 2 formed initially furꢀ
ther undergoes condensation with a carbonyl compounds
(Scheme 1).
Salicylaldehyde and its derivatives, as well as benzꢀ
aldehyde, have been chosen as the carbonyl compounds.
The choice of salicylaldehyde derivatives was justified by
the fact that a simultaneous presence of the OH and the
imino groups on the molecule allows one to use the saliꢀ
cylimines obtained as ligands in the complexation with
dꢀmetals, whereas the benzaldehyde derivative are known to
give good crystals, which is important for the determinaꢀ
tion of absolute configuration.
Thus, we obtained optically active neomenthylsulfenꢀ
imines 3 and 4 in from 32 to 85% yields. The yields of
sulfenimines 3b and 4b in the reactions with aldehydes
containing electronꢀdonating substituents were lower,
whereas electronꢀwithdrawing substituents in the moleꢀ
cule of aldehyde increase their reactivity and, therefore,
the yields of the target sulfenimines.
Earlier, we have already reported the synthesis of new
sulfen/sulfinimines and Nꢀsubstituted sulfinamides based
on isobornanethiol.7 The preparation of neomenthaneꢀ
The structures of sulfenimines obtained were estabꢀ
lished by NMR and IR spectroscopy and confirmed by
elemental analysis data. The NMR spectra of sulfenimines
* Dedicated to Academician of the Russian Academy of Sciences
M. P. Egorov on the occasion of his 60th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2367—2376, Novemer, 2013.
1066ꢀ5285/13/6211ꢀ2367 © 2013 Springer Science+Business Media, Inc.

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Russ.Chem.Bull., Int.Ed., Vol. 62, No. 11, November, 2013
Izmest´ev et al.
Scheme 1
3: R1 = R2 = H (a), But (b), R1 = H, R2 = Br (c); 4: R3 = NO2 (a), NMe2 (b)
3 and 4 exhibit signals characteristic of the CH group at
the CH=N double bond (in the 1H NMR spectrum, as a
singlet at  8.4—8.7, in the 13C NMR spectrum, as a sepaꢀ
rate signal in the lowꢀfield region of  152—162). In the
1H NMR spectra of sulfenimines 3, the signals for the
proton of the OH group are present at  11.6—12.6.
rated to the individual stereoisomers by column chromatoꢀ
graphy.
As oxidants, we used MCPBA and a catalytic system
based on tertꢀbutyl hydroperoxide (TBHP—VO(acac)2).
The use of MCPBA as the oxidant allowed us to syntheꢀ
size sulfinimines 5 and 6 in from 84 to 86% yields and de
16—18% with the predominance of (R)ꢀdiastereomer in
the mixture. The system TBHP—VO(acac)2 oxidized comꢀ
pounds 3 and 4 to sulfinimines 5 and 6 in 80—82% yields
and de 25—26% also with the predominance in the mixꢀ
ture of (R)ꢀisomer (Scheme 2).
The structures of sulfinimines were confirmed by NMR
and IR spectroscopy, whereas their composition was deꢀ
termined by elemental analysis. The absolute configuraꢀ
tion was established by Xꢀray diffraction analysis.
The presence of principal functional groups in the molꢀ
ecules of sulfenimines 3 and 4 was confirmed by IR
spectroscopy. The IR spectra exhibit absorption bands
characteristic of the stretching vibrations of the C=N
bond in the range of frequencies of 1564—1608 cm–1 and
sharp, strong absorption bands of the CAr—OH group at
1249—1276 cm–1
.
All the sulfenimines synthesized were oxidized to
the corresponding sulfinyl derivatives, which were sepaꢀ
Scheme 2
5, 7: R1 = R2 = H (a), R1 = R2 = But (b), R1 = H, R2 = Br (c); 6,8: R3 = NO2 (a), NMe2 (b)

Neomenthane sulfinamides
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 11, November, 2013 2369
The 13C NMR spectra of (R)ꢀ and (S)ꢀdiastereomeric
sulfinimines, the chemical shifts of the signals for the carꢀ
bon atoms belonging to the benzene ring are virtually inꢀ
distinguishable, whereas chemical shifts of the signals for
the carbon atoms of the neomenthane fragment signifiꢀ
cantly differ. This is due to the fact that the S=O group is
bonded directly to the cyclohexane ring of the neoꢀ
menthane fragment, and the change of configuration of
the sulfur atom affects the change of molecular currents
only within this fragment. In the 1H NMR spectra of comꢀ
pounds 5 and 6, the signals for the protons of the CH
group at the CH=N double bond are found as singlets in
the range  8.4—8.7. The signals for the protons of the OH
group in sulfinimines 5 are observed in the region of
 11.0—12.0.
According to the Xꢀray diffraction data, compounds
(R)ꢀ6a and (S)ꢀ6a crystallize in the chiral space group of
symmetry of the orthorhombic and monoclinic system,
respectively. Generally, the molecules are characterized
by close values for the bond distances and bond angles.
The general view of the molecules and the atom numberꢀ
ing system used in the Xꢀray experiment are given
in Fig. 1. The error of the determination of the absoꢀ
lute structural parameter did not allow us with certainꢀ
ty to determine the absolute configuration of the comꢀ
pounds based on the effect of the anomalous scattering,
however, the information on the configuration of the neoꢀ
menthane fragment allows us to draw an unambiguous
conclusion.8
The presence of the S=O group in the structure of
sulfinimines 5 and 6 was confirmed by IR spectroscopy
based on the presence of the strong characteristic bands of
the stretching vibrations in the region of 1070—1091 cm–1
.
A considerable "doubleꢀbond" character of this group is
also confirmed by the Xꢀray diffraction data, which show
that the average S—O bond distance is 1.48(1) Å, which is
significantly shorter than a typical value for the single
bond between these elements.
Depending on conditions, reduction of sulfinimines
can proceed at any of the C=Nꢀ, S—Nꢀ, or S=O groups.
Sulfinimines 5 and 6 were reduced after their separation to
the individual diastereomers. Reduction of neomenthylꢀ
sulfinimines 5a,b and 6a,b at the bond C=N required
5—10 min at –48 C and did not involve other functional
groups. The yields of sulfinamides 7a,b and 8a,b lie within
75—95%. Reduction of sulfinimine 5c was not undertaken.
The structures of Nꢀsubstituted sulfinamides 7 and 8
were confirmed by NMR and IR spectroscopy, their comꢀ
position was determined by elemental analysis. In their
13C NMR spectra, unlike in those for the corresponding
sulfinimines, the signals for carbon atom C(1´) disappear,
whereas the signals for the carbon atom of the CH2 group
appears in the highꢀfield region of  40—50. The protons
1
of the CH2 group in the H NMR spectra of salicylaldeꢀ
hyde derivatives 7a,b are found as a doublet of doublets in
the range  3.8—4.6, whereas in the spectra of the benzꢀ
aldehyde derivatives 8a,b, as a multiplet centered at  4.2.
The signals for the protons of the NH group are found in the
region  3—5. The IR spectra of compounds 7 and 8 exꢀ
hibit strong absorption band of the stretching vibrations of
the NH group in the range of frequencies 3100—3300 cm–1.
The presence of the S=O group was confirmed by the presꢀ
ence of absorption bands in the region of 1030—1090 cm–1.
To find out a possibility of the asymmetric synthesis of
Nꢀsubstituted sulfinamides with an additional chiral cenꢀ
ter on the carbon atom at ꢀposition to the amino group,
we used (1S,2S,5R,E)ꢀNꢀ(5ꢀbromoꢀ2ꢀhydroxybenzylꢀ
idene)ꢀ2ꢀisopropylꢀ5ꢀmethylcyclohexanesulfenamide (5c)
synthesized by us earlier.
C(14)
a
C(12)
C(11)
C(10)
C(13)
O(2)
C(6)
C(5)
C(4)
N(2)
C(7)
S(1)
N(1)
C(8)
C(1)
C(9)
O(3)
C(2)
C(15)
C(17)
C(3)
O(1)
The chiral ꢀbranched Nꢀsulfinamides 9 were obtained
based on the diastereomerically pure compounds (R)ꢀ5c
and (S)ꢀ5c through the nucleophilic addition of the Grigꢀ
nard reagents at the C=N double bond (Scheme 3, Table 1).
The syntheses were carried out at room temperature
in CH2Cl2.
It was found that the diastereoselectivity of addition
depends on the type of the Grignard reagent and increases
with the increase in the size of substituent R. The highest
diastereoselectivity of addition was achieved when PhMgBr
was used (de 53%), however, the presence of two similar in
size substituents at the chiral center C(1´) makes difficult
the separation by column chromatography.9 We found that
the more different in size are substituents at C(1´), the stronꢀ
ger diastereomers differ in their chromatographic mobility.
C(16)
C(17)
b
O(1)
S(1)
C(9)
C(10)
C(8)
C(11)
C(7)
C(1)
C(6)
C(5)
C(12)
C(2)
N(1)
O(3)
N(2)
C(13)
C(3)
C(4)
O(2)
C(14)
C(16)
C(15)
Fig. 1. General view of molecules (SS)ꢀ6a (a) and (RS)ꢀ6a (b)
according to the Xꢀray diffraction data (p = 50%).

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Russ.Chem.Bull., Int.Ed., Vol. 62, No. 11, November, 2013
Izmest´ev et al.
Scheme 3
Table 1. Addition of Grignard reagents to imines 3c and 5c
Subꢀ
strate
Grignard Yield of de (%)
Predominant
diastereomer*
reagent
9 (%)
(S)ꢀ5с PhMgBr
(R)ꢀ5с EtMgBr
(S)ꢀ5с EtMgBr
(R)ꢀ5с MeMgI
(S)ꢀ5с MeMgI
90
76
92
72
84
74
53
48
36
7
5
0
Not determined
(RSS)ꢀ9c
(SSS)ꢀ9c
(RSS)ꢀ9b
(SSS)ꢀ9b
–
3с
EtMgBr
* Compound 9a was obtained as a mixture of two unseparaꢀ
ble diastereomers.
in the region of 1000—1033 cm–1 and the NH groups in
the region of 3145—3292 cm–1
.
In the 13C NMR spectra of compounds 9b,c, unlike in
those of the starting sulfinimines, the signals for the carbon
atom of the C(1´)H group are shifted upfield ( 55—65).
In the spectra of compounds (RS)ꢀ9b and (SS)ꢀ9b, an adꢀ
ditional signal for the carbon atom of the Me group apꢀ
pears at  10—22, whereas in the spectra of compounds
(RS)ꢀ9c and (SS)ꢀ9c, yet another additional signal for the
carbon atom of the CH2 group appears at  30. In the
1H NMR spectra of compounds 9b and 9c, a multiplet in
the region of  4—5 belongs to the proton at atom C(1´)
and the signals at 3.0—5.5 are attributable to the proton of
the NH group. The signals for the protons of the CH2
group in compounds (RS)ꢀ9c and (SS)ꢀ9c at  1.5—2.0 are
found as multiplets overlapping with the signals for the
protons of the neomenthane fragment.
9: R = Ph (a), Me (b), Et (c)
Addition of EtMgBr to compounds 3c and 5c was takꢀ
en as an example to study the effect of chiral induction of
the S=O group on diastereoselectivity. Thus, in the case of
sulfinimine 5c, the reaction proceeds with high diastereoꢀ
selectivity (de 36—45%, see Table 1), whereas such addiꢀ
tion of EtMgBr to sulfenimine 3c proceeds nonselectively
(de 0%) with the formation of a mixture of diastereomers
10a and 10b in the ratio 1 : 1 (Scheme 4). This fact also
indicates the absence of the effect of chiral induction of
the terpene fragment on the addition of EtMgBr to 3c,
apparently, because of its remoteness from the C=N group.
An unambiguous assignment of the absolute configuꢀ
ration for all the chiral centers by Xꢀray diffraction analysis
was successful only for compounds (RSS)ꢀ9b and (SSR)ꢀ9c.
The general view of the molecules and the atom numberꢀ
ing system in the structural experiment are given in Fig. 2.
The absolute configuration of other diastereomers was deꢀ
termined by a comparison of chemical shifts for the carbon
atoms in their 13C NMR spectra with chemical shifts of
compounds, in which the configuration of the chiral cenꢀ
ters was known.
Scheme 4
In conclusion, in the present work, we for the first time
synthesized sulfenimines with the neomenthane fragment
and carried out their oxidation at the sulfur atom. Based
on the neomenthylsulfinimines, a series of Nꢀsubstituted
sulfinamides was obtained through the reduction of the
C=N double bond and through the addition of the Grigꢀ
nard reagents at the named bond. The presence of the
chiral induction of the terpene fragment does not affect
diastereoselectivity of the addition of Grignard reagents to
sulfenimines because of its remoteness from the reaction
center, whereas the addition of the Grignard reagents to
sulfinimines proceeds under the stereocontrol of only the
sulfinyl group. The presence of the chiral induction from
the side of the terpene fragment allowed us to carry out
The structures of compounds obtained were estabꢀ
lished by NMR and IR spectroscopy and Xꢀray diffraction
analysis, their composition was determined by elemental
analysis.
The IR spectroscopy data confirm the presence of the
S=O and NH groups in Nꢀsulfinamines: the IR spectra
exhibit bands of the stretching vibrations of the S=O groups

Neomenthane sulfinamides
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 11, November, 2013 2371
sured at 295(2) K on a Xcalibur 3 (OXFORD DIFFRACTION)
automatic fourꢀcircle diffractometer with a CCDꢀdetector acꢀ
cording to the standard procedure10 using the ꢀ2ꢀscan mode
with a 1 step on a monochromic MoꢀK irradiation.
The structures were solved by direct statistic method and
refined by the fullꢀmatrix least squares method on F2 in anisotroꢀ
pic approximation for all the nonhydrogen atoms. Hydrogen
atoms were placed in the geometrically calculated positions and
refined in isotropic approximation. All the calculations were perꢀ
formed using the SHELXꢀ97 software.11 Parameters of the difꢀ
fraction experiment for the crystals of compound (SS)ꢀ6a were
described earlier.8 Crystallographic data and parameters of
Xꢀray diffraction experiment for compounds (RS)ꢀ6a, (RSS)ꢀ9b,
and (SSR)ꢀ9c are given in Table 2.
a
C(18)
C(10)
O(1)
C(8)
S(1)
C(11)
O(2)
C(9)
C(12)
C(7)
C(2)
N(1)
C(14)
C(1)
C(17)
C(13)
C(6)
C(15)
C(3)
C(4)
C(5)
C(16)
Br(1)
Br(1)
The results of the Xꢀray diffraction experiments were depꢀ
osited with the Cambridge Crystallographic Data Center (CCDC
964915—964917). These data are available free of charge at
www.ccdc.cam.ac.uk/data_request/cif.
(1S,2S,5R)ꢀ2ꢀIsopropylꢀ5ꢀmethylcyclohexanethiol (1) was
synthesized according to the known procedure.8
b
C(16)
C(12)
C(7)
C(8)
C(11)
C(6)
C(13)
Synthesis of neomenthylsulfenimines 3 and 4. The reagent
NCS (0.266 g, 2 mmol) was carefully added to liquid ammonia
(15—20 mL) at –(35—40) C, the mixture was stirred for 5 min,
followed by addition of a solution of neomenthanethiol (0.170 g,
1 mmol) in anhydrous THF (3 mL). After stirring for 10—15 min,
CH2Cl2 (3 mL) was added, and the mixture was warmedꢀup to
room temperature. After evaporation of ammonia, an aldehyde
(2 mmol) in anhydrous THF (3 mL) was added to the mixture,
and it was stirred for 12 h. Then, the reaction mixture was filꢀ
tered under reduced pressure, the solvent was evaporated. The
product was isolated by column chromatography on silica gel,
using eluent CHCl3 or CHCl3 with addition of some Et2O.
(1S,2S,5R,E)ꢀNꢀ(2ꢀHydroxybenzylidene)ꢀ2ꢀisopropylꢀ5ꢀmeꢀ
thylcyclohexanesulfenamide (3a). Yellow oily liquid. The yield
C(5)
C(10)
C(9)
C(3)
C(2)
C(4)
O(2)
N(1)
S(1)
C(14)
C(19)
C(15)
C(1)
C(17)
O(1)
C(18)
Fig. 2. General view of molecules (RSS)ꢀ9b (a) and (SSR)ꢀ9c (b)
according to the Xꢀray diffraction data (p = 50%).
a quantitative separation of all the diastereomers described
in the present work.
22
was 79%, Rf 0.65 (CHCl3), []D +74.3 (c 0.14, acetone).
Found (%): C, 70.10; H, 8.67; N, 4.80; S, 10.98. C17H25NOS.
Experimental
Calculated (%): C, 70.06; H, 8.65; N, 4.81; S, 11.00. IR, /cm–1
:
1273 (CAr—OH), 1593 (C=N). 1H NMR (CDCl3), : 0.95, 1.05
(both d, 3 H each, C(7)H3, C(9)H3, J = 6.5 Hz); 0.86—1.14
(m, 2 H, H(3a), H(4a)); 0.97 (d, 3 H, C(10)H3, J = 6.8 Hz);
1.24—1.34 (m, 1 H, H(2)); 1.32—1.50 (m, 2 H, H(5), H(6a));
1.51—1.73 (m, 1 H, H(8)); 1.73—1.93 (m, 2 H, H(3e), H(4e));
2.32 (ddt, 1 H, H(6e), J = 13.6 Hz, J = 3.1 Hz, J = 2.8 Hz);
3.94—4.02 (n.m,* 1 H, H(1)); 6.87—7.01 (m, 2 H, H(4´), H(6´));
7.17 (dd, 1 H, H(7´), J = 7.6 Hz, J = 1.5 Hz); 8.58 (td, 1 H,
H(5´), J = 7.8 Hz, J = 1.8 Hz); 8.62 (s, 1 H, H(1´)); 11.63 (s, 1 H,
OH). 13C NMR, : 20.82 (C(9)), 21.13 (C(10)), 22.17 (C(7)),
26.96 (C(3)), 27.10 (C(5)), 30.30 (C(8)), 45.19 (C(4)), 40.46
(C(6)), 48.07 (C(2), 53.50 (C(1)), 116.89 (C(4´)), 119.18 (C(6´),
120.31 (C(2´)), 130.21 (C(7´)), 131.37 (C(5´)), 158.91 (C(3´)),
160.34 (C(1´)).
(1S,2S,5R,E)ꢀNꢀ(3,5ꢀDiꢀtertꢀbutylꢀ2ꢀhydroxybenzylidene)ꢀ
2ꢀisopropylꢀ5ꢀmethylcyclohexanesulfenamide (3b). Yellow oily
liquid, the yield was 33%, []D22 +81.1 (c 0.11, acetone), Rf 0.66
(CHCl3). Found (%): C, 74.35; H, 10.22; N, 3.50; S, 7.98.
C25H41NOS. Calculated (%): C, 74.39; H, 10.24; N, 3.47; S, 7.94.
IR, /cm–1: 1269 (CAr—OH), 1564 (C=N). 1H NMR (CDCl3),
: 0.95 (d, 3 H, C(7)H3, J = 6.2 Hz); 0.87—1.13 (m, 2 H,
H(3a), H(4a)); 0.97, 1.06 (both d, 3 H each, C(9)H3, C(10)H3,
IR spectra were recorded on a Shimadzu IR Prestige 21 IR
Fourierꢀtransform spectrometer for neat samples or in KBr pelꢀ
lets. Melting points were determined on a GallencampꢀSanyo
apparatus. 1H and 13C NMR spectra were recorded on a Bruker
Avanceꢀ300 spectrometer (300.17 MHz (1H) and 75.48 MHz
(13C)) in CDCl3, using residual signals of the solvent as a referꢀ
ence. The full assignment of the signals in the 1H and 13C NMR
1
spectra of were made using 2D homoꢀ (1H—1H COSY, H—1H
NOESY) and heteronuclear (1H—13C HSQC, HMBC) experiꢀ
ments. Diastereomeric excess was calculated from the 1H NMR
data based on the ratio of the integral intensities of the signals for
the hydrogen atoms of the C(2)HS group. Angles of optical rotaꢀ
tion were measured on a P3002RS automatic digital polarimeter
(Kruss). Thinꢀlayer chromatography was performed on Sorbfil
plates, using solvent systems based on CHCl3, AcOEt, Et2O,
benzene, and light petroleum; spots of substances were visualꢀ
ized by a solution of phosphomolybdic acid in ethanol or KMnO4
in water. Elemental analysis was performed on an EA 1110
CHNSꢀO automatized analyzer. Freshly distilled solvents were
used for all the reactions. Column chromatography was perꢀ
formed on Alfa Aesar silica gel (0.06—0.2 mm), using similar
solvent systems as in thinꢀlayer chromatography (see below).
Xꢀray diffraction studies. Parameters of the unit cell and the set
experimental reflections in the diffraction experiments were meaꢀ
* Here and further n.m stands for narrowed multiplet.

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Izmest´ev et al.
Table 2. Crystallographic data and parameters of Xꢀray diffraction experiment for compounds (RS)ꢀ6a, (RSS)ꢀ9b,
and (SSR)ꢀ9c
Parameter
(RS)ꢀ6a
(RSS)ꢀ9b
(SSR)ꢀ9c
Molecular formula
Molecular weight
Crystal system
Space group
a/Å
b/Å
c/Å
/deg
C17H24N2O3S
336.45
Monoclinic
P21
8.0703(8)
6.6709(5)
16.9647(15)
90
C18H28BrNO2S
402.39
C19H30BrNO2S
416.42
Orthorhombic
P212121
9.3905(8)
9.7713(4)
21.8416(15)
90
Tetragonal
P41212
12.2950(6)
12.2950(6)
26.3545(13)
90
/deg
103.572(8)
90
887.81(14)
2
1.259
0.198
90
90
90
90
2873
4
1.380
2.166
/deg
3
V/Å
3983.9(3)
8
1.342
Z
dcalc/g cm–3
/mm–1
2.177
 range of data collection/deg
Number of measured reflections
Rint
Number of independent reflections
Number of reflections with I  2(I)
Number of refined parameters
R1 (I  2(I))
3.13 <  < 28.29
4926
3.81 <  < 26.38
12211
2.80 <  < 28.29
11616
0.0193
3885
2382
212
0.0319
0.0537
0.0598
0.0558
0.0525
4059
2025
219
0.0338
0.0326
0.0893
0.0343
0.0525
4853
2873
221
0.0290
0.0351
0.0620
0.0361
1.002
wR2 (I  2(I))
R1 (on all the reflections)
wR2 (on all the reflections)
S
1.006
0.946
Residual electron
density (min/max)/e Å
–0.188/0.155
–0.43/40.383
–0.369/0.439
–3
J = 6.5 Hz); 1.22—1.34 (m, 1 H, H(2)); 1.33 (s, 9 H, C(13´)H3,
C(14´)H3, C(15´)H3)); 1.33—1.49 (m, 2 H, H(5), H(6a)); 1.48
(s, 9 H, C(9´)H3, C(10´)H3, C(11´)H3)); 1.55—1.69 (m, 1 H,
H(8); 1.73—1.95 (m, 2 H, H(3e), H(4e)); 2.28 (ddt, 1 H, H(6e),
J = 13.5 Hz, J = 2.3 Hz, J = 2.2 Hz); 3.97—4.06 (n.m, 1 H,
H(1)); 7.01 (d, 1 H, H(7´), J = 2.1 Hz); 7.37 (d, 1 H, H(5´),
J = 2.0 Hz); 8.64 (s, 1 H, H(1´)); 11.98 (s, 1 H, OH). 13C NMR,
: 20.86 (C(9)), 21.15 (C(10)), 22.19 (C(7)), 26.95 (C(3)), 27.06
(C(5)), 29.46 (C(9´), C(10´), C(11´)), 30.28 (C(8)), 31.49
(C(13´), C(14´), C(15´)), 34.15 (C(12´)), 35.04 (C(8´)), 35.24
(C(4)), 40.49 (C(6)), 48.13 (C(2)), 53.09 (C(1)), 119.56 (C(2´)),
125.11 (C(7´)), 126.21 (C(5´)), 136.57 (C(4´)), 140.63 (C(6´)),
155.90 (C(3´)), 162.27 (C(1´)).
(C(10)), 22.14 (C(7)), 26.95 (C(3)), 27.11 (C(5)), 30.29 (C(8)),
35.13 (C(4)), 40.41 (C(6)), 48.02 (C(2)), 53.68 (C(1)), 110.76
(C(2´)), 118.82 (C(4´)), 121.65 (C(6´)), 132.24 (C(7´)), 133.90
(C(5´)), 157.90 (C(3´)), 159.04 (C(1´)).
(1S,2S,5R,E)ꢀNꢀ(4ꢀNitrobenzylidene)ꢀ2ꢀisopropylꢀ5ꢀmethylꢀ
cyclohexanesulfenamide (4a). Yellow oily liquid, the yield was
22
85%, []D +65.5 (c 0.20, acetone), Rf 0.51 (light petroꢀ
leum—Et2O, 10 : 1). Found (%): C, 63.75; H, 7.50; N, 8.72;
S, 10.00. C17H24N2O2S. Calculated (%): C, 63.72; H, 7.55;
N, 8.74; S, 10.01. IR, /cm–1: 1342 (NO2), 1517 (NO2), 1597
1
(C=N). H NMR (CDCl3), : 0.94, 1.06 (both d, 3 H each,
C(7)H3, C(9)H3, J = 6.5 Hz); 0.92—1.08 (m, 1 H, H(4a)); 0.97
(d, 3 H, C(10)H3, J = 6.8 Hz); 1.13 (qd, 1 H, H(3a), J = 12.5 Hz,
J = 2.7 Hz); 1.32 (ddt, 1 H, H(2), J = 12.8 Hz, J = 10.0 Hz,
J = 3.0 Hz); 1.37—1.51 (m, 1 H, H(6a)); 1.55—1.72 (m, 1 H,
H(8)); 1.72—1.93 (m, 3 H, H(3e), H(4e), H(5)); 2.32 (ddt, 1 H,
H(6e), J = 13.3 Hz, J = 2.3 Hz, J = 2.8 Hz); 4.02—4.13 (n.m,
1 H, H(1)); 7.76 (d, 2 H, H(3´), H(7´), J = 8.7 Hz); 8.26 (d, 2 H,
H(4´), H(6´), J = 8.7 Hz); 8.58 (s, 1 H, H(1´)). 13C NMR,
: 20.83 (C(9)), 21.13 (C(10)), 22.29 (C(7)), 26.92 (C(3)), 27.43
(C(5)), 30.19 (C(8)), 45.20 (C(4)), 40.83 (C(6)), 48.25 (C(2)),
53.97 (C(1)), 124.02 (C(4´), C(6´)), 127.15 (C(3´), C(7´)), 141.83
(C(5´)), 147.99 (C(2´)), 152.59 (C(1´)).
(1S,2S,5R,E)ꢀNꢀ(5ꢀBromoꢀ2ꢀhydroxybenzylidene)ꢀ2ꢀisoproꢀ
pylꢀ5ꢀmethylcyclohexanesulfenamide (3c). Yellow oily liquid, the
yield was 69%, []D22 +49.5 (c 0.29, acetone), Rf 0.65 (CHCl3).
Found (%): C, 55.10; H, 6.55; N, 3.70; S, 8.67. C19H30BrN2S.
Calculated (%): C, 55.13; H, 6.53; N, 3.78; S, 8.66. IR, /cm–1
:
1077 (C—Br), 1271 (CAr—OH), 1587 (C=N). 1H NMR (CDCl3),
: 0.95, 0.97, 1.04 (all d, 3 H each, C(7)H3, C(10)H3, C(9)H3,
J = 6.6 Hz); 0.87—1.15 (m, 2 H, H(3a), H(4a)); 1.23—1.48
(m, 3 H, H(2), H(5), H(6a)); 1.53—1.71 (m, 1 H, H(8)); 1.73—1.92
(m, 2 H, H(3e), H(4e)); 2.24 (ddt, 1 H, H(6e), J = 13.3 Hz,
J = 2.5 Hz, J = 2.3 Hz); 3.93—4.03 (n.m, 1 H, H(1)); 6.86
(d, 1 H, H(4´), J = 8.8 Hz); 7.28 (d, 1 H, H(7´), J = 2.4 Hz);
7.36 (dd, 1 H, H(5´), J = 8.8 Hz, J = 2.4 Hz); 8.53 (s, 1 H,
H(1´)); 11.61 (s, 1 H, OH). 13C NMR, : 20.79 (C(9)), 21.10
(1S,2S,5R,E)ꢀNꢀ(4ꢀDimethylaminobenzylidene)ꢀ2ꢀisopropylꢀ
5ꢀmethylcyclohexanesulfenamide (4b). Yellow oily liquid, the yield
was 32%, []D22 +50.3 (c 0.18, acetone), Rf 0.61 (CCl4—AcOEt,
20 : 1). Found (%): C, 71.66; H, 9.47; N, 8.73; S, 10.14.

Neomenthane sulfinamides
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 11, November, 2013 2373
C19H30N2S. Calculated (%): C, 71.64; H, 9.49; N, 8.79; S, 10.07.
IR, /cm–1: 1175 (C—N), 1581 (C=N). 1H NMR (CDCl3),
: 0.93, 1.08 (both d, 3 H each, C(7)H3, C(9)H3, J = 6.6 Hz);
0.87—1.01 (m, 1 H, H(4a)); 0.95 (d, 3 H, C(10)H3, J = 6.9 Hz);
1.10—1.44 (m, 3 H, H(2), H(3a), H(6a)); 1.59—1.73 (m, 1 H,
H(8)); 1.72—1.90 (m, 3 H, H(3e), H(4e), H(5)); 2.35 (ddt, 1 H,
H(6e), J = 13.6 Hz, J = 2.9 Hz, J = 2.7 Hz); 3.03 (s, 6 H, C(8´),
C(9´)); 3.97—4.05 (n.m, 1 H, H(1)); 6.70 (d, 2 H, H(4´), H(6´)),
J = 8.7 Hz); 7.52 (d, 1 H, H(3´), H(7´), J = 8.8 Hz); 8.42 (s, 1 H,
H(1´)). 13C NMR, : 21.01 (C(9)), 21.23 (C(10)), 22.41 (C(7)),
26.86 (C(3)), 27.38 (C(5)), 30.15 (C(8)), 35.40 (C(4)), 40.28
(C(8´), C(9´)), 40.90 (C(6)), 48.52 (C(2)), 52.65 (C(1)), 111.73
(C(4´), C(6´)), 125.79 (C(2´)), 128.23 (C(3´), C(7´)), 156.32
(C(5´)), 156.32 (C(1´)).
Oxidation of sulfenimines using the system TBHP—VO(acac)2
(general procedure). Sulfenimine (1 mmol) in CHCl3 (5 mL) and
VO(acac)2 (2.7 mg, 0.01 mmol) were placed into a flask equipped
with a stirrer. The mixture was stirred for 5 min, followed by
a slow addition of a solution of TBHP (1 mmol) in CHCl3. After
stirring for 3—4 h at room temperature, the solvent was evapoꢀ
rated in vacuo, the reaction products were isolated by column
chromatography on silica gel, visualizing with KMnO4.
Oxidation of sulfenimines using MCPBA was performed simꢀ
ilarly, the solvent CHCl3, the reaction time 3 h, an equimolar
amount of the oxidant was used. After the reaction was comꢀ
plete, the mixture was workedꢀup with NH4HCO3, stirred for
10 min, and filtered. The solvent was evaporated in vacuo, the
product was isolated by column chromatography. The yields of
sulfinimines were 80—86%, de 16—26%.
1.81—2.04 (m, 2 H, H(3e), H(4e)); 2.02—2.25 (m, 3 H, H(6e),
H(5), H(8)); 3.24—3.34 (n.m, 1 H, H(1)); 7.37 (d, 1 H, H(7´),
J = 2.1 Hz); 7.56 (d, 1 H, H(5´), J = 2.1 Hz); 8.74 (s, 1 H, H(1´));
11.43 (s, 1 H, OH). 13C NMR, : 21.50 (C(9)), 21.68 (C(10)),
22.82 (C(7)), 26.26 (C(3)), 27.91 (C(5)), 29.44 (C(9´, C(10´),
C(11´)), 29.89 (C(8)), 31.41 (C(13´), C(14´), C(15´)), 33.21
(C(6), C(12´)), 34.26 (C(8´)), 35.15 (C(4)), 47.28 (C(2)), 62.49
(C(1)), 117.77 (C(2´)), 127.86 (C(7´)), 129.52 (C(5´)), 137.09
(C(4´)), 141.46 (C(6´)), 157.25 (C(3´)), 165.45 (C(1´)).
(RS,1S,2S,5R,E)ꢀNꢀ(5ꢀBromoꢀ2ꢀhydroxybenzylidene)ꢀ2ꢀisoꢀ
propylꢀ5ꢀmethylcyclohexanesulfinamide ((RS)ꢀ5c). Yellow powꢀ
22
der, m.p. 139—140 C, []D +45.0 (c 0.25, acetone), Rf 0.32
(benzene). Found (%): C, 52.84; H, 6.31; N, 3.68; S, 8.27.
C17H24BrNO2S. Calculated (%): C, 52.85; H, 6.26; N, 3.63;
S, 8.30. IR, /cm–1: 1074 (S=O), 1277 (CAr—OH), 1599 (C=N).
1H NMR (CDCl3), : 0.85 (d, 3 H, C(7)H3, J = 6.2 Hz); 0.96
(qd, 1 H, H(4a), J = 12.6 Hz, J = 3.5 Hz); 1.09 (d, 6 H, C(9)H3,
C(10)H3, J = 6.6 Hz); 1.16 (ddd, 1 H, H(6a), J = 14.9 Hz,
J = 12.4 Hz, J = 4.8 Hz); 1.50 (ddt, 1 H, H(2), J = 12.7 Hz,
J = 9.2 Hz, J = 3.2 Hz); 1.74 (dtd, 1 H, H(3a), J = 13.1 Hz,
J = 13.0 Hz, J = 3.6 Hz); 1.84—2.01 (m, 2 H, H(4e), H(3e));
2.00—2.18 (m, 3 H, H(5), H(8), H(6e)); 3.25—3.34 (m, 1 H,
H(1)); 6.96 (d, 1 H, H(4´), J = 8.8 Hz); 7.54 (dd, 1 H, H(5´),
J = 8.8 Hz, J = 2.4 Hz); 7.63 (d, 1 H, H(7´), J = 2.4 Hz); 8.67
(s, 1 H, H(1´)); 11.02 (s, 1 H, OH). 13C NMR, : 21.37 (C(9)),
21.63 (C(10)), 22.75 (C(7)), 26.11 (C(3)), 27.85 (C(5)), 29.88
(C(8)), 33.34 (C(6)), 35.01 (C(4)), 47.19 (C(2)), 62.71 (C(1)),
111.37 (C(2´)), 119.30 (C(4´)), 119.68 (C(6´)), 135.02 (C(7´)),
137.09 (C(5´)), 159.11 (C(3´)), 163.37 (C(1´)).
Characteristics of sulfinimines 3a,b, 4a,b with (S)ꢀconfiguꢀ
ration of the sulfur atom are given in work.8
(SS,1S,2S,5R,E)ꢀNꢀ(5ꢀBromoꢀ2ꢀhydroxybenzylidene)ꢀ2ꢀisoꢀ
propylꢀ5ꢀmethylcyclohexanesulfinamide ((SS)ꢀ5c). Yellow powꢀ
der, m.p. 118—119 C. []D +89.4 (c 0.26, acetone), Rf 0.29
(benzene). Found (%): C, 52.82; H, 6.28; N, 3.60; S, 8.25.
C17H24NO2SBr. Calculated (%): C, 52.85; H, 6.26; N, 3.63;
S, 8.30. IR, /cm–1: 1087 (S=O), 1271 (CAr—OH), 1611 (C=N).
22
(RS,1S,2S,5R,E)ꢀNꢀ(2ꢀHydroxybenzylidene)ꢀ2ꢀisopropylꢀ5ꢀ
methylcyclohexanesulfinamide ((RS)ꢀ5a). White powder, m.p.
22
120—121 C, []D +155.7 (c 0.10, acetone), Rf 0.25 (AcOH).
Found (%): C, 66.45; H, 8.17; N, 4.55; S, 10.43. C17H25NO2S.
Calculated (%): C, 66.41; H, 8.20; N, 4.56; S, 10.43. IR, /cm–1
1070 (S=O), 1273(CAr—OH), 1598 (C=N). 1H NMR (CDCl3),
: 0.84, 1.09, 1.10 (all d, 3 H each, C(7)H3, C(10)H3, C(9)H3,
J = 6.5 Hz); 0.93 (qd, 1 H, H(4a), J = 12.6 Hz, J = 3.5 Hz); 1.15
(ddd, 1 H, H(6a), J = 14.4 Hz, J = 12.4 Hz, J = 5.0 Hz); 1.50
(ddt, 1 H, H(2), J = 12.8 Hz, J = 9.3 Hz, J = 3.7 Hz); 1.74 (qd, 1 H,
H(3a), J = 12.8 Hz, J = 3.0 Hz); 1.83—2.00 (m, 2 H, H(4e),
H(3e)); 2.00—2.21 (m, 3 H, H(5), H(6e), H(8)); 3.25—3.32
(m, 1 H, H(1)); 7.00—7.08 (m, 2 H, H(4´), H(6´)); 7.43—7.54
(m, 2 H, H(5´), H(7´)); 8.74 (s, 1 H, H(1´)); 11.01 (s, 1 H, OH).
13C NMR, : 21.40 (C(9)), 21.66 (C(10)), 22.77 (C(7)),
26.13 (C(3)), 27.88 (C(5)), 29.86 (C(8)), 33.33 (C(6)), 35.05
(C(4)), 47.22 (C(2)), 62.66 (C(1)), 117.29 (C(4´)), 118.36 (C(2´)),
119.84 (C(6´)), 133.19 (C(7´)), 134.57 (C(5´)), 160.13 (C(3´)),
164.46 (C(1´)).
:
1H NMR (CDCl3), : 0.92 (d, 3 H, C(7)H3, J = 6.4 Hz);
0.93—1.14 (m, 1 H, H(4a)); 1.00 (d, 3 H, C(10)H3, J = 6.4 Hz);
1.04 (d, 3 H, C(9)H3, J = 6.4 Hz); 1.20—1.35 (m, 1 H, H(6a));
1.44 (ddt, 1 H, H(2), J = 12.7 Hz, J = 10.0 Hz, J = 3.0 Hz); 1.77
(qd, 1 H, H(3a), J = 13.0 Hz, J = 3.0 Hz); 1.70—1.87 (m, 1 H,
H(5)); 1.88—2.19 (m, 3 H, H(3e), H(4e), H(8)); 2.33 (ddt, 1 H,
H(6e), J = 14.4 Hz, J = 2.7 Hz, J = 2.1 Hz); 3.17—3.25 (m, 1 H,
H(1)); 6.94 (d, 1 H, H(4´), J = 9.0 Hz); 7.51 (dd, 1 H, H(5´),
J = 8.9 Hz, J = 2.4 Hz); 7.58 (d, 1 H, H(7´), J = 2.3 Hz); 8.70
(s, 1 H, H(1´)); 11.16 (s, 1 H, OH). 13C NMR, : 21.71 (C(9)),
21.74 (C(10)), 22.51 (C(7)), 26.51 (C(3)), 28.39 (C(5)), 29.50
(C(8)), 35.35 (C(4)), 37.01 (C(6)), 49.15 (C(2)), 68.26 (C(1)),
111.36 (C(4´)), 119.30 (C(2´)), 119.88 (C(6´)), 135.01 (C(7´)),
137.13 (C(5´)), 159.11 (C(3´)), 163.46 (C(1´)).
(RS,1S,2S,5R,E)ꢀNꢀ(4ꢀNitrobenzylidene)ꢀ2ꢀisopropylꢀ5ꢀmeꢀ
thylcyclohexanesulfinamide ((RS)ꢀ6a). Yellow crystals, m.p.
134—135 C, []D22 +151.0 (c 0.14, acetone), Rf 0.21 (benzene).
Found (%): C, 60.73; H, 7.15; N, 8.31; S, 9.61. C17H24N2O3S.
(RS,1S,2S,5R,E)ꢀNꢀ(3,5ꢀDiꢀtertꢀbutylꢀ2ꢀhydroxybenzylꢀ
idene)ꢀ2ꢀisopropylꢀ5ꢀmethylcyclohexanesulfinamide ((RS)ꢀ5b).
Yellow oily liquid, []D22 +129.6 (c 0.28, acetone), Rf 0.47 (benzꢀ
ene). Found (%): C, 71.52; H, 9.83; N, 3.36; S, 7.62. C25H41NO2S.
Calculated (%): C, 60.69; H, 7.19; N, 8.33; S, 9.53. IR, /cm–1
:
Calculated (%): C, 71.55; H, 9.85; N, 3.34; S, 7.64. IR, /cm–1
:
1080 (S=O), 1342 (NO2), 1518 (NO2), 1587 (C=N). H NMR
(CDCl3), : 0.84 (d, 3 H, C(7)H3, J = 6.3 Hz); 0.89—1.06
(m, 1 H, H(4a)); 1.09 (d, 3 H, C(10)H3, J = 6.5 Hz); 1.10
(d, 3 H, C(9)H3, J = 6.4 Hz); 1.17 (ddd, 1 H, H(6a), J = 14.5 Hz,
J = 12.3 Hz, J = 4.8 Hz); 1.48 (ddt, 1 H, H(2), J = 12.9 Hz,
J = 9.3 Hz, J = 3.3 Hz); 1.70 (qd, 1 H, H(3a), J = 12.7 Hz,
J = 3.0 Hz); 1.85—2.04 (m, 2 H, H(3e), H(4e)); 2.03—2.22
1
1
1088 (S=O), 1571 (C=N). H NMR (CDCl3), : 0.86 (d, 3 H,
C(7)H3, J = 6.2 Hz); 0.97 (qd, 1 H, H(4a), J = 13.0 Hz, J = 3.6 Hz);
1.11 (d, 3 H, C(10)H3, J = 6.5 Hz); 1.12 (d, 3 H, C(9)H3,
J = 6.5 Hz); 1.07—1.22 (m, 1 H, H(6a)); 1.37 (s, 9 H, C(13´)H3,
C(14´)H3, C(15´)H3); 1.39—1.58 (m, 1 H, H(2)); 1.49 (s, 9 H,
C(9´)H3, C(10´)H3, C(11´)H3); 1.60—1.82 (m, 1 H, H(3a));

2374
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 11, November, 2013
Izmest´ev et al.
(m, 3 H, H(5), H(8), H(6e)); 3.33—3.43 (m, 1 H, H(1)); 8.06
(d, 2 H, H(3´), H(7´), J = 8.7 Hz); 8.37 (d, 2 H, H(4´), H(6´),
J = 8.7 Hz); 8.73 (s, 1 H, H(1´)). 13C NMR, : 21.48 (C(9)), 21.51
(C(10)), 22.72 (C(7)), 26.19 (C(3)), 27.83 (C(5)), 29.75 (C(8)),
33.93 (C(6)), 35.14 (C(4)), 47.55 (C(2)), 62.75 (C(1)), 124.22
(C(4´), C(6´)), 129.99 (C(3´), C(7´)), 138.98 (C(5´)), 149.78
(C(2´)), 159.38 (C(1´)).
S, 7.59. C25H43NO2S. Calculated (%): C, 71.21; H, 10.28;
N, 3.32; S, 7.60. IR, /cm–1: 1037 (S=O), 1227 (CAr—OH),
3226 (NH). 1H NMR (CDCl3), : 0.93 (d, 3 H, C(7)H3, J = 6.2 Hz);
0.92—1.04 (m, 1 H, H(4a)); 0.99 (d, 3 H, C(10)H3, J = 6.5 Hz);
1.02 (d, 3 H, C(9)H3, J = 6.5 Hz); 1.09—1.31 (m, 1 H, H(6a));
1.33 (s, 9 H, C(13´)H3, C(14´)H3, C(15´)H3); 1.31—1.42
(m, 1 H, H(2)); 1.46 (s, 9 H, C(9´)H3, C(10´)H3, C(11´)H3);
1.47—1.63 (m, 1 H, H(3a)); 1.76—2.04 (m, 4 H, H(3e), H(4e),
H(5), H(8)); 2.45 (ddt, 1 H, H(6e), J = 14.0 Hz, J = 2.9 Hz,
J = 2.6 Hz); 3.30—3.39 (n.m, 1 H, H(1)); 4.03 (dd, 1 H, NH,
J = 7.4 Hz, J = 2.4 Hz); 4.19 (dd, 1 H, H(1a´), J = 13.2 Hz,
J = 2.6 Hz); 4.43 (dd, 1 H, H(1b´), J = 13.2 Hz, J = 7.3 Hz); 7.05
(d, 1 H, H(7´), J = 2.6 Hz); 7.36 (d, 1 H, H(5´), J = 2.4 Hz);
7.97 (s, 1 H, OH). 13C NMR, : 21.28 (C(9)), 21.69 (C(10)),
22.58 (C(7)), 25.91 (C(3)), 27.83 (C(8)), 28.87 (C(5)), 29.80
(C(9´), C(10´), C(11´)); 31.62 (C(13´), C(14´), C(15´)), 34.25
(C(12´)), 35.05 (C(4)), 35.20 (C(8´)), 35.43 (C(6)), 43.54 (C(1´)),
47.67 (C(2)), 61.64 (C(1)), 123.25 (C(2´)), 124.65 (C(7´)), 125.03
(C(5´)), 137.95 (C(4´)), 142.01 (C(6´)), 152.17 (C(3´)).
(RS,1S,2S,5R,E)ꢀNꢀ(4ꢀDimethylaminobenzylidene)ꢀ2ꢀisoꢀ
propylꢀ5ꢀmenthylcyclohexanesulfinamide ((RS)ꢀ6b). Yellow powꢀ
22
der, m.p. 94—95 C, []D +219.0 (c 0.11, acetone), Rf 0.29
(benzene). Found (%): C, 68.21; H, 8.94; N, 8.30; S, 9.61.
C19H30NO2S. Calculated (%): C, 68.22; H, 9.04; N, 8.37; S, 9.59.
IR, /cm–1: 1077 (S=O), 1177 (C—N), 1609 (C=N). 1H NMR
(CDCl3), : 0.84 (d, 3 H, C(7)H3, J = 6.5 Hz); 0.87—1.04
(m, 1 H, H(4a)); 1.06 (d, 3 H, C(10)H3, J = 6.5 Hz); 1.10
(d, 3 H, C(9)H3, J = 6.5 Hz); 1.04—1.16 (m, 1 H, H(6a)); 1.43
(ddt, 1 H, H(2), J = 12.5 Hz, J = 9.6 Hz, J = 3.7 Hz); 1.73
(qd, 1 H, H(3a), J = 12.6 Hz, J = 3.2 Hz); 1.83—1.98 (m, 2 H,
H(3e), H(4e)); 1.99—2.18 (m, 1 H, H(5)); 2.14—2.31 (m, 2 H,
H(6e), H(8)); 3.09 (s, 9 H, N(CH3)2); 3.17—3.27 (n.m, 1 H,
H(1)); 6.74 (d, 2 H, H(4´), H(6´), J = 8.8 Hz); 7.75 (d, 2 H,
H(3´), H(7´), J = 8.8 Hz); 8.49 (s, 1 H, H(1´)). 13C NMR,
: 21.59 (C(9)), 21.66 (C(10)), 22.83 (C(7)), 26.23 (C(3)), 27.81
(C(5)), 29.63 (C(8)), 33.89 (C(6)), 35.41 (C(4)), 40.12 (C(8´),
C(9´)), 47.72 (C(2)), 62.55 (C(1)), 111.44 (C(4´), C(6´)), 122.65
(C(2´)), 131.16 (C(3´), C(7´)), 152.95 (C(5´)), 160.44 (C(1´)).
Synthesis of Nꢀsubstituted sulfinamides 7 and 8 (general proꢀ
cedure). Lithium aluminum hydride (0.11 g, 3 mmol) was careꢀ
fully added to the corresponding sulfinimine (1 mmol) in dry
THF (20 mL) cooled to –48 C. The stirring was continued for
10—20 min, the solution was filtered under reduced pressure,
the filtrate was washed with water (5 mL), extracted with AcOEt
(3×10 mL), dried with Na2SO4. After evaporation of the solvent
in vacuo, the product was isolated by column chromatography
on silica gel. The eluent used for each substance is specified
among their characteristics. Characteristics of Nꢀsubstituted sulꢀ
finamides 7, 8 with (S)ꢀconfiguration of the sulfur atom are
given in the work.8
(RS,1S,2S,5R)ꢀNꢀ(4ꢀNitrobenzyl)ꢀ2ꢀisopropylꢀ5ꢀmethylꢀ
cyclohexanesulfinamide ((RS)ꢀ8a). Yellow powder, the yield was
22
90%, m.p. 85—86 C, []D +18.2 (c 0.27, acetone), Rf 0.50
(AcOEt). Found (%): C, 60.30; H, 7.76; N, 8.28; S, 9.46.
C17H26N2O3S. Calculated (%): C, 60.33; H, 7.74; N, 8.28;
S, 9.47. IR, /cm–1: 1040 (S=O), 1344 (NO2), 1519 (NO2),
3102 (NH). 1H NMR (CDCl3), : 0.89 (d, 3 H, C(7)H3,
J = 6.2 Hz); 0.93—1.06 (m, 1 H, H(4a)); 0.95 (d, 3 H, C(10)H3,
J = 6.5 Hz); 0.97 (d, 3 H, C(9)H3, J = 6.6 Hz); 1.13—1.28 (ddd,
1 H, H(6a), J = 14.2 Hz, J = 12.2 Hz, J = 4.1 Hz); 1.30—1.42
(m, 1 H, H(2)); 1.41—1.58 (m, 1 H, H(3a)); 1.73—2.02 (m, 4 H,
H(3e), H(4e), H(5), H(8)); 2.34—2.46 (m, 1 H, H(6e)); 3.17—3.24
(n.m, 1 H, H(1)); 4.27 (t, 1 H, NH, J = 6.3 Hz); 4.33—4.49
(m, 2 H, C(1´)H2); 7.55 (d, 2 H, H(3´), H(7´), J = 8.8 Hz); 8.21
(d, 2 H, H(4´),H(6´), J = 8.8 Hz). 13C NMR, : 21.24 (C(9)),
21.72 (C(10)), 22.62 (C(7)), 25.88 (C(3)), 27.70 (C(5)), 28.84
(C(8)), 35.04 (C(4)), 35.15 (C(6)), 47.62 (C(2)), 47.80 (C(1´)),
63.14 (C(1)), 123.83 (C(4´), C(6´)), 128.92 (C(3´), C(7´)), 145.65
(C(2´)), 147.47 (C(5´)).
(RS,1S,2S,5R)ꢀNꢀ(2ꢀHydroxybenzyl)ꢀ2ꢀisopropylꢀ5ꢀmethylꢀ
cyclohexanesulfinamide ((RS)ꢀ7a). White powder, the yield was
95%, m.p. 127—128 C, []D +10.0 (c 0.17, acetone), Rf 0.60
(RS,1S,2S,5R)ꢀNꢀ(4ꢀDimethylaminobenzyl)ꢀ2ꢀisopropylꢀ5ꢀ
methylcyclohexanesulfinamide ((RS)ꢀ8b). Yellow oily liquid,
the yield was 75%, []D +29.9 (c 0.16, acetone), Rf 0.21
22
22
(AcOEt—hexane, 5 : 1). Found (%): C, 65.93; H, 8.76; N, 4.54;
S, 10.33. C19H30NO2S. Calculated (%): C, 65.98; H, 8.79;
N, 4.53; S, 10.36. IR, /cm–1: 1026 (S=O), 1263 (CAr—OH),
(CHCl3—Et2O, 3 : 1). Found (%): C, 67.82; H, 9.54; N, 8.35;
S, 9.51. C19H32N2OS. Calculated (%): C, 67.81; H, 9.58;
N, 8.32; S, 9.53. IR, /cm–1: 1051 (S=O), 3170 (NH). 1H NMR
(CDCl3), : 0.90 (d, 3 H, C(7)H3, J = 6.5 Hz); 0.90—1.04 (m, 1 H,
H(4a)); 0.97 (d, 3 H, C(10)H3, J = 6.5 Hz); 0.99 (d, 3 H, C(9)H3,
J = 5.9 Hz); 1.17 (ddd, 1 H, H(6a), J = 14.2 Hz, J = 12.3 Hz,
J = 4.1 Hz); 1.27—1.40 (m, 1 H, H(2)); 1.55 (qd, 1 H, H(3a),
J = 13.0 Hz, J = 3.0 Hz); 1.76—2.09 (m, 4 H, H(3e), H(4e), H(5),
H(8)); 2.41 (ddt, 1 H, H(6e), J = 14.0 Hz, J = 2.7 Hz, J = 2.4 Hz);
2.97 (s, 6 H, N(CH3)2); 3.11—3.20 (n.m, 1 H, H(1)); 4.80 (t, 1 H,
NH, J = 6.0 Hz); 4.14—4.28 (m, 2 H, C(1´)H2); 6.74 (d, 2 H,
H(4´), H(6´), J = 8.5 Hz); 7.24 (d, 2 H, H(3´), H(7´), J = 8.5 Hz).
13C NMR, : 21.29 (C(9)), 21.81 (C(10)), 22.66 (C(7)),
25.88 (C(3)), 27.66 (C(8)), 28.86 (C(5)), 35.20 (C(4)), 35.28
(C(6)), 40.70 (C(8´), C(9´)), 47.59 (C(1´)), 47.74 (C(2)), 62.70
(C(1)), 112.73 (C(2´), C(4´), C(6´)), 129.41 (C(3´), C(7´)),
150.35 (C(5´)).
1
852 (S—N), 3251 (NH). H NMR (CDCl3), : 0.90 (d, 3 H,
C(7)H3, J = 6.2 Hz); 0.88—1.11 (m, 1 H, H(4a)); 0.95 (d, 3 H,
C(10)H3, J = 6.2 Hz); 0.97 (d, 3 H, C(9)H3, J = 6.5 Hz);
1.13—1.29 (m, 1 H, H(6a)); 1.29—1.44 (m, 1 H, H(2));
1.44—1.61 (m, 1 H, H(3a)); 1.70—2.05 (m, 4 H, H(3e), H(4e),
H(5), H(8)); 2.37—2.50 (m, 1 H, H(6e)); 3.27—3.35 (n.m, 1 H,
H(1)); 4.20—4.46 (m, 3 H, C(1´)H2, NH); 6.85 (t, 1 H, H(6´),
J = 7.5 Hz); 6.93 (d, 1 H, H(4´), J = 7.9 Hz); 7.13—7.26 (m, 2 H,
H(5´), H(7´)); 8.63 (br.s, 1 H, OH). 13C NMR, : 21.24 (C(9)),
21.64 (C(10)), 22.56 (C(7)), 25.89 (C(3)), 27.78(C(8)), 28.86
(C(5)), 35.05 (C(4)), 35.48 (C(6)), 43.83 (C(1´)), 47.69 (C(2)),
62.31 (C(1)), 117.48 (C(4´)), 119.96 (C(6´)), 123.99 (C(2´)),
129.83 (C(5´)), 130.19 (C(7´)), 155.62 (C(3´)).
(RS,1S,2S,5R)ꢀNꢀ(3,5ꢀDiꢀtertꢀbutylꢀ2ꢀhydroxybenzyl)ꢀ2ꢀ
isopropylꢀ5ꢀmethylcyclohexanesulfinamide ((RS)ꢀ7b). Yellow oily
liquid, the yield was 80%, []D22 +3.0 (c 0.17, acetone), Rf 0.52
(CHCl3—Et2O, 3 : 1). Found (%): C, 71.25; H, 10.26; N, 3.29;
Addition of Grignard reagents to sulfenimine 3c and sulfinꢀ
imine 5c. A corresponding sulfenimine or sulfinimine (1 mmol)
in anhydrous CH2Cl2 (5—10 mL) was placed in a roundꢀbottom

Neomenthane sulfinamides
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 11, November, 2013 2375
flask equipped with a magnetic stirrer. A 3 M Grignard reagent
(1.5 mmol) in Et2O was added dropwise under argon, and the
mixture was stirred for 24 h, quenched with water (2 mL), and
after stirring for 5 min extracted with AcOEt (3×5 mL). The
organic layers were combined, dried with Na2SO4, the solvent
was evaporated in vacuo, the residue was separated by column
chromatography, using a mixture of benzene—AcOEt in differꢀ
ent ratios as an eluent. The total yields of the products and
diastereoselectivity of addition are given in Table 1.
(SS,1S,2S,5R)ꢀNꢀ[(S)ꢀ1ꢀ(5ꢀBromoꢀ2ꢀhydroxyphenyl)ethyl]ꢀ
2ꢀisopropylꢀ5ꢀmethylcyclohexanesulfinamide ((SSS)ꢀ9b). Yellow
crystals, m.p. 66—67 C, []D22 +86.0 (c 0.22, acetone), Rf 0.41
(benzene—AcOEt, 5 : 2). Found (%): C, 53.72; H, 7.06; N, 3.48;
S, 7.96. C18H28BrNO2S. Calculated (%): C, 53.73; H, 7.01;
N, 3.48; S, 7.97. IR, /cm–1: 1024 (S=O), 1273 (CAr—OH), 3171
(NH). 1H NMR (CDCl3), : 0.90 (d, 3 H, C(7)H3, J = 6.2 Hz);
0.94 (d, 3 H, C(10)H3, J = 6.7 Hz); 0.97—1.07 (m, 1 H, H(4a));
1.08 (d, 3 H, C(9)H3, J = 6.2 Hz); 1.18—1.48 (m, 2 H, H(2),
H(6a)); 1.57 (d, 3 H, C(8´)H3, J = 6.7 Hz); 1.48—1.71 (m, 2 H,
H(3a), H(5)); 1.82—2.02 (m, 2 H, H(3e), H(4e)); 2.01—2.17
(m, 1 H, H(8)); 2.21—2.34 (m, 1 H, H(6e)); 3.34—3.36 (n.m,
1 H, H(1)); 4.27—4.43 (s, 1 H, NH); 4.76—4.91 (m, 1 H, H(1´));
6.72 (d, 1 H, H(4´), J = 8.7 Hz); 7.21 (dd, 1 H, H(5´), J = 8.7 Hz,
J = 2.6 Hz); 7.31 (d, 1 H, H(7´), J = 2.1 Hz); 9.08 (br.s, 1 H,
OH). 13C NMR, : 21.97 (C(8´), C(10)), 22.56 (C(9)), 22.71
(C(7)), 26.06 (C(3)), 27.79 (C(5)), 29.06 (C(8)), 35.58 (C(4)),
38.13 (C(6)), 48.12 (C(1´)), 49.46 (C(2)), 63.19 (C(1)), 111.72
(C(2´)), 119.00 (C(4´)), 123.63 (C(7´)), 130.73 (C(6´)), 131.50
(C(5´)), 154.14 (C(3´)).
(q, 1 H, H(1´), J = 6.8 Hz); 6.66 (d, 1 H, H(4´), J = 8.7 Hz);
7.15 (dd, 1 H, H(5´), J = 8.7 Hz, J = 2.6 Hz); 7.28 (d, 1 H,
H(7´), J = 2.1 Hz); 8.55 (br.s, 1 H, OH). 13C NMR, : 21.11
(C(9)), 21.29 (C(10)), 22.44 (C(7)), 23.00 (C(8´)), 25.84 (C(3)),
27.64 (C(8)), 28.64 (C(5)), 34.95 (C(4)), 35.06 (C(6)),
47.42 (C(2)), 50.29 (C(1´)), 63.20 (C(1)), 111.58 (C(2´)),
117.80 (C(4´)), 130.11 (C(7´)), 130.94 (C(5´)), 131.34 (C(6´)),
153.61 (C(3´)).
(RS,1S,2S,5R)ꢀNꢀ[(R)ꢀ1ꢀ(5ꢀBromoꢀ2ꢀhydroxyphenyl)ethyl]ꢀ
2ꢀisopropylꢀ5ꢀmethylcyclohexanesulfinamide ((RSR)ꢀ9b). Yellow
crystals, m.p. 101—102 C, []D22 +61.0 (c 0.26 acetone), Rf 0.33
(benzene—AcOEt, 5 : 2). Found (%): C, 53.73; H, 7.03; N, 3.46;
S, 7.96. C18H28BrNO2S. Calculated (%): C, 53.73; H, 7.01;
N, 3.48; S, 7.97. IR, /cm–1: 1034 (S=O), 1275 (CAr—OH),
3159 (NH). 1H NMR (CDCl3), : 0.90 (d, 3 H, C(7)H3,
J = 6.7 Hz); 1.00 (d, 3 H, C(10)H3, J = 6.4 Hz); 1.02 (d, 3 H,
C(9)H3, J = 6.4 Hz); 0.94—1.12 (m, 1 H, H(4a)); 1.15—1.29
(m, 1 H, H(6a)); 1.31—1.45 (m, 1 H, H(2)); 1.45—1.68 (m, 1 H,
H(3e)); 1.54 (d, 1 H, C(8´), J = 6.7 Hz); 1.80—2.04 (m, 4 H,
H(3e), H(4e), H(5), H(8)); 2.33—2.46 (m, 1 H, H(6e));
3.17—3.29 (n.m, 1 H, H(1)); 4.47 (br.s, 1 H, NH); 5.26 (n.m,
1 H, H(1´)); 6.42 (d, 1 H, H(4´), J = 8.7 Hz); 7.02 (dd, 1 H,
H(5´), J = 8.5 Hz, J = 2.3 Hz); 7.20 (d, 1 H, H(7´), J = 2.6 Hz);
9.29 (br.s, 1 H, OH). 13C NMR, : 21.34 (C(9)), 21.66 (C(10)),
21.79 (C(8´)), 22.58 (C(7)), 25.97 (C(3)), 27.69 (C(8)), 28.91
(C(5)), 35.06 (C(4)), 35.53 (C(6)), 47.90 (C(2)), 55.32 (C(1´)),
64.51 (C(1)), 111.20 (C(2´)), 118.50 (C(4´)), 129.63 (C(7´)),
130.96 (C(6´)), 131.37 (C(5´)), 154.02 (C(3´)).
(SS,1S,2S,5R)ꢀNꢀ[(S)ꢀ1ꢀ(5ꢀBromoꢀ2ꢀhydroxyphenyl)propꢀ
yl]ꢀ2ꢀisopropylꢀ5ꢀmethylcyclohexanesulfinamide ((SSS)ꢀ9c). Yellow
(SS,1S,2S,5R)ꢀNꢀ[(R)ꢀ1ꢀ(5ꢀBromoꢀ2ꢀhydroxyphenyl)ethyl]ꢀ
2ꢀisopropylꢀ5ꢀmethylcyclohexanesulfinamide ((SSR)ꢀ9b). Yellow
22
powder, m.p. 71—72 C, []D +1.4 (c 0.44, acetone), Rf 0.42
22
crystals, m.p. 66—67 C, []D –0.4 (c 0.23, acetone), Rf 0.32
(benzene—AcOEt, 5 : 2). Found (%): C, 54.81; H, 7.24; N, 3.36;
S, 7.65. C19H30BrNO2S. Calculated (%): C, 54.80; H, 7.26;
N, 3.36; S, 7.70. IR, /cm–1: 1028 (S=O), 1267 (CAr—OH), 3292
(NH). 1H NMR (CDCl3), : 0.88 (t, 3 H, C(9´)H3, J = 7.2 Hz);
0.95 (d, 6 H, C(7)H3, C(9)H3, J = 6.2 Hz); 1.04 (d, 3 H, C(10)H3,
J = 6.2 Hz); 0.95—1.17 (m, 1 H, H(4a)); 1.22—1.47 (m, 2 H,
H(2), H(6a)); 1.57—2.20 (m, 6 H, H(3a), H(3e), H(4e), H(5),
H(8), H(8´)); 2.36—2.49 (m, 1 H, H(6e)); 3.22—3.35 (n.m, 1 H,
H(1)); 3.97 (q, 1 H, H(1´), J = 7.9 Hz); 5.33 (t, 1 H, NH, J = 4.7 Hz);
6.16 (d, 1 H, H(4´), J = 8.7 Hz); 6.89 (dd, 1 H, H(5´), J = 8.7 Hz,
J = 2.6 Hz); 7.11 (d, 1 H, H(7´), J = 2.1 Hz); 9.60 (s, 1 H, OH).
13C NMR, : 11.40 (C(9´)), 21.75 (C(9)), 21.80 (C(10)), 22.68
(C(7)), 25.76 (C(3)), 27.98 (C(5)), 28.78 (C(8)), 29.44 (C(8´)),
35.49 (C(4)), 37.57 (C(6)), 49.11 (C(2)), 64.38 (C(1´)), 64.76
(C(1)), 110.81 (C(2´)), 118.34 (C(4´)), 129.85 (C(6´)), 130.31
(C(7´)), 131.28 (C(5´)), 154.10 (C(3´)).
(benzene—AcOEt, 5 : 2). Found (%): C, 53.71; H, 7.03; N, 3.45;
S, 7.95. C18H28BrNO2S. Calculated (%): C, 53.73; H, 7.01;
N, 3.48; S, 7.97. IR, /cm–1: 1030 (S=O), 1273 (CAr—OH),
3163 (NH). 1H NMR (CDCl3), : 0.93 (d, 3 H, C(7)H3,
J = 6.6 Hz); 0.95 (d, 3 H, C(10)H3, J = 6.7 Hz); 0.97—1.11
(m, 1 H, H(4a)); 1.04 (d, 3 H, C(9)H3, J = 6.2 Hz); 1.16—1.48
(m, 2 H, H(2), H(6a)); 1.53 (d, 3 H, C(8´)H3, J = 6.9 Hz);
1.50—1.83 (m, 2 H, H(3a), H(5)); 1.84—2.02 (m, 2 H, H(3e),
H(4e)); 2.00—2.17 (m, 1 H, H(8)); 2.24—2.41 (m, 1 H, H(6e));
3.19—3.30 (n.m, 1 H, H(1)); 4.44 (t, 1 H, NH, J = 6.7 Hz); 5.08
(d, 1 H, H(1´), J = 6.9 Hz); 6.40 (d, 1 H, H(4´), J = 8.5 Hz);
7.00 (dd, 1 H, H(5´), J = 8.5 Hz, J = 2.3 Hz); 7.19 (d, 1 H,
H(7´), J = 2.6 Hz); 9.37 (br.s, 1 H, OH). 13C NMR, : 21.81
(C(8´), C(10)), 22.02 (C(9)), 22.39 (C(7)), 25.83 (C(3)), 27.94
(C(5)), 28.89 (C(8)), 35.47 (C(4)), 38.12 (C(6)), 49.00 (C(2)),
55.29 (C(1´)), 64.34 (C(1)), 111.13 (C(2´)), 118.47 (C(4´)),
129.61 (C(7´)), 130.91 (C(6´)), 131.37 (C(5´)), 154.08 (C(3´)).
(RS,1S,2S,5R)ꢀNꢀ[(S)ꢀ1ꢀ(5ꢀBromoꢀ2ꢀhydroxyphenyl)ethyl]ꢀ
2ꢀisopropylꢀ5ꢀmethylcyclohexanesulfinamide ((RSS)ꢀ9b). Yellow
(SS,1S,2S,5R)ꢀNꢀ[(R)ꢀ1ꢀ(5ꢀBromoꢀ2ꢀhydroxyphenyl)propꢀ
yl]ꢀ2ꢀisopropylꢀ5ꢀmethylcyclohexanesulfinamide ((SSR)ꢀ9c). Yellow
22
powder, m.p. 193—194 C, []D +98.0 (c 0.13, acetone),
Rf 0.23 (benzene—AcOEt, 5 : 2). Found (%): C, 54.82; H, 7.26;
N, 3.38; S, 7.68. C19H30BrNO2S. Calculated (%): C, 54.80;
H, 7.26; N, 3.36; S, 7.70. IR, /cm–1: 1013 (S=O), 1277
22
crystals, m.p. 196—197 C, []D –44.0 (c 0.10, acetone),
Rf 0.41 (benzene—AcOEt, 5 : 2). Found (%): C, 53.74; H, 7.03;
N, 3.47; S, 7.98. C18H28BrNO2S. Calculated (%): C, 53.73;
H, 7.01; N, 3.48; S, 7.97. IR, /cm–1: 995 (S=O), 1279 (CAr—OH),
3188 (NH). 1H NMR (CDCl3), : 0.83 (d, 6 H, C(7)H3, C(10)H3,
J = 6.2 Hz); 0.88 (d, 3 H, C(9)H3, J = 6.2 Hz); 0.82—0.96
(m, 1 H, H(4a)); 1.06—1.43 (m, 3 H, H(2), H(3a), H(6a)); 1.49
(d, 3 H, C(8´)H3, J = 6.7 Hz); 1.52—1.68 (m, 1 H, H(5));
1.71—1.93 (m, 3 H, H(3e), H(4e), H(8)); 2.27—2.41 (m, 1 H,
H(6e)); 3.12—3.22 (n.m, 1 H, H(1)); 3.47 (br.s, 1 H, NH); 4.73
1
(CAr—OH), 3271 (NH). H NMR (CDCl3), : 0.74 (d, 3 H,
C(7)H3, J = 6.7 Hz); 0.78—0.90 (m, 6 H, C(9´)H3, C(10)H3);
0.96 (d, 3 H, C(9)H3, J = 6.2 Hz); 0.84—0.97 (m, 1 H, H(4a));
1.07—1.49 (m, 4 H, H(2), H(3a), H(5), H(6a)); 1.70—2.01
(m, 5 H, H(3e), H(4e), H(8), C(8´)H2); 2.08—2.22 (m, 1 H, H(6e)),
3.19—3.29 (n.m, 1 H, H(1)), 4.47 (s, 2 H, NH, OH), 4.84 (t, 1 H,
H(1´), J = 7.2 Hz), 6.66 (d, 1 H, H(4´), J = 8.7 Hz), 7.15 (dd,
1 H, H(5´), J = 8.7 Hz, J = 2.1 Hz), 7.20 (d, 1 H, H(7´),

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Izmest´ev et al.
J = 2.1 Hz). 13C NMR, : 10.43 (C(9´)), 21.71 (C(9)), 21.75
(C(10)), 22.35 (C(7)), 25.94 (C(3)), 27.62 (C(5)), 28.92 (C(8)),
29.66 (C(8´)), 35.44 (C(4)), 38.15 (C(6)), 49.29 (C(2)), 55.53
(C(1´)), 63.82 (C(1)), 111.60 (C(2´)), 117.96 (C(4´)), 129.93
(C(6´)), 130.71 (C(7´)), 131.01 (C(5´)), 154.11 (C(3´)).
68.04 (C(1´)), 111.37 (C(2´)), 118.88 (C(4´)), 127.68 (C(6´)),
131.53 (C(5´)), 132.65 (C(7´)), 155.63 (C(3´)).
(1S,2S,5R)ꢀNꢀ[1ꢀ(2ꢀHydroxyꢀ5ꢀbromophenyl)propyl]ꢀ2ꢀ
isopropylꢀ5ꢀmethylcyclohexanesulfenamide (10b). Yellow oily liquid,
[]D22 +141.0 (c 0.19, acetone), Rf 0.32 (benzene—AcOEt, 5 : 2).
Found (%): C, 56.96; H, 7.55; N, 3.49; S, 8.03. C19H30BrNOS.
(RS,1S,2S,5R)ꢀNꢀ[(S)ꢀ1ꢀ(5ꢀBromoꢀ2ꢀhydroxyphenyl)propꢀ
yl]ꢀ2ꢀisopropylꢀ5ꢀmethylcyclohexanesulfinamide ((RSS)ꢀ9c). Yellow
powder, m.p. 99—100 C, []D22 +46.0 (c 0.41, acetone), Rf 0.41
(benzene—AcOEt, 5 : 2). Found (%): C, 54.83; H, 7.25; N, 3.37;
S, 7.68. C19H30BrNO2S. Calculated (%): C, 54.80; H, 7.26;
N, 3.36; S, 7.70. IR, /cm–1: 1028 (S=O), 1271 (CAr—OH),
3177 (NH). 1H NMR (CDCl3), : 0.84 (t, 3 H, C(9´)H3,
J = 7.2 Hz); 0.91 (d, 3 H, C(7)H3, J = 6.2 Hz); 1.01 (d, 3 H,
C(10)H3), J = 6.7 Hz); 1.04 (d, 3 H, C(9)H3, J = 6.7 Hz);
0.87—1.10 (m, 1 H, H(4a)); 1.17—1.44 (m, 2 H, H(2), H(6a));
1.45—1.62 (m, 1 H, H(3a)); 1.75—2.05 (m, 6 H, H(3e), H(4e),
H(5), H(8), H(8´)); 1.35—2.47 (m, 1 H, H(6e)); 3.20—3.30 (n.m,
1 H, H(1)); 4.03 (q, 1 H, H(1´), J = 7.7 Hz); 5.55 (d, 1 H, NH,
J = 9.2 Hz); 6.18 (d, 1 H, H(4´), J = 8.7 Hz); 6.91 (dd, 1 H, H(5´),
J = 8.5 Hz, J = 1.8 Hz); 7.11 (d, 1 H, H(7´), J = 2.1 Hz); 9.59
(s, 1 H, OH). 13C NMR, : 11.35 (C(9´)), 21.41 (C(9)), 21.72
(C(10)), 22.65 (C(7)), 25.89 (C(3)), 27.62 (C(8)), 28.99 (C(5)),
29.32 (C(8´)), 35.09 (C(4)), 39.43 (C(6)), 47.99 (C(2)), 64.21
(C(1´)), 64.50 (C(1)), 110.86 (C(2´)), 118.32 (C(4´)), 129.58
(C(6´)), 130.43 (C(7´)), 131.30 (C(5´)), 154.04 (C(3´)).
Calculated (%): C, 56.99; H, 7.55; N, 3.50; S, 8.01. IR, /cm–1
:
1248 (CAr—OH), 3292 (NH). 1H NMR (CDCl3), : 0.79—0.98
(m, 13 H, C(7)H3, C(9)H3, C(9´)H3, C(10)H3, H(4a)); 0.91—1.11
(m, 1 H, H(3a)); 1.07—1.34 (m, 2 H, H(2), H(6a)); 1.33—1.51
(m, 1 H, H(8)); 1.63—2.00 (m, 6 H, H(3e), H(4e), H(5), H(6e),
H(8´)); 3.17 (br.s, 1 H, NH); 3.47—3.55 (n.m, 1 H, H(1)); 3.80
(t, 1 H, H(1´), J = 7.2 Hz); 6.77 (d, 1 H, H(4´), J = 8.7 Hz); 7.12
(d, 1 H, H(7´), J = 2.6 Hz); 7.30 (dd, 1 H, H(5´), J = 8.7 Hz,
J = 2.6 Hz); 9.08 (s, 1 H, OH). 13C NMR, : 11.09 (C(9´)), 20.47
(C(9)), 21.23 (C(10)), 22.18 (C(7)), 26.32 (C(8´)), 26.36 (C(5)),
29.95 (C(8´)), 27.64 (C(3)), 29.86 (C(8)), 35.33 (C(4)), 38.68
(C(6)), 47.30 (C(1)), 47.93 (C(2)), 65.77 (C(1´)), 111.24 (C(2´)),
118.82 (C(4´)), 127.43 (C(6´)), 131.49 (C(5´)), 132.28 (C(7´)),
155.58 (C(3´)).
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 12ꢀ03ꢀ31338
mol_a) and the Ural Branch of the Russian Academy of
Sciences (Project No. 13ꢀ3ꢀHPꢀ127).
(RS,1S,2S,5R)ꢀNꢀ[(R)ꢀ1ꢀ(5ꢀBromoꢀ2ꢀhydroxyphenyl]propꢀ
yl)ꢀ2ꢀisopropylꢀ5ꢀmethylcyclohexanesulfinamide ((RSR)ꢀ9c). Yellow
powder, m.p. 59—60 C, []D22 –31.0 (c 0.12, acetone), Rf 0.22
(benzene—AcOEt, 5 : 2). Found (%): C, 54.81; H, 7.24; N, 3.37;
S, 7.69. C19H30BrNO2S. Calculated (%): C, 54.80; H, 7.26;
N, 3.36; S, 7.70. IR, /cm–1: 1020 (S=O), 1275 (CAr—OH),
3171 (NH). 1H NMR (CDCl3), : 0.80—1.07 (m, 13 H, C(7)H3,
C(9)H3, C(9´)H3, C(10)H3, H(4a)); 1.15—1.53 (m, 3 H, H(2),
H(3a), H(6a)); 1.59—1.77 (m, 1 H, H(5)); 1.77—2.11 (m, 5 H,
H(3e), H(4e), H(8); C(8´)H2); 2.39—2.52 (m, 1 H, H(6e));
3.15—3.28 (n.m, 1 H, H(1)); 4.45—4.59 (m, 2 H, H(1´),
NH); 6.72 (d, 1 H, H(4´), J = 8.2 Hz); 7.18—7.30 (m, 2 H,
H(5´), H(7´)); 8.99 (s, 1 H, OH). 13C NMR, : 10.69 (C(9´)),
21.27 (C(9)), 21.36 (C(10)), 22.64 (C(7)), 25.97 (C(3)),
27.70 (C(8)), 28.94 (C(5)), 29.53 (C(8´)), 35.01 (C(4, 6)),
47.72 (C(2)), 56.83 (C(1´)), 63.32 (C(1)), 111.44 (C(2´)),
118.41 (C(4´)), 128.27 (C(6´)), 131.21 (C(7´)), 131.35 (C(5´)),
154.66 (C(3´)).
The authors are grateful to the employees of the Laboꢀ
ratory of physicochemical methods of studies of the Instiꢀ
tute of Chemistry, Komi Scientific Center of the Ural
Branch of the Russian Academy of Sciences E. N. Zainulliꢀ
na and S. P. Kuznetsov for recording NMR spectra and
E. U. Ipatova for recording IR spectra.
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(1S,2S,5R)ꢀNꢀ[1ꢀ(5ꢀBromoꢀ2ꢀhydroxyphenyl)propyl]ꢀ2ꢀisoꢀ
propylꢀ5ꢀmethylcyclohexanesulfenamide (10a). Yellow oily liquid,
[]D22 +104.4 (c 0.19, acetone), Rf 0.48 (benzene—AcOEt, 5 : 2).
Found (%): C, 56.93; H, 7.56; N, 3.50; S, 7.99. C19H30BrNOS.
Calculated (%): C, 56.99; H, 7.55; N, 3.50; S, 8.01. IR, /cm–1
:
1246 (CAr—OH), 3290 (NH). 1H NMR (CDCl3), : 0.62 (d, 3 H,
C(9)H3, J = 6.4 Hz); 0.83 (d, 3 H, C(10)H3, J = 6.7 Hz); 0.87
(d, 3 H, C(9´)H3, J = 7.7 Hz); 0.91 (d, 3 H, C(7)H3, J = 6.4 Hz);
0.85—1.14 (m, 3 H, H(2), H(3a), H(4a)); 1.16—1.32 (m, 1 H,
H(6a)); 1.57 (ddq, 1 H, H(8), J = 9.4 Hz, J = 6.7 Hz, J = 6.5 Hz);
1.60—1.80 (m, 2 H, H(3e), H(4e)); 1.77—1.95 (m, 3 H, H(5),
H(8´)); 1.95—2.06 (m, 1 H, H(6e)); 4.15 (br.s, 1 H, NH);
3.34—3.42 (n.m, 1 H, H(1)); 3.78 (dd, 1 H, H(1´), J = 8.1 Hz,
J = 6.3 Hz); 6.75 (d, 1 H, H(4´), J = 8.7 Hz); 7.14 (d, 1 H, H(7´),
J = 2.3 Hz); 7.28 (dd, 1 H, H(5´), J = 8.6 Hz, J = 2.4 Hz); 9.05
(s, 1 H, OH). 13C NMR, : 11.03 (C(9´)), 19.92 (C(9)), 21.22
(C(10)), 22.16 (C(7)), 26.30 (C(3), C(5)), 27.60 (C(8´)), 29.95
(C(8)), 35.32 (C(4)), 39.55 (C(6)), 49.18 (C(2)), 49.91 (C(1)),
11. G. M. Sheldrick, Acta Crystallogr., Sect A: Found. Crystalꢀ
logr., 2008, 64, 112.
Received June 24, 2013;
in revised form September 24, 2013