A novel method for the stereoselective synthesis of thiiran-2-ylmethyl alkylcarbamates

Article abstract of DOI:10.1055/s-0030-1260175

A highly efficient stereoselective conversion of N-alkyl-5-(acyloxymethyl)- 1,3-oxathiolane-2-imines into thiiran-2-ylmethyl alkylcarbamates is described. The reaction is catalyzed by sodium methoxide and proceeds under mild conditions at room temperature

Full text of DOI:10.1055/s-0030-1260175

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PAPER
A Novel Method for the Stereoselective Synthesis of Thiiran-2-ylmethyl Alkyl-
carbamates
A
Novel Method
f
n
or the Synthe
d
sis of
T
hiira
r
nes ey Shiryaev,*a Vadim Shiryaev,a Alexander Korlukov,b Daniya Khamitovab
a
Samara State Technical University, Galaktionovskaya St. 244, 443100 Samara, Russian Federation
Fax +7(846)3322122; E-mail: andrey_shiryaev@yahoo.com
b
Nesmeyanov Institute of Organoelement Compounds, Vavilov St. 28, 119991 Moscow, Russian Federation
Received 7 June 2011; revised 9 July 2011
compounds such as insecticides, herbicides and anti-can-
cer agents.14
Abstract: A highly efficient stereoselective conversion of N-alkyl-
5-(acyloxymethyl)-1,3-oxathiolane-2-imines into thiiran-2-ylmeth-
yl alkylcarbamates is described. The reaction is catalyzed by sodi-
um methoxide and proceeds under mild conditions at room
temperature in methanol.
Herein, we report a novel method for the synthesis of thi-
iranes 2 from N-alkyl-5-(acyloxymethyl)-1,3-oxathiolan-
2-imines 1. We intended to take advantage of the proper-
ties of imines 1, which contain both imino and ester
groups, to enable their simultaneous or preferential hy-
drolysis. Our initial attempts to hydrolyze preferentially
the ester group in aqueous methanolic sodium hydroxide
yielded predominantly polymeric products. To avoid po-
lymerization and to improve the yield of the target prod-
ucts, we explored the effectiveness of methanolysis in the
presence of a catalyst. We found that sodium methoxide
catalyzed effectively the formation of thiiran-2-ylmethyl
carbamates 2a,b (Scheme 1). Thin-layer chromatographic
monitoring showed that the reaction was complete within
ten minutes at room temperature, with no polymeric prod-
ucts being detected. In the case of the 5-(benzoyloxy-
methyl) derivatives 1a and 1b, the corresponding products
were isolated in high yields by means of column chroma-
tography. The products formed from the 5-(acetyloxy-
methyl) derivatives 1c and 1d did not require chromato-
graphic purification. It was proposed that the reaction of
1,3-oxathiolane-2-imines with anionic nucleophiles
should lead to the formation of S-(oxiran-2-ylmethyl) car-
bamothioates.13,15 Interestingly, under our conditions, the
products of these reactions were thiiran-2-ylmethyl car-
bamates 2a,b.
Key words: thiiranes, imines, esters, tandem reaction, stereoselec-
tivity
Thiiranes are used in organic synthesis, polymer chemis-
try and for preparing medicines, insecticides and herbi-
cides.1 For instance, thiiran-2-ylmethyl derivatives are
employed as inhibitors of human matrix metallo-
proteinases1 and of topoisomerases.2 The reaction of thi-
iranes with ammonia and amines is utilized for preparing
taurine derivatives,3 a class of naturally occurring amino
sulfonic acids. To date, the most efficient method for thi-
irane synthesis involves the conversion of oxiranes into
the corresponding thiiranes using various reagents such as
thiourea and thiocyanic acid salts,4 phosphine sulfide5 or
N,N-dimethylthioformamide.6 Since non-racemic thi-
iranes are required for the synthesis of enzyme
inhibitors1,2 and chelating chiral ligands,7 additional steps
for separating racemic mixtures must be performed. To
improve the existing methods for thiirane synthesis, sev-
eral groups have investigated approaches for the produc-
tion of enantiomerically pure thiiranes. One of these
studies involved reactions of enantiomerically enriched
oxiranes with thiourea in methanol.8 An alternative meth-
od used b-hydroxythiocyanates which are known interme-
diates for the synthesis of thiiranes. Enantiomerically
enriched 1-substituted 3-thiocyanatopropan-2-ols have
been prepared by lipase-catalyzed hydrolysis of the corre-
sponding racemic acetates9 and by asymmetric reduction
of a-thiocyanatoketones with Baker’s yeast.10
In order to investigate the mechanism of this reaction we
synthesized (5R)-N-(1-adamantyl)-5-(benzoyloxymeth-
yl)-1,3-oxathiolan-2-imine (1a) from (2S)-oxiran-2-yl-
methyl benzoate,16a itself prepared by a method described
elsewhere.16 The R-configuration of compound 1a was
confirmed by X-ray analysis (Figure 1). Our data showed
that each crystal cell contained two molecules of 1a in dif-
ferent twisted conformations of the oxathiolane ring and
that the imino group of each molecule had the E-configu-
ration. The reaction of dextrorotatory (R)-1a yielded the
levorotatory product (S)-2a whilst the dextrorotatory car-
bamate 2b was prepared from the levorotatory imine 1d.
The configurations of the thiiran-2-ylmethyl derivatives
2a and 2b were deduced based on the fact that all known
(S)-thiiran-2-ylmethyl esters and ethers are levorotato-
ry.3a,8c,9b,10 We have confirmed the configuration of (R)-2b
from time-dependent density functional theory (TDDFT)
calculations of specific rotations according to the corre-
Taking advantage of the faster alkylation of the thiocy-
anato group compared to the intramolecular cyclization of
b-hydroxythiocyanates, we previously developed a con-
venient method for the synthesis of N-alkyl-1,3-oxathi-
olan-2-imines of type 1.11 These compounds proved to be
useful substrates for the synthesis of alkoxy ureas,11c 1,3-
oxathioles,12 1,3-dithiolanes,13 and biologically active
SYNTHESIS 2011, No. 19, pp 3204–3207
x
x.
x
x
.
2
0
1
1
Advanced online publication: 18.08.2011
DOI: 10.1055/s-0030-1260175; Art ID: T58911SS
© Georg Thieme Verlag Stuttgart · New York

PAPER
A Novel Method for the Synthesis of Thiiranes
3205
H
O
N
S
R1
S
S
NaOMe (10 mol%)
MeOH, r.t.
O
O
N
R1
N
R1
O–
H
N
O
O
O
O
O
S
R1
R2
1a: R1 =1-adamantyl; R2 = Ph
1b: R1 = t-Bu; R2 = Ph
2a: R1 = 1-adamantyl
2b: R1 = t-Bu
1c: R1 = 1-adamantyl; R2 = Me
1d: R1 = t-Bu; R2 = Me
Scheme 1 Synthesis of thiiran-2-ylmethyl carbamates 2a,b
sponding calculations on (S)-epichlorohydrin.17 Calcula- using the B3LYP/aug-cc-pVDZ level gave the Boltzmann
tions of the energies of the conformers of carbamate (R)- averaged values. A comparison of the calculated and
2b at the B3LYP/6-311+G* level of theory indicated eight experimental (in parentheses, c 1.11, CH2Cl2, 20 °C) spe-
stable conformers with populations of not less than 1% in cific rotation values confirmed the (R)-configuration of
dichloromethane at 298 °K. The following specific rota- carbamate 2b according to the known criteria:18 +49.4
tion calculations of these conformers at five wavelengths (+31.2) at 589 nm, +57.6 (+36.5) at 546 nm, +89.4 (+53.1)
at 436 nm, +101.4 (+64.3) at 405 nm, and +115.0 (+77.6)
at 365 nm.
These data suggest that the transformation of (5R)-N-(1-
adamantyl)-5-(benzoyloxymethyl)-1,3-oxathiolan-2-im-
ine (1a) into (2S)-thiiran-2-ylmethyl 1-adamantylcarbam-
ate (2a) proceeds via several intermediates, which are
shown in Scheme 2. Structures A and C could form stable
products whilst the bicyclic structure B could exist as an
intermediate or a transition state. The formation of a sim-
ilar cage bicyclic intermediate or transition state could be
postulated for the transformation of the azidomethyl lac-
tone fragment of pyridooxazinones into the hydroxy lac-
tam fragment of pyridodiazepinones via Staudinger
reduction.19 Also, a proposed mechanism for the 2,3-ep-
oxy alcohol O-thiocarbamate rearrangement includes an
N,N-dimethyl-1,3-oxathiolane-2-immonio intermediate
which is transformed into a mixture of thiiran-2-ylmethyl
dimethylcarbamate derivatives via the same bicyclic
structure.20
In conclusion, we have described a new method for the
synthesis of thiiranes via a tandem reaction. Initial alkali-
catalyzed methanolysis of the ester group of the N-alkyl-
5-(acyloxymethyl)-1,3-oxathiolane-2-imine is then fol-
lowed by spontaneous intramolecular rearrangement lead-
ing to thiirane formation. The reaction is characterized by
stereoselectivity, high yields and mild conditions. We be-
lieve that this reaction provides a practical alternative to
existing methods available for the synthesis of both race-
mic and enantiomerically enriched thiiranes.
Figure 1 Crystal structure of (R)-N-(1-adamantyl)-5-(benzoyloxy-
methyl)-1,3-oxathiolan-2-imine (1a) (ORTEP view); hydrogen atoms
are omitted for clarity. Selected bond lengths (Å) and angles (°): C11–
N1 = 1.257, C11–S1 = 1.767, C11–O1 = 1.368, C11–S1–C10 = 91.9,
C11–O1–C9 = 112.9, O1–C9–C10–S1 = 35.4, O4–C30–C31–S2 =
–41.4.
O
MeO–
S
S
N–
N
N
O
OBz
S–
O–
S
O
1a
O
– BzOMe
R
R
R
R
A
B
H
N
MeOH
N
N
O
S
O
O
S
R
R
– MeO–
O–
O
O
2a
C
Scheme 2 Transformation of 1a into thiirane 2a
Synthesis 2011, No. 19, 3204–3207 © Thieme Stuttgart · New York

3206
A. Shiryaev et al.
PAPER
Anal. Calcd for C15H19NO3S: C, 61.41; H, 6.53; N, 4.77; S, 10.93.
Found: C, 61.38; H, 6.58; N, 4.61; S, 10.66.
All commercially obtained reagents were used without further puri-
fication unless stated otherwise. All solvents were distilled prior to
use. Melting points were obtained using a PTP melting point appa-
ratus and are uncorrected. All the reactions were monitored by TLC
performed on precoated silica gel plates (Merck). Compounds were
made visual with I2. IR spectra of samples prepared as KBr pellets
were recorded on a Shimadzu FTIR-8500S spectrometer. NMR
spectra were recorded on a Bruker AM 300 spectrometer; TMS was
used as an internal standard. The number of signals in the 13C NMR
spectra for compounds 1a–d correspond to the fact that these com-
pounds are mixtures of Z/E-isomers11b in solution. Mass spectra
were recorded in DEP mode on a Finnigan DSQ GC–MS. Elemen-
tal analyses were obtained using a EuroEA Elemental Analyzer.
Optical rotations were measured with an Autopol V Plus polarime-
ter. All calculations were performed using the Gaussian program21
with the PCM implicit solvation model. (2R)-Oxiran-2-ylmethyl ac-
etate was prepared by hydrolytic kinetic resolution22 of the corre-
sponding racemate catalyzed by (S,S)-(salen)Co(III)OAc complex;
[a]D22 29.6 (neat) {Lit.23[a]D22 29.9 (neat)}.
(5R/S)-N-(1-Adamantyl)-5-(acetyloxymethyl)-1,3-oxathiolan-2-
imine (1c)
Yield: 2.26 g (61%); white needles; mp 90–91 °C (acetone).
IR (KBr): 2904, 1735, 1666, 1276, 1064 cm–1.
1H NMR (300 MHz, CDCl3): d = 1.50–1.66 (m, 6 H), 1.75–1.90 (m,
6 H), 1.92–2.08 (m, 3 H), 2.10 (s, 3 H), 3.05–3.40 (m, 2 H), 4.25–
4.30 (m, 2 H), 4.42–4.52 (m, 0.5 H), 4.72–4.82 (m, 0.5 H).
13C NMR (75 MHz, CDCl3): d = 20.5, 20.6, 29.5, 29.7, 31.5, 34.5,
36.2, 36.4, 41.6, 42.4, 53.0, 56.4, 63.2, 63.4, 74.9, 80.1, 152.9,
154.8, 170.2, 170.3.
MS (EI, 70 eV): m/z (%) = 309 (10) [M]+, 177 (15), 135 (36), 132
(72), 120 (47), 73 (42), 72 (100), 43 (36).
Anal. Calcd for C16H23NO3S: C, 62.11; H, 7.49; N, 4.53; S, 10.36.
Found: C, 62.15; H, 7.40; N, 4.48; S, 10.10.
(5S)-N-tert-Butyl-5-(acetyloxymethyl)-1,3-oxathiolan-2-imine
(1d)
N-Alkyl-5-(acyloxymethyl)-1,3-oxathiolan-2-imines; General
Procedure
Yield: 1.97 g (71%); colorless oil; [a]D20 –15.5 (c 1.12, benzene).
NH4SCN (0.95 g, 12 mmol) was added to a soln of the appropriate
oxirane (12 mmol) in glacial AcOH (6 mL, 100 mmol) at 15 °C, and
the mixture stirred for 2 h at 15 °C. Next, this mixture was added
dropwise to a soln of 1-adamantanol (1.8 g, 12 mmol) in H2SO4 (12
mL, d 1.84) at 0–5 °C. In the case of tert-butyl derivatives 1b,d,
t-BuOH (1.4 mL, 15 mmol) was dissolved in the NH4SCN–ox-
irane–AcOH mixture and the resulting soln added dropwise to
H2SO4 (12 mL, d 1.84) at 0–5 °C. The mixture was poured onto ice
and extracted with CHCl3 (3 × 20 mL). The aq layer was neutralized
with Na2CO3 (until pH >9), extracted with CH2Cl2 (2 × 20 mL). The
combined organic layer was dried (Na2SO4), filtered over silica gel
(5 g) and the solvent removed by distillation.
IR (KBr): 2968, 1746, 1669, 1234, 1047 cm–1.
1H NMR (300 MHz, CDCl3): d = 1.15 (s, 9 H), 1.97 (s, 3 H), 3.02–
3.38 (m, 2 H), 4.12–4.28 (m, 2 H), 4.40–4.50 (m, 0.5 H), 4.60–4.70
(m, 0.5 H).
13C NMR (75 MHz, CDCl3): d = 20.4, 20.6, 28.9, 29.6, 30.6, 31.7,
52.6, 55.5, 63.2, 63.3, 75.1, 80.2, 154.2, 155.3, 170.1, 170.2.
MS (EI, 70 eV): m/z (%) = 231 (1) [M]+, 216 (19), 133 (8), 84 (100),
73 (21), 72 (26), 57 (30), 43 (40).
Anal. Calcd for C10H17NO3S: C, 51.92; H, 7.41; N, 6.06; S, 13.86.
Found: C, 51.91; H, 7.29; N, 5.95; S, 13.51.
(5R)-N-(1-Adamantyl)-5-(benzoyloxymethyl)-1,3-oxathiolan-2-
imine (1a)
Thiiran-2-ylmethyl Carbamates; General Procedure
N-Alkyl-5-(acyloxymethyl)-1,3-oxathiolan-2-imine 1 (9.7 mmol)
was added to a soln of Na (20 mg, 0.9 mmol) in abs MeOH (20 mL).
The mixture was stirred for 10 min at r.t. and then neutralized with
AcOH (0.1 mL, 1.7 mmol). The solvent was removed in vacuo and
the residue purified by column chromatography (silica gel, PE–
CH2Cl2, 5:1). No chromatographic purification was required for the
acetoxymethyl derivative.
Yield: 1.92 g (43%); white needles; mp 105–107 °C (acetone);
[a]D20 +21.0 (c 1.25, benzene).
IR (KBr): 2908, 1720, 1662, 1261, 1056, 714 cm–1.
1H NMR (300 MHz, CDCl3): d = 1.63–1.73 (m, 6 H), 1.92–2.03 (m,
6 H), 2.10–2.20 (m, 3 H), 3.15–3.48 (m, 2 H), 4.35–4.45 (m, 2 H),
4.51–4.59 (m, 0.5 H), 4.81–4.90 (m, 0.5 H), 7.40–7.50 (m, 2 H),
7.51–7.60 (m, 1 H), 8.02–8.11 (m, 2 H).
(2R/S)-Thiiran-2-ylmethyl 1-Adamantylcarbamate (2a)
Yield: 2.15 g (83%); colorless powder; mp 64–65 °C.
IR (KBr): 3317, 2908, 1708, 1531, 1234, 1057 cm–1.
13C NMR (75 MHz, CDCl3): d = 29.7, 29.9, 31.7, 34.9, 36.5, 36.6,
41.8, 42.5, 53.3, 56.7, 64.1, 64.2, 75.2, 80.4, 128.5, 129.4, 129.9,
133.5, 153.4, 155.4, 166.2.
MS (EI, 70 eV): m/z (%) = 371 (12) [M]+, 194 (91), 177 (12), 161
(25), 135 (35), 120 (30), 105 (100), 93 (17), 77 (38), 72 (60).
1H NMR (300 MHz, CDCl3): d = 1.58–1.68 (m, 6 H), 1.84–1.96 (m,
6 H), 2.02–2.12 (m, 3 H), 2.25 (d, J = 7.2 Hz, 1 H), 2.50 (d, J = 7.2
Hz, 1 H), 3.04–3.17 (m, 1 H), 4.07 (d, J = 7.8 Hz, 2 H), 4.64 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 23.7, 29.4, 31.6, 36.2, 41.0, 50.8,
68.0, 154.1.
Anal. Calcd for C21H25NO3S: C, 67.89; H, 6.78; N, 3.77; S, 8.63.
Found: C, 67.81; H, 6.77; N, 3.67; S, 8.45.
(5R/S)-N-tert-Butyl-5-(benzoyloxymethyl)-1,3-oxathiolan-2-
imine (1b)
Yield: 2.64 g (70%); colorless oil.
IR (KBr): 2966, 1724, 1670, 1272, 1095 cm–1.
1H NMR (300 MHz, CDCl3): d = 1.19 (s, 9 H), 3.11–3.44 (m, 2 H),
4.35–4.49 (m, 2 H), 4.55–4.65 (m, 0.5 H), 4.85–4.95 (m, 0.5 H),
7.30–7.40 (m, 2 H), 7.41–7.51 (m, 1H), 7.95–7.98 (m, 2 H).
13C NMR (75 MHz, CDCl3): d = 28.8, 29.6, 31.4, 34.2, 52.5, 55.4,
63.7, 64.8, 75.1, 80.2, 128.1, 128.2, 129.0, 129.2, 129.4, 129.5,
133.0, 133.1, 165.6.
MS (EI, 70 eV): m/z (%) = 267 (9) [M]+, 234 (2), 196 (9), 135 (100),
73 (63), 72 (17), 45 (42).
Anal. Calcd for C14H21NO2S: C, 62.89; H, 7.92; N, 5.24; S, 11.99.
Found: C, 62.78; H, 7.99; N, 5.15; S, 11.71.
(2S)-Thiiran-2-ylmethyl 1-Adamantylcarbamate (2a)
Yield: 2.20 g (85%); colorless powder; mp 62–63 °C; [a]D20 –20.0
(c 1.04, CH2Cl2).
Anal. Calcd for C14H21NO2S: C, 62.89; H, 7.92; N, 5.24; S, 11.99.
Found: C, 62.81; H, 7.90; N, 5.18; S, 11.69.
MS (EI, 70 eV): m/z (%) = 293 (2) [M]+, 195 (16), 105 (80), 84
(100), 77 (45), 73 (38), 72 (27), 57 (29).
(2R)-Thiiran-2-ylmethyl tert-Butylcarbamate (2b)
Yield: 1.49 g (81%); pale-yellow oil; [a]D20 +31.2 (c 1.11, CH2Cl2).
Synthesis 2011, No. 19, 3204–3207 © Thieme Stuttgart · New York

PAPER
A Novel Method for the Synthesis of Thiiranes
3207
IR (KBr): 3348, 2970, 1728, 1712, 1269, 1080 cm–1.
Wong, C.-H. J. Org. Chem. 1990, 55, 4897. (b) Zunszain,
P. A.; Varela, O. Tetrahedron: Asymmetry 2000, 11, 765.
(c) Herault, D.; Saluzzo, C.; Lemaire, M. Tetrahedron:
Asymmetry 2006, 17, 1944.
1H NMR (300 MHz, CDCl3): d = 1.27 (s, 9 H), 2.19 (d, J = 7.2 Hz,
1 H), 2.45 (d, J = 7.2 Hz, 1 H), 3.00–3.10 (m, 1 H), 4.02 (d, J = 7.8
Hz, 2 H), 4.81 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 23.5, 28.8, 31.4, 50.3, 67.9, 154.2.
MS (EI, 70 eV): m/z (%) = 189 (29) [M]+, 118 (11), 90 (62), 73
(100), 72 (94), 57 (83), 45 (60).
(9) (a) Łukowska, E.; Plenkiewicz, J. Tetrahedron: Asymmetry
2005, 16, 2149. (b) Łukowska, E.; Plenkiewicz, J.
Tetrahedron: Asymmetry 2007, 18, 493.
(10) Łukowska, E.; Plenkiewicz, J. Tetrahedron: Asymmetry
2007, 18, 1202.
Anal. Calcd for C8H15NO2S: C, 50.77; H, 7.99; N, 7.40; S, 16.94.
Found: C, 50.71; H, 7.92; N, 7.33; S, 16.69.
(11) (a) Shiryaev, A. K.; Moiseev, I. K.; Popov, V. A. Zh. Org.
Khim. 1992, 28, 418. (b) Shiryaev, A. K.; Moiseev, I. K.;
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K.; Kong Thoo lin, P.; Moiseev, I. K. Synthesis 1997, 38.
(12) Shiryaev, A. K.; Kryslov, I. Y.; Moiseev, I. K. Zh. Org.
Khim. 2000, 36, 458.
(13) Shiryaev, A. K. Zh. Org. Khim. 2003, 39, 1877.
(14) (a) Condreay, L. D.; Condreay, J. P.; Jansen, R. W.; Paff, M.
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(d) Irikuri, T.; Suzue, S.; Hasegawa, Y.; Kawasaki, H. Jap.
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(e) Pflugfelder, B. US Patent 3639610, 1972; Chem. Abstr.
1972, 76, 140770v. (f) Oyamada, K.; Nagano, M.;
Tobizuka, J.; Matsui, K. Jap. Patent 7246064, 1972; Chem.
Abstr. 1973, 78, 124598f. (g) Sauer, W.; Goldner, H.;
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X-ray Crystallographic Data of Compound 1a
C21H25NO3S, M = 371.48, monoclinic, space group P21,
a = 6.380(3) Å, b = 17.906(8) Å, c = 16.520(7) Å, b = 99.585(7)°,
V = 1861.0(14) Å3, Z = 4, Dc = 1.326 g·cm–3. Intensities of 10084
independent reflections were measured on a Bruker Smart 1000
CCD diffractometer, 2q ≤59.9°, l[Mo-Ka] = 0.71073 Å. The struc-
ture was solved by the direct method and refined using full matrix
least-squares on F2 using SHELXTL PLUS 5.10 software. All non-
hydrogen atoms were refined anisotropically. The hydrogen atoms
were placed in the calculated positions and refined isotropically.
The absolute crystal structure and absolute molecular configuration
were determined using the Flack parameter [absolute structure pa-
rameter –0.07(5)]. The refinement converged to R1 = 0.049,
wR2 = 0.110, GOF = 0.998 [7526 observed reflections with I2 >
2s(I)]. Atomic coordinates, bond lengths, bond angles and thermal
parameters have been deposited with the Cambridge Crystallo-
graphic Data Centre as supplementary publication no. CCDC
783390 and can be obtained free of charge on application to CCDC,
12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(1223)336033;
e-mail: deposit@ccdc.cam.ac.uk; or via www.ccdc.cam.uk/conts/
retrieving.html.
(15) (a) Wagner-Jauregg, T.; Häring, M. Helv. Chim. Acta 1958,
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Acknowledgment
This work was financially supported by Samara State Technical
University (Reg. No. 554/11).
(19) Chen, Y.; Porco, J. A. Jr.; Panek, J. S. Org. Lett. 2007, 9,
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