Highly diastereoselective synthesis of 2-monosubstituted 1R,5S(1S,5R)-glycoluriles on the basis of S- and R-N-carbamoyl-α-amino acids

Article abstract of DOI:10.1070/MC2003v013n06ABEH001802

The reactions of 4,5-dihydroxyimidazolidin-2-one with chiral S- and R-N-carbamoyl-α-amino acids occur diastereoselectively with the formation of corresponding 1R,5S(1S,5R)-glycoluriles as predominant diastereomers; the absolute configuration is determined

Full text of DOI:10.1070/MC2003v013n06ABEH001802

, 2003, 13(6), 269–271
Highly diastereoselective synthesis of 2-monosubstituted 1R,5S(1S,5R)-glycoluriles
on the basis of S- and R-N-carbamoyl-α-amino acids
Angelina N. Kravchenko,*a Konstantin Yu. Chegaev,a Il’ya E. Chikunov,a Pavel A. Belyakov,a
Elena Yu. Maksareva,a Konstantin A. Lyssenko,b Oleg V. Lebedeva and Nina N. Makhovaa
a N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow, Russian Federation.
Fax: +7 095 135 5328; e-mail:kani@.ioc.ac.ru
b A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 119991 Moscow, Russian Federation.
Fax: +7 095 135 5085; e-mail: kostya@xrlab.ineos.ac.ru
10.1070/MC2003v013n06ABEH001802
The reactions of 4,5-dihydroxyimidazolidin-2-one with chiral S- and R-N-carbamoyl-α-amino acids occur diastereoselectively
with the formation of corresponding 1R,5S(1S,5R)-glycoluriles as predominant diastereomers; the absolute configuration is
determined for three stereoisomers by X-ray diffraction analysis.
The synthesis and stereochemistry of glycoluriles and their
O(3)
sulfo analogues is of considerable interest.1–6 Recently, we
H(4O)
H(5)
H(1)
N(4)
synthesised racemic 2-monosubstituted glycoluriles using the
reactions of 4,5-dihydroxyimidazolidin-2-one 1 with 1-mono-
substituted ureas.6 The formation of two diastereomers would
be expected with the use of monosubstituted ureas with substi-
tuents having a specified configuration in the reaction of bicycle
formation.
In this work, we studied in detail the reactions of compound
1 with chiral S- (Scheme 1) and R-N-carbamoyl-α-amino acids
2a–d, which were prepared by the interaction of KCNO with
S-norvaline, S-α-aminobutyric acid, S-methionine, S-glutamine
and R-methionine, respectively. Depending on the solubility of
the parent compounds, cyclocondensation was performed in
aqueous or aqueous isopropanol solutions at pH 1–2. In all
cases, target glycoluriles 3 and 3' were obtained in preparative
yields.
C(13)
C(1)
C(5)
H(8N)
O(4)
N(2)
N(6)
H(4N)
C(9)
N(8)
H(6N)
O(2)
O(1)
C(10)
C(3)
C(7)
C(11)
S(1)
C(12)
Figure 1 The general view of 3c. The selected bond lengths (Å): N(2)–
C(1) 1.462(2), N(2)–C(3) 1.366(2), N(2)–C(9) 1.455(2), N(8)–C(1)
1.438(2), N(8)–C(7) 1.350(2), N(4)–C(3) 1.353(2), N(4)–C(5) 1.436(2),
N(6)–C(5) 1.452(2), N(6)–C(7) 1.358(2), O(1)–C(3) 1.234(2), O(2)–C(7)
1.238(2); bond angles (°): N(8)–C(1)–N(2) 114.4(1), N(8)–C(1)–C(5)
103.1(1), N(2)–C(1)–C(5) 102.2(1), C(3)–N(2)–C(9) 122.2(1), C(3)–N(2)–
C(1) 111.3(1), C(9)–N(2)–C(1) 123.7(1), O(1)–C(3)–N(4) 125.3(1), O(1)–
C(3)–N(2) 125.7(1), N(4)–C(3)–N(2) 108.9(1), C(3)–N(4)–C(5) 112.7(1),
N(4)–C(5)–N(6) 115.0(1), N(4)–C(5)–C(1) 103.0(1), N(6)–C(5)–C(1)
101.9(1), C(7)–N(6)–C(5) 111.6(1), O(2)–C(7)–N(8) 124.0(1), O(2)–C(7)–
N(6) 127.0(1), N(8)–C(7)–N(6) 109.0(1), C(7)–N(8)–C(1) 112.3(1). Con-
formation: C(1)N(2)C(3)N(4)C(5) – envelope [deviation of N(2) 0.16 Å];
C(1)N(1)C(3)N(2)C(2) – envelope [deviation of C(5) 0.22 Å].
H
H2N
OH
N
N
*
*
O
i
O
HN
OH
(
)
S
R
COOH
H
1
2
H
N
H
H
H
N
O
( )
S
(R)
NH
N
N
O
O
O
O
HN
R2
and 3'c is 15:1, as well as for 3d and 3'd. This fact is indicative
of the high diastereoselectivity of the reactions of 1 with 2a–d.
The signals of the CH protons of major diastereomers are down-
field shifted with respect to the corresponding signals of minor
diastereomers. The signals of the other protons manifest them-
selves as multiplets. To determine accurately the chemical shifts
and spin–spin coupling constants of C(1)H and C(5)H protons
in test compounds 3 (all signals were broadened), calculations
were performed by the NUMMRIT method with the use of the
Xsim (Linux) program.
We failed to separate the mixtures of diastereomers 3a and
3'a, 3b and 3'b because their physico-chemical properties are
similar. Individual diastereomers 3c and 3'c were obtained by
recrystallization of the resulting mixture from water. For stereo-
isomers 3c (major) and 3'c (minor), the angles of optical rota-
tion were found to be +18.50° and –77.78° (c 2, 1 N NaOH),
respectively. In the course of separation of a predominant
isomer from the product of reaction of 1 and 2d, which was
recrystallised from methanol in the presence of trace hydrochloric
acid, the amide group underwent hydrolysis to the carboxyl
group followed by esterification of both of the carboxyl groups
to methyl esters with the formation of 3d.†
(
)
( )
R
S
N
H
N
N
H
N
O
COOR1
R
COOR1
( )
S
(S)
R
3
3'
(minor)
4
(major)
2 a R = Pr
b R = Et
3, 3' a R = Pr, R1 = H
b R = Et, R1 = H
c R = CH2CH2SMe
d R = CH2CH2CONH2
c R = CH2CH2SMe, R1 = H
d R = CH2CH2COOMe, R1 = Me
4 a R2 = H
b R2 = Pr
c R2 = Et
d R = CH2CH2SMe
Scheme 1 Reagents and conditions: i, H2O (H2O/PriOH), HCl, 90 °C, 1 h.
The diastereomeric composition of reaction products was
determined by H NMR spectroscopy. We found that isolated
1
glycoluriles were formed as two diastereomers 3a–d and 3'a–d,
which appeared as the doubling of signals from all groups of
protons. An analysis of the most informative region of the spectra
of these compounds (the region 3.7–4.5 ppm for the signals of
CH protons from the amino acid fragment) indicated that the
ratio of diastereomers for glycoluriles 3a and 3'a, 3b and 3'b is
» 3:1 or 5:1, respectively, whereas the ratio for compounds 3c
The interaction of compound 1 with R-N-carbamoylmethio-
nine also occurred with high diastereoselectivity (the diastereomer
ratio 15:1), and predominant diastereomer 3''c was separated
– 269 –

, 2003, 13(6), 269–271
by crystallization from water; the angle of optical rotation was
–18.52°. Note that stereoisomers 3c and 3'c exhibited opposite
rotation angles, equal melting temperatures, and identical NMR
spectra; that is, they are enantiomers.
In the reactions of compounds 1 with S- and R-N-carbamoyl-
α-amino acids, the products of two side processes were also
found: the rearrangement of 4,5-dihydroxyimidazolidin-2-one 1
into hydantoin 4a and the self-cyclization of N-carbamoyl-α-
amino acids 2a–c into hydantoins 4b–d (Scheme 1). Yields of
4a–d were in the 38–40% region. These processes are well
known, and the resulting hydantoins were described in the lite-
rature.7,8
H(4O)
O(3)
O(4)
H(5)
C(5)
H(1)
C(13)
C(1)
N(4)
H(6N)
O(2)
N(6)
N(2)
C(3)
C(9)
H(4N)
N(8)
H(8N)
C(10)
C(7)
O(1)
C(12)
C(11)
To determine the configurations of asymmetric C(1) and C(5)
atoms in the glycoluriles synthesised, we performed X-ray dif-
fraction analysis of single crystals of the predominant isomers
of compounds 3c,d and minor stereoisomer 3'c.‡
S(1)
Figure 2 The general view of 3'c. The selected bond lengths (Å): N(2)–
C(1) 1.450(3), N(2)–C(3) 1.382(3), N(2)–C(9) 1.463(3), N(4)–C(3)
1.351(4), N(4)–C(5) 1.435(4), N(6)–C(5) 1.439(4), N(6)–C(7) 1.341(4),
N(8)–C(1) 1.445(3), N(8)–C(7) 1.346(4), O(1)–C(3) 1.223(4), O(2)–C(7)
1.231(4); bond angles (°): N(8)–C(1)–N(2) 115.0(2), N(8)–C(1)–C(5)
102.4(2), N(2)–C(1)–C(5) 103.9(2), C(3)–N(2)–C(1) 111.0(2), C(3)–N(2)–
C(9) 121.9(2), C(1)–N(2)–C(9) 118.5(2), O(1)–C(3)–N(4) 125.6(2), O(1)–
C(3)–N(2) 126.2(3), N(4)–C(3)–N(2) 108.2(2), C(3)–N(4)–C(5) 113.2(2),
N(4)–C(5)–N(6) 114.7(3), N(4)–C(5)–C(1) 103.2(2), N(6)–C(5)–C(1)
103.5(2), C(7)–N(6)–C(5) 112.4(3), O(2)–C(7)–N(6) 125.2(3), O(2)–C(7)–
N(8) 126.1(3), N(6)–C(7)–N(8) 108.7(3), C(7)–N(8)–C(1) 112.7(3). Con-
formation: C(1)N(2)C(3)N(4)C(5) cycle – envelope [deviation of C(3)
0.09 Å], C(1)C(5)N(6)C(7)N(8) cycle – envelope [deviation of C(7) 0.06 Å].
The main geometry parameters in 3c, 3'c and 3d are similar.‡
The torsion angles H(1)C(1)C(5)H(5) are 2° and 12° in 3d
and 3c, respectively. The conformation of five-membered rings
is a flattened envelope. In the ring with the substituted nitro-
gen atom, the C(3) atom projects out of the plane, whereas the
C(5) or C(7) atom projects out of the plane in the other ring
(Figures 1–3). Nitrogen atoms are planar with an insignificant
pyramidalization of the substituted N(2) atom [the sum of
angles at N(2) varied from 351.7(2)° to 357.2(2)°].
The presence of a great number of proton donors and proton
acceptors in the molecules resulted in a complex supramole-
cular organization in crystals. In this case, despite considerable
differences, the systems of hydrogen bonds in the three test
compounds were somewhat similar. Thus, the H(6N) atoms in
all of the structures participate in intermolecular H-bonds with
O(1) atoms [N(6)···O(1) varied from 2.876(2) to 3.001(2) Å].
Moreover, in 3c and 3'c, the H-bond systems for the H(4N)
atom [N(4)–H(4N)···O(3)] and the hydroxyl group [O(4)–
H(4O)···O(2)] are coincident, whereas the H(8N) atom partici-
†
All new compounds exhibited satisfactory elemental analyses, and
their structures were confirmed by IR, H and 13C NMR spectroscopy.
1
1H and 13C NMR spectra were recorded on Bruker WM-250 (250 MHz)
and Bruker AM-300 (75.5 MHz) spectrometers, respectively. Chemical
shifts were measured with reference to the residual protons of a
[2H6]DMSO solvent (d 2.50 ppm).
Initial 4,5-dihydroxyimidazolidin-2-one 1 was synthesised according
to a known method from urea and glyoxal;9 N-carbamoyl-α-amino
acids 2a–d were synthesised analogously to the published methods from
α-amino acids and KOCN.10,11
2-[(1R,5S)+(1S,5R)-(3,7-Dioxo-2,4,6,8-tetraazabicyclo[3.3.0]oct-2-
yl)]-2(S)-pentanoic acid 3a + 3'a: yield 33%. 1H NMR ([2H6]DMSO) d:
0.81–0.95 (m, 3H, Me), 1.15–1.51 (m, 2H, CH2), 1.63–2.06 (m, 2H,
CH2), 3.85 (dd, 1H, CH, 3J 4.89 Hz, 3J 10.37 Hz) for 3'a, 4.23 (dd, 1H,
CH, J 6.11 Hz, J 9.27 Hz) for 3a, 5.11–5.43 (m, 2H, CH–CH), 7.11,
7.27 7.36. 7.36 7.43, 7.61 (5br. s, 3H, 3NH), 12.61 (br. s, 1H, COOH).
2-[(1R,5S)+(1S,5R)-(3,7-Dioxo-2,4,6,8-tetraazabicyclo[3.3.0]oct-2-
yl)]-2(S)-butanoic acid 3b + 3'b: yield 35%. 1H NMR ([2H6]DMSO) d:
0.81–1.02 (m, 3H, Me), 1.67–2.04 (m, 2H, CH2), 3.78 (dd, 1H, CH,
3J 6.10 Hz, 3J 9.76 Hz) for 3'b, 4.15 (dd, 1H, CH, 3J 4.89 Hz, 3J
10.38 Hz) for 3b, 5.18–5.50 (m, 2H, CH–CH), 7.11, 7.28, 7.33, 7.41,
7.61 (5br. s, 3H, NH), 12.65 (br. s, 1H, COOH).
‡
Crystallographic data for compounds 3c, 3'c and 3d.
The crystal of 3c (C9H14N4O4S) is orthorhombic at 110 K, space
group P212121, a = 8.9981(9) Å, b = 10.808(1) Å, c = 12.589(1) Å, V =
= 1224.2(2) Å3, Z = 4 (Z' = 1), M = 274.30, dcalc = 1.488 g cm–3,
m(MoKα) = 2.79 cm–1, F(000) = 576.
The crystal of 3'c (C9H14N4O4S) is orthorhombic at 298 K, space
group P212121, a = 6.084(5) Å, b = 9.744(7) Å, c = 20.607(17) Å, V =
= 1221.7(16) Å3, Z = 4 (Z' = 1), M = 274.30, dcalc = 1.491 g cm–3,
m(MoKα) = 2.79 cm–1, F(000) = 576.
The crystal of 3d (C11H16N4O6) is trigonal at 298 K, space group
P3221, a = 10.492(2) Å, c = 22.149(4) Å, V = 2111.5(6) Å3, Z = 6
(Z' = 1), M = 300.28, dcalc = 1.417 g cm–3, m(MoKα) = 1.16 cm–1,
F(000) = 948.
Intensities of 10347 (3c), 2075 (3'c) and 3032 (3d) reflections were
measured with a Smart 1000 CCD diffractometer [l(MoKα) = 0.71072 Å,
w-scan with a 10 s exposure, 2q < 60°] at 100 K (3c) and with Siemens
P3/PC [l(MoKα) = 0.71072 Å, q/2q scan, 2q < 60° and 52°] at 298 K
(3'c and 3e), 3582 (3c), 2075 (3'c) and 2739 (3d) independent reflec-
tions were used in the further refinement. The structures were solved by
a direct method and refined by the full-matrix least-squares technique
against F2 in the anisotropic-isotropic approximation. The analysis of
the Fourier synthesis has revealed that ester groups in 3d are disordered.
The absolute configurations of 3c and 3'c were determined on the basis
of the Flack parameter. The refinement converged to wR2 = 0.0827 and
GOF = 1.043 for all independent reflections [R1 = 0.0364 was calculated
against F for 3245 observed reflections with I > 2s(I)] for 3c; to wR2 =
= 0.1419 and GOF = 1.025 for all independent reflections [R1 = 0.0492
was calculated against F for 1621 observed reflections with I > 2s(I)]
for 3'c and to wR2 = 0.1550 and GOF = 0.954 for all independent reflec-
tions [R1 = 0.0552 was calculated against F for 1828 observed reflections
with I > 2s(I)] for 3d. All calculations were performed using SHELXTL
PLUS 5.0.
Atomic coordinates, bond lengths, bond angles and thermal param-
eters have been deposited at the Cambridge Crystallographic Data Centre
(CCDC). These data can be obtained free of charge via www.ccdc.cam.uk/
conts/retrieving.html (or from the CCDC, 12 Union Road, Cambridge
CB2 1EZ, UK; fax: +44 1223 336 033; or deposit@ccdc.cam.ac.uk).
Any request to the CCDC for data should quote the full literature citation
and CCDC reference number 227399–227401. For details, see ‘Notice to
Authors’, Mendeleev Commun., Issue 1, 2003.
3
3
(+)-2-[(1R,5S)-(3,7-Dioxo-2,4,6,8-tetraazabicyclo[3.3.0]oct-2-yl)]-2(S)-
4-methylthiobutanoic acid 3c: yield 37%, mp 256–258 °C (decomp.), [a]D20
+18.50° (c 2; 1 N NaOH). 1H NMR ([2H6]DMSO) d: 2.05–2.17 (m, 5H,
3
Me + CH2), 2.36–2.64 (m, 2H, CH2), 4.47 (dd, 1H, CH, 3J 9.4 Hz, J
6.3 Hz), 5.29 [dt, 1H, C(1)H, 3J 8.44 0.04 Hz, 3J 1.7 Hz], 5.41 [dd, 1H,
3
3
C(5)H, J 8.44 0.04 Hz, J 2.4 Hz], 7.25 (br. s, 2H, 2NH), 7.48 (br. s,
1H, NH), 12.81 (br. s, 1H, OH). 13C NMR ([2H6]DMSO) d: 14.64 (Me),
28.79 (CH2), 30.28 (CH2), 53.18 (CH), 62.99 (CH), 67.48 (CH), 160.02
(CO), 161.53 (CO), 173.01 (COOH).
(–)-2-[(1S,5R)-(3,7-Dioxo-2,4,6,8-tetraazabicyclo[3.3.0]oct-2-yl)]-2(S)-
4-methylthiobutanoic acid 3'c: yield 6%, mp 233–235 °C (decomp.), [a]D20
–77.78° (c 2; 1 N NaOH). 1H NMR ([2H6]DMSO) d: 2.10–2.19 (m, 5H,
Me + CH2), 2.51–2.61 (m, 2H, CH2), 4.07 (dd, 1H, CH, 3J 4.89 Hz,
3J 10.36 Hz), 5.29 [br. d, 1H, C(1)H, 3J 8.16 0.03 Hz], 5.34 [br. d, 1H,
3
C(5)H, J 8.16 0.03 Hz], 7.28 (s, 1H, NH), 7.38 (s, 1H, NH), 7.51 (s,
1H, NH), 12.75 (br. s, 1H, OH).
(–)-2-[(1S,5R)-(3,7-Dioxo-2,4,6,8-tetraazabicyclo[3.3.0]oct-2-yl)]-2(R)-
4-methylthiobutanoic acid 3''c: yield 37%, mp 256–258 °C (decomp.), [a]2D0
–18.50° (c 2; 1 N NaOH). For 1H NMR and 13C NMR ([2H6]DMSO) see
3c.
Dimethyl ester of 2-[(1R,5S)-(3,7-Dioxo-2,4,6,8-tetraazabicyclo[3.3.0]-
oct-2-yl)]-2(S)-pentanedioic acid 3d: yield 34%, mp 248–250 °C.
1H NMR ([2H6]DMSO) d: 2.00–2.21 (m, 2H, CH2), 2.28–2.46 (m, 2H,
CH2), 3.59 (s, 3H, OMe), 3.65 (s, 3H, OMe), 4.39 (dd, 1H, CH, 3J
5.15 Hz, 3J 11.03 Hz), 5.24 [br. d, 1H, C(1)H, 3J 8.32 0.02 Hz], 5.48
[br. d, 1H, C(5)H, 3J 8.32 0.02 Hz], 7.36 (br. s, 2H, 2NH), 7.64 (s, 1H,
NH). 13C NMR ([2H6]DMSO) d: 24.35 (CH2), 29.85 (CH2), 51.31 (Me),
52.14 (Me), 53.47 (CH), 62.82 (CH), 67.22 (CH), 159.53 (CO), 161.12
(CO), 171.27 (COOMe), 172.58 (COOMe).
– 270 –

, 2003, 13(6), 269–271
So, it was found that C(1) and C(5) carbon atoms in 3c and
3d exhibit an (1R,5S) configuration (Figures 1 and 3), whereas
an opposite (1S,5R) configuration was found in stereoisomer
3'c (Figure 2). A comparison between X-ray diffraction data
and the spectroscopic characteristics of the prepared compounds
demonstrates that in all cases predominant isomers in the reac-
tions of 1 with S-N-carbamoyl-α-amino acids or R-N-carbamoyl-
α-amino acids exhibit 1R,5S- or 1S,5R-configuration, respec-
tively.
Thus, as a result of a study of the interaction of 4,5-di-
hydroxyimidazolidin-2-one 1 with S- and R-N-carbamoyl-α-
amino acids, we found that these reactions occur with high
diastereoselectivity. This fact provides an opportunity to syn-
thesise glycoluriles with specified configurations of bridging
carbon atoms. The use of N-carbamoyl-α-amino acids with
asymmetric centres of opposite configurations is a simple method
for the preparation of individual glycolurile enantiomers.
C(10)
O(4)
O(3)
C(9)
H(5)
H(1)
C(1)
C(5)
N(8)
N(6)
C(8)
C(11)
N(2)
N(4)
H(4N)
H(6N)
O(2)
H(8N)
C(7)
C(3)
O(1)
O(5)
C(12)
C(13)
O(6)
C(14)
This work was supported by INTAS (grant no. 99-0157), the
Russian Foundation for Basic Research (grant no. 02-03-33257)
and the President of the Russian Federation (Leading Schools
SSc-1917.2003.3).
Figure 3 The general view of 3d. The disordered ester groups are omitted
for clarity. The selected bond lengths (Å): N(2)–C(1) 1.451(4), N(2)–C(3)
1.373(4), N(2)–C(8) 1.459(3), N(4)–C(3) 1.332(4), N(4)–C(5) 1.431(4),
N(6)–C(5) 1.443(4), N(6)–C(7) 1.354(3), N(8)–C(7) 1.343(3), N(8)–C(1)
1.427(4), O(1)–C(3) 1.229(4), O(2)–C(7) 1.232(3); bond angles (°): N(8)–
C(1)–N(2) 115.0(2), N(8)–C(1)–C(5) 102.9(2), N(2)–C(1)–C(5) 102.9(2),
C(3)–N(2)–C(1) 111.4(2), C(3)–N(2)–C(8) 119.1(3), C(1)–N(2)–C(8)
123.4(2), O(1)–C(3)–N(4) 126.5(3), O(1)–C(3)–N(2) 124.8(3), N(4)–C(3)–
N(2) 108.6(3), C(3)–N(4)–C(5) 114.0(2), N(4)–C(5)–N(6) 114.7(3), N(4)–
C(5)–C(1) 102.6(2), N(6)–C(5)–C(1) 102.4(2), C(7)–N(6)–C(5) 112.6(2),
O(2)–C(7)–N(8) 125.8(2), O(2)–C(7)–N(6) 125.6(2), N(8)–C(7)–N(6)
108.7(2), C(7)–N(8)–C(1) 113.4(2). Conformation: C(1)N(2)C(3)N(4)C(5)
cycle – envelope [deviation of C(3) 0.09 Å], C(1)C(5)N(6)C(7)N(8) cycle –
envelope [deviation of C(5) 0.03 Å].
References
1
(a) H. Petersen, Synthesis, 1973, 243; (b) K. E. Pryor and J. Rebek,
Org. Lett., 1999, 1, 39; (c) A. A. Bakibaev, A. Yu. Yagovkin and S. N.
Vostretsov, Usp. Khim., 1998, 67, 333 (Russ. Chem. Rev., 1998, 67,
295); (d) A. Wu, J. C. Fettinger and L. Isaacs, Tetrahedron, 2002, 58,
9769.
2
R. G. Kostyanovsky, K. A. Lyssenko, G. K. Kadorkina, O. V. Lebedev,
A. N. Kravchenko, I. I. Chervin and V. R. Kostyanovsky, Mendeleev
Commun., 1998, 231.
pates in different H-bonds with the O(1) atom in 3c or S(1) in
3'c. It is likely that these differences in the H-bond systems of
3c and 3'c result in a change in the conformation of the substi-
tuent at the N(2) atom [the torsion angle C(12)S(1)C(11)C(10)
is equal to –79° to –64.5°, respectively].
In all cases, a three-dimensional H-bound framework is the
supramolecular structure; in this case, because of the trigonal
symmetry of a 3d crystal, N–H···O bound bicyclic molecules
form honeycombs, within which ester substituents are arranged
(Figure 4).
3
4
5
K. Yu. Chegaev, A. N. Kravchenko, O. V. Lebedev and Yu. A. Strelenko,
Mendeleev Commun., 2001, 32.
G. A. Gazieva, K. A. Lyssenko, R. G. Gaziev, A. N. Kravchenko, O. V.
Lebedev and V. M. Zhulin, Mendeleev Commun., 2001, 107.
G. A. Gazieva, A. N. Kravchenko, O. V. Lebedev, K. A. Lyssenko,
M. O. Dekaprilevich, V. M. Menshov, Yu. A. Strelenko and N. N.
Makhova, Mendeleev Commun., 2001, 138.
6
A. N. Kravchenko, E. Yu. Maksareva, P. A. Belyakov, A. S. Sigachev,
K. Yu. Chegaev, K. A. Lyssenko, O. V. Lebedev and N. N. Makhova,
Izv. Akad. Nauk, Ser. Khim., 2003, 180 (Russ. Chem. Bull., Int. Ed.,
2003, 52, 192).
7
8
9
W. Dietz and R. Mayer, J. Pract. Chem., 1968, 37, 78.
V. Stella and T. Hugochi, J. Org. Chem., 1973, 38, 1527.
H. Petersen, Liebigs Ann. Chem., 1969, 726, 89.
10 J. Taillades, L. Boiteau, I. Beuzelin, O. Lagrille, J.-P. Biron, W. Vayaboury,
O. Vandenabeele-Trambouze, O. Giani and A. Commeyras, J. Chem.
Soc., Perkin Trans. 2, 2001, 1247.
11 A. G. Pechenkin, A. V. Evseeva, A. P. Gilev and T. V. Mikhailova, Izv.
Tomsk. Politekh. Inst., 1974, 233, 73 (in Russian).
Figure 4 The scheme illustrating formation of the N–H…O bonded
honeycombs in the crystal structure of 3d. The ester substituent is shown
without ball representation of atoms.
Received: 22nd May 2003; Com. 03/2128
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