1902
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 9, September, 2009
Siyutkin et al.
2ꢀ[Hydroxy(5ꢀnitroꢀ2ꢀthienyl)methyl]cyclopentanone (12d).
Light yellow oil. 1H NMR of antiꢀisomer, δ: 1.73—1.90 (m, 1 H,
HCH); 1.92—2.27 (m, 4 H, 2CH2); 2.37—2.50 (m, 1 H, HCH);
2.50—2.62 (m, 1 H, CHCO); 4.86 (s, 1 H, OH); 5.01 (d, 1 H,
CHOH, J = 9.5 Hz); 6.88 (d, 1 H, CHSCHNO2, J = 4.0 Hz);
7.80 (d, CHNO2, J = 4.0 Hz). 1H NMR of synꢀisomer, δ:
1.73—1.90 (m, 1 H, HCH); 1.92—2.27 (m, 4 H, 2 CH2);
2.37—2.50 (m, 1 H, HCH); 2.50—2.62 (m, 1 H, CHCO); 2.95
(d, 1 H, OH, J = 5.5 Hz); 5.51 (s, 1 H, CHOH); 6.88 (d, 1 H,
CHSCHNO2, J = 4.0 Hz); 7.83 (d, CHNO2, J = 4.0 Hz).
13C NMR of antiꢀisomer, δ: 22.0, 24.9, 38.8, 55.0, 68.3, 122.8,
130.1, 148.8, 159.5, 217.5 13C of synꢀisomer, δ: 20.0, 22.0, 38.6,
54.7, 66.8, 122.6, 130.4, 148.8, 161.2, 217.2. Found (%):
С, 49.98; H, 4.68; N, 5.70. C10H11NO4S. Calculated (%): C, 49.78;
H, 4.60; N, 5.81. Rf 0.40 (nꢀhexane—EtOAc, 2 : 1). HPLC
(Chiralcel OJꢀH column, eluent nꢀhexane—PriOH (7 : 3),
λ = 254 nm, v = 0.8 mL min–1), τ/min: 9.8 (anti), 11.2 (entꢀanti),
11.6 (syn), 12.9 (entꢀsyn).
7ꢀ[Hydroxy(5ꢀnitroꢀ2ꢀthienyl)methyl]ꢀ1,4ꢀdioxaspiro[4.5]ꢀ
decanꢀ8ꢀone (12e). Light yellow oil. 1H NMR of antiꢀisomer, δ:
1.74—2.15 (m, 4 H, CH2CCH2); 2.42—2.83 (m, 2 H, CH2CO);
2.98—3.13 (m, 1 H, CHCO); 3.92—4.05 (m, 4 H, OCH2CH2O);
4.08 (d, 1 H, OH, J = 4.0 Hz); 5.02—5.11 (m, 1 H, CHOH,
J = 6.6 Hz); 6.89 (d, 1 H, CHSCHNO2, J = 4.0 Hz); 7.80 (d,
1 H, CHNO2, J = 4.4 Hz). 1H NMR of synꢀisomer, δ: 1.74—2.15
(m, 4 H, CH2CCH2); 2.42—2.83 (m, 2 H, CH2CO); 2.98—3.13
(m, 1 H, CHCO); 3.29 (d, 1 H, OH, J = 3.7 Hz); 3.92—4.05 (m,
4 H, OCH2CH2O); 5.59 (s, 1 H, CHOH); 6.83 (d, 1 H,
CHSCHNO2, J = 4.4 Hz); 7.84 (d, 1 H, CHNO2, J = 4.4 Hz).
13C NMR of antiꢀisomer, δ: 33.3, 34.2, 38.4, 52.9, 64.7, 64.9,
67.7, 107.2, 121.9, 128.8, 150.6, 155.2, 211.0. 13С NMR of
synꢀisomer, δ: 34.3, 37.4, 38.7, 53.3, 64.7, 64.9, 70.6, 106.8,
124.0, 128.2, 151.3, 153.8, 212.2. Found (%): С, 50.08; H, 4.96;
N, 4.28. C13H15NO6S. Calculated (%): C, 49.83; H, 4.83;
N, 4.47. Rf 0.26 (nꢀhexane—EtOAc, 2 : 1). HPLC (Chiralcel
OJꢀH column, eluent nꢀhexane—PriOH (7 : 3), λ = 254 nm,
v = 0.8 mL min–1), τ/min: 16.1 (anti), 16.9 (entꢀanti), 18.2
(syn), 20.8 (entꢀsyn).
1ꢀBenzyloxycarbonylꢀ3ꢀ[hydroxy(5ꢀnitroꢀ2ꢀtheinyl)methyl]ꢀ
piperidinꢀ4ꢀone (12f). Light yellow oil. 1H NMR of antiꢀisomer,
δ: 2.46—2.96 (m, 2 H, CH2CO); 3.05—3.45 (m, 2 H, NCH2CH2);
4.05—4.25 (m, 2 H, NCH2CH); 5.05—5.24 (m, 3 H, CHOH,
CH2Ph); 6.63—6.95 (m, 1 H, CHSCHNO2); 7.21—7.43 (m,
5 H, C6H5); 7.62—7.90 (m, 1 H, CHNO2). 1H NMR of
synꢀisomer, δ: 2.46—2.96 (m, 2 H, CH2CO); 3.05—3.45 (m,
2 H, NCH2CH2); 4.05—4.25 (m, 2 H, NCH2CH); 5.05—5.24
(m, 2 H, CH2Ph); 5.58 (s, 1 H, CHOH); 6.63—6.95 (m, 1 H,
CHSCHNO2); 7.21—7.43 (m, 5 H, C6H5); 7.62—7.90 (m, 1 H,
CHNO2). 13C NMR of antiꢀisomer, δ: 41.4, 43.2, 43.7, 56.4,
67.7, 68.0, 124.1, 128.0, 128.1, 128.3, 128.5, 136.0, 151.4, 154.3,
183.1, 208.9. 13C NMR of synꢀisomer, δ: 41.4, 43.2, 43.7, 55.9,
66.9, 68.0, 122.1, 128.0, 128.3, 128.5, 128.7, 136.0, 150.8, 155.3,
183.1, 207.7. Found (%): С, 55.60; H, 4.87; N, 7.08. C18H18N2O6S.
Calculated (%): C, 55.38; H, 4.65; N, 7.18. Rf 0.39 (nꢀhexane—
EtOAc, 1 : 1). HPLC (Chiralcel OJꢀH column, eluent nꢀhexane—
PriOH (7 : 3), λ = 254 nm, v = 0.8 mL min–1), τ/min: 9.8 (anti),
10.4 (syn), 10.9 (entꢀanti), 11.5 (entꢀsyn).
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 09ꢀ03ꢀ00384).
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Received March 4, 2009;
in revised form June 3, 2009