308
PESTOVA et al.
22
96.64 C(1), 108.60 C(7), 109.28 C(10). Found, %: C,
in [16]. The yield 77%,
– 15.6 (с 0.30, CHCl3);
[α]D
62.35; H, 8.80; S, 13.72. C24H42S2O5. Calculated, %:
C, 60.72; H, 8.92; S, 13.51.
22
ref. [16]: yield 99%,
– 15.0 (с 1.80, CHCl3).
[α]D
1-Deoxy-1-iodo-2,3:4,5-di-O-isopropylidene-β-
1-[((1S,2S,4S)-1,7,7-Trimethylbicyclo[2.2.1]-
hept2-yl)sulfanyl]-2-(6-deoxy-1,2:3,4-di-O-isopro-
pylidene-α-D-galactopyranosyl-6-sulfanyl)ethane (IIIBa).
D-fructopyranose (VIIIb) was obtained as described in
22
[17]. The yield 64%,
– 47.6 (с 0.88, СНCl3).
1-Deoxy-1-thioacetyl-2,3:4,5-di-O-isopropylidene-
β-D-fructopyranose (IXb) was synthesized as
described in [18]. The yield 72%,
(CH ) CO); ref. [18]: the yield 76%, 22 –2.9 (с 1.00,
[α]D
[α]2D0
The yield 80%. Viscous yellow liquid,
–28.5
(с 0.50; CHCl3), Rf 0.51 (CHCl3–Et2O, 60 : 1). IR, ν,
cm–1: 646 (C–S), 1071 (С–О), 1169 (О–С–О), 2951.
1H NMR: 0.84 (s, 3H, Me(9')), 0.97 (s, 3H, Me(8')),
1.01 (s, 3H, Me(10')), 1.10–1.23 (m, 2H, Н5'en,
Н6'en), 1.36 (s, 3H, Me(8)), 1.38 (s, 3H, Me(12)),
1.48 (s, 3H, Me(11)), 1.57 (s, 3H, Me(9)), 1.66–1.78
(m, 3H, Н5'ex, Н6'ex, Н4'), 1.84–1.99 (m, 2H, H3'),
2.62–2.90 (m, 7H, Н2', Н2'', H1'', Н6), 3.84–3.94
(m, 1Н, Н5), 4.27–4,38 (m, 2Н, Н2, H3), 4.65 (dd,
1H, H4, J 7.8, 2.3), 5.55 (d, 1Н, Н1, J 5.0). 13C NMR:
14.01 С(10'), 20.20 С(8'), 20.42 С(9'), 24.47 С(12),
24.92 C(8), 26.00 C(11), 26.16C(9), 27.36 С(5'), 31.82
С(2''), 32.92 С(6), 34.76 С(1''), 38.53 С(6'), 41.19
С(3'), 45.90 С(4'), 47.33 С(1'), 49.48 С(7'), 54.93
С(2'), 68.02 C(5), 70.54 C(2), 70.90 С(4), 71.60 C(3),
96.64 C(1), 108.60 C(7), 109.28 C(10). Found, %: C,
61.27; H, 8.55; S, 13.54. C24H40S2O5. Calculated, %:
C, 60.98; H, 8.53; S, 13.57.
22
–3.1 (с 0.95,
[α]D
[α]D
3 2
СНCl3).
6-Deoxy-6-thio-1,2:3,4-di-O-isopropylidene-α-D-
galactopyranose (IIa) was obtained as described in
[19]. Viscous yellow liquid. The yield 91%, 22 – 70.0
[α]D
(c 0.47, CHCl3), ref. [19]: the yield 70%, – 88.7 (con-
centration not given, СНCl3).
1-Deoxy-1-thio-2,3:4,5-di-O-isopropylidene-β-
D-fructopyranose (IIb) was obtained as described in
[α]2D2
[20]. White powder. The yield 94%,
(c 0.40, CHCl3); ref. [20]: the yield 65%, not shown.
– 44.0
Monoterpene- and monosaccharide derived bis-sul-
fides. A carbohydrate-containing thiol (0.359 g,
1.3 mmol), cesium carbonate (0.424 g, 1.3 mmol), and
tetrabutylammonium iodide (0.480 g, 1.3 mmol) were
dissolved in EtOH (3 mL) under stirring in an argon
atmosphere. Terpenyl sulfanyl ethyl chlorides (IА) or
(IB) (1.0 mmol) were added in 5 min and the mixture
was refluxed for 6 h. The solvent was removed in vac-
uum and the product was isolated by column chroma-
tography on silica gel eluting with 60 : 1 CHCl3–Et2O.
1-((1S,2S,5R)-2-Isopropyl-5-methylcyclohexyl-
sulfanyl)-2-(1-deoxy-2,3:4,5-di-O-isopropylidene-β-
D-fructopyranosyl-1-sulfanyl)ethane (IIIAb). The
20
yield 98%. Viscous yellow liquid,
+10.6 (с 1.00;
[α]D
CHCl3), Rf 0.42 (CHCl3–Et2O, 60 : 1). IR, ν, cm–1:
1
640 (C–S), 1063 (C–O), 1167 (О–С–О), 2918. H
NMR: 0.89 (d, 3H, Me(7'), J 6.3), 0.92 (d, 3H,
Me(9'), J 6.3), 0.84–0.94 (m, 1H, H4'e), 0.96 (d, 3H,
Me(10'), J 6.6), 1.05–1.25 (d, 3H, H2', H3'e, H6'e),
1.37 (s, 3H, Me(12)), 1.48 (s, 3H, Me(8)), 1.50 (s, 3H,
Me(11)), 1.56 (s, 3H, Me(9)), 1.59–1.80 (m, 3H, H8',
H3'a, H4a'), 1.85–2.06 (m, 2H, Н5', H6'a), 2.68–
2.94 (m, 4H, Н2'', H1''), 2.84 (d, 1H, Н1А, J 13.8),
3.10 (d, 1H, Н1B, J 13.8), 3.14–3.20 (m, 1Н, H1'),
4.30 (d, 1Н, Н6А, J 13.0), 4.63 (d, 1Н, Н6B, J 12.6),
4.26 (d, 1H, H5, J 7.7), 4.34 (d, 1H, H3, J 2.5), 4.63
(dd, 1H, H4, J 8.0, 2.5). 13C NMR: 20.80 С(10'), 21.06
С(9'), 22.18 С(7'), 24.07 С(12), 25.49 С(10), 25.93
C(3'), 25.98 C(5'), 26.37 C(11), 26.63 C(9), 29.94
C(8'), 31.50 C(2''), 24.16 C(1''), 35.37 С(4'), 40.14
С(6'), 40.95 С(1), 46.94 С(1'), 48.94 С(2'), 61.68
С(6), 70.39 C(4), 70.89 С(5), 72.25 C(3), 103.64
C(2), 108.55 C(7), 109.06 C(10). Found, %: C, 63.10;
H, 8.77; S, 13.42. C24H42S2O5. Calculated, %: C,
60.72; H, 8.92; S, 13.51.
1-((1S,2S,5R)-2-Isopropyl-5-methylcyclohexyl-
sulfanyl)-2-(6-deoxy-1,2:3,4-di-O-isopropylidene-α-
D-galactopyranosyl-6-sulfanyl)ethane (IIIАа). The
20
yield 98%. Viscous yellow liquid,
– 8.0 (с 0.80;
[α]D
CHCl3), Rf 0.37 (CHCl3–Et2O, 60 : 1). IR, ν, cm–1:
646 (C–S), 999, 1071(C–O), 1169 (O–C–O), 1211,
1
2916. H NMR: 0.83–0.94 (m, 1Н, H4'e), 0.90 (d,
3H, Me(7'), J 6.6), 0.92 (d, 3H, Me(10'), J 6.6), 0.97
(d, 3H, Me(9'), J 6.6), 1.07–1.32 (m, 3H, H2', H6'e,
H3'e), 1.36 (с, 3H, Me(8)), 1.38 (s, 3H, Me(12)), 1.48
(s, 3H, Me(11)), 1.57 (s, 3H, Me(9)), 1.66–1.80 (m,
3H, Н4'а, Н8', Н3'a), 1.87–2.10 (m, 1H, Н5'), 1.88–
2.03 (m, 1H, Н6'a), 2.67–2.89 (m, 6H, H6, H1'',
H2''), 3.14–3.24 (m, 1H, H1'), 3.84–3.95 (m, 1H,
H5), 4.31–4.42 (m, 2Н, Н2, Н3), 4.65 (dd, 1H, H4, J
8.0, 2.2), 5.56 (d, 1Н, Н1, J 5.0). 13C NMR: 20.83
С(10'), 21.05 С(9'), 22.18 С(7'), 24.48 С(12), 24.92
С(8), 25.91 С(3'), 25.98 C(11), 25.99 C(5'), 26.36
C(9), 29.94 C(8'), 31.68 С(1''), 31.85 С(2''), 33.01
1-[((1S,2S,4S)-1,7,7-Trimethylbicyclo[2.2.1]hept-2-
С(6), 35.37 С(4'), 40.95 С(6'), 46.82 С(1'), 48.92 yl)sulfanyl]-2-(1-deoxy-2,3:4,5-di-O-isopropylidene-
С(2'), 68.00 С(5), 70.54 C(2), 70.91 С(4), 71.56 C(3), β-D-fructopyranosyl-1-sulfanyl)ethane (IIIBb). The
RUSSIAN JOURNAL OF BIOORGANIC CHEMISTRY
Vol. 43
No. 3
2017