1104
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 6, June, 2001
Miftakhov et al.
(LiBHEt3) (Aldrich); THF was distilled under Ar over ben-
zophenone-Na. The reactions were carried out under Ar. Pre-
parative chromatography was performed using silica gel
L (40100 µm) (Chemapol, Czech Republic) and light petro-
leum with b.p. 4070 °C. TLC analysis was carried out using
Silufol plates (Czech Republic).
(dd, 1 H, H(7)exî, J = 6.8, 7.2 Hz); 3.70 (dd, 1 H, H(5),
J = 0.9, 1.1 Hz); 3.73 (dd, 1 H, H(7)endo, J = 1.8, 7.2 Hz); 4.53
(dd, 1 H, H(6), J = 1.8, 6.8 Hz); 5.68 (d, 1 H, H(1),
J = 3.1 Hz); 7.257.55 (m, 5 H, SPh). 13C NMR (CDCl3),
δ: 47.40 (C(2)); 49.31 (C(4)); 54.11 (C(5)); 68.49 (C(7)); 71.92
(C(6)); 98.18 (C(1)); 127.87, 129.37, 131.95, 133.30 (SPh).
(1R,2S,3S,4R,5R)-2,4-Bis(phenylthio)-6,8-dioxabicyc-
lo[3.2.1]octan-3-ol (5). Rf 0.45 (benzeneEtOAc, 7 : 3). M.p.
106108 °C, [α]D 51.4 (c 1.0, CHCl3) (cf. Ref. 11: m.p.
(1R,2S,3S,4R,5R)-2,4-Dimethylsulfonyloxy-6,8-dioxa-
bicyclo[3.2.1]octan-3-ol. Mesyl chloride (5.90 mL, 76.24 mmol)
was added at 5 °C to a solution of levoglucosan (5.03 g,
31.03 mmol) in 25 mL of Ðó. The mixture was stirred for 2 h at
this temperature and for 24 h at 20 °C. Then the reaction
mixture was diluted with 100 mL of water and extracted with
EtOAc (3½100 mL). The combined organic extracts were washed
with water and brine, dried with MgSO4, and concentrated.
The residue was crystallized from an acetonelight petroleum
mixture (1 : 1) to give 7.02 g (72%) of dimethanesulfonate,
Rf 0.30 (EtOAcheptane, 2 : 1). M.p. 111112 °C, [α]D 36.3
(c 1.0, Me2CO). Found (%): C, 30.60; H, 4.42; S, 20.37.
C8H14O9S2. Calculated (%): C, 30.18; H, 4.43; S, 20.15. IR,
ν/cm1: 1200, 1320 (SO2), 3520 (COH). 1H NMR (DMF-d6),
δ: 3.32, 3.36 (both s, each 3 H, SO2Me); 3.74 (dd, 1 H,
H(7)exî, J = 5.5, 7.5 Hz); 4.04 (s, 1 H, H(4)); 4.20 (d, 1 H,
H(7)endo, J = 7.5 Hz); 4.37 (s, 1 H, H(3)); 4.65 (s, 1 H, H(2));
4.85 (d, 1 H, H(1), J = 5.5 Hz); 5.57 (s, 1 H, H(5)). 13C NMR
(DMF-d6), δ: 38.01 (Me); 65.84 (C(7)); 70.08 (C(1)); 75.20
(C(4)); 78.43 (C(3)); 79.69 (C(2)); 100.47 (C(5)).
(1R,2R,4S,5R,6R)-5-Methylsulfonyloxy-3,7,9-triîxatri-
cyclo[4.2.1.02,4]nonane (6). A 5 M solution of MeONa (15 mL)
in MeOH was added to a solution of the dimethanesulfonate
(7.10 g, 22.30 mmol) (see above) in 50 mL of CH2Cl2. The
reaction mixture was stirred for 22 h at 20 °C, diluted with
300 mL of CH2Cl2, washed with water and brine, dried with
MgSO4, and concentrated. Crystallization from an acetonelight
petroleum mixture (3 : 7) gave 2.97 g (59.8%) of mesyloxy
epoxide 6. The mother liquor was concentrated, the residue was
chromatographed on a column with SiO2 using a hexaneEtOAc
(7 : 3) mixture as the eluent to give 1.28 g (25.8%) of mesyloxy
epoxide 6. The total yield was 4.25 g (85.6%). Rf 0.46
(EtOAcbenzene, 7 : 3). M.p. 148150 °C, [α]D 48.7
(c 1.1, CHCl3). Found (%): C, 37.65; H, 4.27; S, 14.47.
C7H10O6S. Calculated (%): C, 37.83; H, 4.54; S, 14.43. IR,
ν/cm1: 1190, 1370 (SO2). 1H NMR (CDCl3), δ: 3.15 (s, 3 H,
SO2Me); 3.34 (dd, 1 H, H(4), J = 1.6, 4.2 Hz); 3.57 (dd, 1 H,
H(8)exî, J = 4.8, 6.7 Hz); 3.69 (dd, 1 H, H(1), J = 4.4,
4.8 Hz); 4.03 (d, 1 H, H(8)endo, J = 5.5 Hz); 4.67 (br.s, 1 H,
H(5)); 4.88 (t, 1 H, H(1), J = 4.8 Hz); 5.39 (s, 1 H, H(6)).
13C NMR (CDCl3), δ: 38.50 (Me); 47.75 (C(4)); 52.89 (C(2));
64.88 (C(8)); 70.86 (C(5)); 71.75 (C(1)); 98.21 (C(6)).
20
9394 °C, [α]D 51 (c 1.6, CHCl3)). Found (%): C, 62.48;
H, 5.15; S, 14.06. C18H18O3S2. Calculated (%): C, 62.40;
H, 5.24; S, 18.51. IR, ν/cm1: 3490 (COH). 1H NMR
(CDCl3), δ: 3.20 (d, 1 H, OH, J = 6.3 Hz); 3.31 (s, 1 H, H(4)),
3.36 (s, 1 H, H(2)); 3.77 (dd, 1 H, H(7)exî, J = 5.0, 7.4 Hz);
4.15 (br.s, 1 H, H(3)); 4.18 (d, 1 H, H(7)endo, J = 7.4 Hz); 4.69
(d, 1 H, H(1)); 5.71 (s, 1 H, H(5)); 7.207.55 (m, 10 H,
2 SPh). 13C NMR (CDCl3), δ: 52.44 (C(4)); 52.99 (C(2));
68.38 (C(7)); 71.47 (C(1)); 75.50 (C(3)); 102.53 (C(5));
127.26, 127.54, 129.22, 129.27, 131.04, 131.87, 134.47,
134.84 (2 SPh).
(1R,2S,3R,5R)-2-Phenylthio-6,8-dioxabicyclo[3.2.1]octan-
3-ol (7). A 1.0 Ì solution of LiBHEt3 (25 mL) was added at
20 °C to a solution of epoxide 3 (2.53 g, 10.71 mmol) in 20 mL
of THF. The reaction mixture was stirred for 6 h, NaHCO3
(6.30 g, 75.00 mmol) was added, and 30% H2O2 (7.60 mL,
75.00 mmol) was carefully added dropwise. The mixture was
stirred for 1 h at 4050 °C. The reaction mixture was diluted
with 200 mL of EtOAc and washed successively with a satu-
rated solution of Na2S2O3, H2O, and brine, dried with MgSO4,
and concentrated. The residue was chromatographed on SiO2,
using a benzeneEtOAc mixture (9 : 1, then 7 : 3) as the
eluent to give 2.17 g (85%) of alcohol 9. Rf 0.30 (ben-
zeneEtOAc, 7 : 3). M.p. 125.5127 °C, [α]D 39.6 (c 1.0,
CHCl3). Found (%): C, 60.20; H, 5.94; S, 13.52. C12H14O3S.
Calculated (%): C, 60.48; H, 5.92; S, 13.46. IR, ν/cm1: 1450,
1580, 1630 (SPh), 3450 (COH). 1H NMR (CDCl3), δ: 1.86
(dd, 1 H, H(4)àx, J = 0.8, 15.0 Hz); 2.33 (ddd, 1 H, H(4)åq,
J = 1.2, 4.9, 15.0 Hz); 3.25 (br.s, 1 H, OH); 3.43 (s, 1 H,
H(2)); 3.77 (dd, 1 H, H(7)exî, J = 5.0, 7.4 Hz); 3.98 (m, 1 H,
H(3)); 4.36 (d, 1 H, H(7)endo, J = 7.4 Hz); 4.69 (d, 1 H, H(1),
J = 5.0 Hz); 5.67 (d, 1 H, H(5), J = 1.2 Hz); 7.207.50 (m,
5 H, SPh). 13C NMR (CDCl3), δ: 35.33 (C(4)); 52.40 (C(2));
67.79 (C(7)); 68.26 (C(3)); 75.28 (C(1)); 101.45 (C(5)); 127.00,
129.23, 130.81, 134.63 (SPh).
(1R,2S,4S,5R)-2-Phenylthio-6,8-dioxabicyclo[3.2.1]octan-
i
4-ol (8). A 4.0 Ì solution of Bu2 AlH (6.30 mL) in THF was
slowly added dropwise to a solution of epoxide 3 (2.00 g,
8.47 mmol) in 15 mL of THF cooled to 20 °C. The reaction
mixture was stirred for 1 h, and 2 mL of a saturated solution of
NH4Cl and 100 mL of EtOAc were added. The organic layer
was separated, washed successively with 1 Ì HCl, a saturated
solution of NaHCO3, and brine, dried with Na2SO4, and
concentrated. The residue was chromatographed on SiO2, using
a light petroleumEtOAc mixture (9 : 1, then 7 : 3) as the
eluent to give 1.65 g (82%) of alcohol 8. Rf 0.20 (light pe-
troleumEtOAc, 1 : 1). M.p. 107109 °C, [α]D 70.8
(c 0.85, CHCl3). Found (%): C, 60.61; H, 6.02; S, 13.50.
C12H14O3S. Calculated (%): C, 60.48; H, 5.92; S, 13.46. IR,
ν/cm1: 1376, 1464, 1580 (SPh), 3424 (COH). 1H NMR
(CDCl3), δ: 1.77 (m, 1 H, H(3)àx); 2.12 (dd, 1 H, H(3)åq,
J = 5.7, 14.0 Hz); 2.33 (d, 1 H, OH, J = 9.3 Hz); 3.25 (d, 1 H,
Reaction of mesyloxy epoxide 6 with PhSNa. PhSH (0.97 g,
8.82 mmol) and NaOH (0.38 g, 9.62 mmol) were added to a
solution of mesyloxy epoxide 6 (1.78 g, 8.02 mmol) in 20 mL of
a THFH2O (9 : 1) mixture. The reaction mixture was stirred
for 3 h at 55 °C, diluted with 200 mL of EtOAc, and washed
successively with 1 Ì HCl, a saturated solution of NaHCO3,
and brine. The organic layer was dried with Na2SO4 and
concentrated, and the residue was chromatographed on SiO2
using a light petroleumEtOAc mixture (9 : 1, then 7 : 3) as
the eluent to give 1.66 g (87.8%) of phenylthio epoxide 3 and
0.1 g of bis(phenylthio) derivative 5.
(1R,2S,4R,5S,6R)-5-Phenylthio-3,8,9-trioxatricyc-
lo[4.2.1.02,4]nonane (3). Rf 0.63 (benzeneEtOAc, 7 : 3).
M.p. 112.5114 °C, [α]D +8.4 (c 1.0, CHCl3). Found (%):
C, 60.84; H, 5.13; S, 13.37. C12H12O3S. Calculated (%):
C, 61.00; H, 5.12; S, 13.57. IR, ν/cm1: 1256 (epoxide), 1460,
H(2), J = 5.4 Hz); 3.703.80 (m, 3 H, H(4), H(7)endo
,
H(7)eõo); 4.46 (d, 1 H, H(1), J = 4.5 Hz); 5.32 (s, 1 H, H(5));
7.057.45 (m, 5 H, SPh). 13C NMR (CDCl3), δ: 31.34 (C(3));
47.57 (C(2)); 66.46 (C(7)); 68.52 (C(4)); 74.99 (C(1)); 103.26
(C(5)); 127.56, 129.20, 132.18, 134.34 (SPh).
1
1580 (SPh). H NMR (acetone-d6), δ: 3.13 (dd, 1 H, H(4),
J = 0.9, 3.8 Hz); 3.44 (dd, 1 H, H(2), J = 3.1, 3.8 Hz); 3.65