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org. phases were washed with brine, dried (Na2SO4), and evaporated. FC (light petroleum ether/AcOEt 3 :2)
gave 0.16 g (36%) of 10, 2 :1 diastereoisomer mixture. Colorless oil. UV (MeCN): 248 (1530), 233 (1200). IR
(film): 3340, 2985, 1695, 1415, 1165, 1125, 1050, 985, 905. 1H-NMR (400 MHz, CDCl3; major isomer): 7.37
(m, Ph); 5.82 (m, HÀC(3)); 5.64 (s, HÀC(1)); 4.69 (m, PhCH2, HÀC(5), HÀC(1')); 4.20 3.64 (m, HÀC(3'),
HÀC(4'), HÀC(2'), H−exo×ÀC(6), HÀC(4), HaÀC(5')); 3.49 (dd, 2J 12.4, 3J(4',5'b) 5.2, HbÀC(5')); 3.38
(m, H−endo×ÀC(6)); 1.49 (s, Me3C); 1.30 (s, Me2C). 13C-NMR (100.6 MHz, CDCl3; major isomer): 154.9
(s, NCOO); 143.7 (s, C(2)); 138.1 (s, arom. C); 128.3, 127.5(3 d, 1J(C,H) 140, arom. C); 118.9 (d, J 68,
C(3)); 111.3 (s, Me2C); 95.8 (d, J 167, C(1)); 80.1 (s, Me3C); 79.4 (d, J 145, C(3')); 78.9 (d, J 144, C(4'));
74.4 (d, J 144, C(2')); 72.4 (d, J 145, C(1')); 70.2 (t, J 144, C(6)); 67.5( d, J 145, C(4)); 67.3 (d, J 145,
C(5)); 53.8 (d, J 144, C(5')); 28.3 (q, J 144, Me3C); 26.9, 24.8 (2q, J 144, Me2C). CI-MS (NH3): 91 (39), 142
(89), 172 (32), 233 (100), 272 (55), 326 (17), 490 (78, [M 1] ). Anal. calc. for C26H35NO8 (489.57): C 63.79,
H 7.21, N 2.86; found: C 63.90, H 7.15, N 2.91.
Methyl 4-O-Benzyl-3-deoxy-2-O-[(trifluoromethyl)sulfonyl]-a-d-erythro-hex-2-enopyranoside (()-11).
BF3 ¥ Et2O (0.7 ml, 5.4 mmol) was added to a soln. of 2 [17] (0.5g, 1.4 mmol) in MeOH (4 ml) at 0 8. The
mixture was left at 208 overnight. Evaporation and FC (light petroleum ether/AcOEt 1:1) gave 0.36 g (67%) of
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()-11. White solid. M.p. 85 86 8. [a] 102, [a] 130, [a] 142, [a] 152, [a] 163 (c
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0.1, CHCl3). UV (MeCN): 218 (19480), 206 (5380). IR (KBr): 3855, 3445, 3005, 1715, 1635, 1495, 1390, 1140,
910, 700. 1H-NMR (400 MHz, CDCl3): 7.39 (m, arom. C); 6.07 (d, 3J(4,3) 2.0, HÀC(3)); 4.91 (s, HÀC(1));
4.62 (AB, 2J 11.6, PhCH2); 4.35( dd, 3J(5,4) 9.6, 3J(3,4) 2.0, HÀC(4)); 3.92 (ddd, 3J(4,5) 9.6, 3J(6b,5)
3.6, 3J(6a,5) 1.6, HÀC(5)); 3.38 (dd, 2J 11.6, 3J(5,6a) 1.6, HaÀC(6)); 3.37 (dd, 2J 11.6, 3J(5,6b) 3.6,
HbÀC(6)); 3.48 (s, MeO). 13C-NMR (100.6 MHz, CDCl3): 145.0 (s, CF3); 137.1 (s, C(2)); 137.2 (s, arom. C);
128.6, 128.3, 127.9 (3d, J 161, arom. C); 119.5( d, J 168, C(3)); 94.6 (d, J 167, C(1)); 71.5( d, J 145, C(5));
70.1 (t, J 143, PhCH2); 69.9 (d, J 144, C(4)); 61.3 (t, J 144, C(6)); 56.5 (q, J 144, MeO). 19F-NMR
(376 MHz, CDCl3): À77.6 (s, CF3). CI-MS (NH3): 91 (64), 108 (25), 338 (9), 384 (22), 415 (76, [ M NH3] ).
Anal. calc. for C15H17F3O7S (398.01): C 45.23, H 4.30, S 8.05; found: C 45.33, H 4.40, S 7.98.
Methyl 4-O-Benzyl-6-O-[(benzyloxy)methyl]-3-deoxy-2-O-[(trifluoromethyl)sulfonyl]-a-d-erythro-hex-2-
i
enopyranoside (()-12). At 08, ()-11 (0.36 g, 0.91 mmol) and Pr2NH (0.2 ml, 1.2 mmol) were mixed with
benzyl chloromethyl ether (0.2 ml, 1.2 mmol). The mixture was allowed to stand at 208 overnight. Then 1n aq.
HCl (1 ml) was added, the org. phase separated, dried, (Na2SO4) and evaporated. FC (light petroleum ether/
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AcOEt 4 :1) gave 0.32 g (68%) of ()-12. Colorless oil. [a] 36, [a] 48, [a] 52, [a] 123,
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[a] 175( c 0.1, CHCl3). UV (MeCN): 218 (18000), 209 (4300). IR (film): 3440, 3005, 1715, 1635, 1485,
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1490, 1380, 1140, 900, 700. 1H-NMR (400 MHz, CDCl3): 7.35( m, arom. H); 6.09 (d, 3J(4,3) 2.4, HÀC(3)); 4.95
(s, HÀC(1)); 4.79 (AB, 2J 11.6, PhCH2); 4.64 (m, CH2); 4.41 (dd, 3J(4,5) 9.6, 3J(3,4) 2.0, HÀC(4)); 4.04
(ddd, 3J(4,5) 9.6, 3J(6b,5) 3.6, 3J(6a,5) 1.6, HÀC(5)); 3.81 (m, HÀC(6)); 3.48 (s, MeO). 13C-NMR
(100.6 MHz, CDCl3): 145.0 (s, CF3); 138.3 (s, C(2)); 137.1 (s, arom. C); 129.4, 129.5, 129.0, 128.7, 127.8, 127.4
(5d, J 161, arom. C); 119.5( d, J 168, C(3)); 94.6 (d, J 167, C(1)); 94.5( t, J 167, OCH2O); 70.1 (t, J 143,
PhCH2); 69.9 (d, J 144, C(4)); 68.3 (d, J 145, C(5)); 65.4 (t, J 143, CH2); 61.3 (t, J 144, C(6)); 56.5 (q, J
144, MeO). 19F-NMR (376 MHz, CDCl3): À77.6 (s, CF3). CI-MS (NH3): 91 (62), 108 (25), 217 (14), 535 (100,
[M NH3] ). Anal. calc. for C23H25F3O8S (518.03): C 53.25, H 4.82, S 6.17; found: C 53.26, H 4.89, S 6.13.
Methyl 4-O-Benzyl-6-O-[(benzyloxy)methyl]-2-{(1S)-2,5-{[(tert-butoxy)carbonyl]imino}-2,5-dideoxy-3,4-
O-isopropylidene-l-ribitol-1-C-yl}-3-deoxy-a-d-erythro-hex-2-enopyranoside (()-13). As described for 10,
with ()-12 (0.27 g, 0.52 mmol), (À)-9 (0.1 g, 0.37 mmol), DMF (2 ml), CrCl2 (0.33 g, 2.68 mmol), NiCl2
(2.6 mg, 0.012 mmol), and O2 (3 ml, 0.14 mmol). FC (light petroleum ether/AcOEt 1:1) gave 0.11 g (48%) of
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()-13. Colorless oil. [a] 229, [a] 234, [a] 248, [a] 312, [a] 456 (c 0.8, CHCl3).
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UV (MeCN): 218 (16600), 260 (2212). IR (film): 3370, 2985, 1710, 1655, 1435, 1550, 1105, 1015, 970, 855, 775,
705. 1H-NMR (400 MHz, CDCl3): 7.34 7.28 (m, arom. H); 6.01 (m, HÀC(3)); 5.12 (s, HÀC(1)); 4.81, 4.78
(AB, 2J 16.4, PhCH2); 4.69 (m, HÀC(4), HÀC(5), HaÀC(6)); 4.63 (s, CH2O); 4.42 (dd, 2J 11.2, J(5,6b)
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3.6, HbÀC(6)); 4.04 (m, HÀC(1')); 4.14 (m, HÀC(2')); 3.48 (s, MeO); 3.95( d, 2J 12.0, HaÀC(5')); 3.86
(m, HÀC(3')); 3.81 (dd, 3J(3',4') 3J(5'b,4') 4.8, HÀC(4')); 3.42 (dd, 2J 12.0, 3J(4',5'b) 4.8, HbÀC(5'));
1.48 (s, Me3C); 1.46, 1.33 (2s, Me2C). 13C-NMR (100.6 MHz, CDCl3): 154.1 (s, NCOO); 138.3 (s, C(2)); 136.5
(s, arom. C); 129.4, 129.5, 129.0, 128.7, 127.8, 127.4 (6d, J 161, arom. C); 124.1 (d, J 168, C(3)); 111.5
(s, Me2C); 95.8 (d, J 167, C(1)); 94.5( t, J 144, OCH2O), 82.5( s, Me3C); 80.1 (d, J 145, C(3')); 79.0 (d, J
144, C(4')); 72.4 (d, J 144, C(2')); 71.4 (d, J 145, C(1')); 70.8 (d, J 143, CH2O); 69.1 (t, J 144, C(6)); 68.9
(d, J 144, C(4)); 67.2 (d, J 145, C(5)); 66.3 (d, J 143, CH2O); 55.7 (q, J 144, MeO); 53.1 (d, J 144,
C(5')); 28.9, 28.5, 28.1 (3q, J 144, Me3C); 27.3, 25.0 (2q, J 144, Me2C). CI-MS (NH3): 91 (40), 142 (31), 172