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Helvetica Chimica Acta Vol. 86 (2003)
mixture was diluted with AcOEt and filtered through Celite. After evaporation of the filtrate, the residue was
purified by CC (CH2Cl2/MeOH 80 :1 ! 20 :1): 16 (63 mg, 76%). Oil. [a]2D5 8 (c 1.2, CH2Cl2). IR (film):
3465 (OH), 1595, 1110 (CÀO), 740, 695. 1H-NMR (500 MHz, CDCl3): 7.37 7.24 (m, 15 H, Ph); 4.66, 4.58 (2d,
1H each, 2J 11.7, CH2Ph); 4.53 (s, 2 PhCH2); 4.33 (m, HÀC(6)); 4.12 (t, J(1,2) (1,7a) 4.5, HÀC(1)); 4.09
(t, J(2,3) 4.6, HÀC(2)); 3.60 (ddd, J(7a,7) 9.1, J(7a,7') 4.5, HÀC(7a)); 3.55 (d, J(CH2 ,3) 6.5,
CH2ÀC(3)); 3.47 (dt, HÀC(3)); 3.22 (dd, J(5a,6) 4.5, 2J(5a,5b) 12.2, HaÀC(5)); 2.99 (br. d, HbÀC(5));
2.86 (br. s, OH); 2.22 (ddd, J(7,6) 5.5, 2J(7,7') 13.8, HÀC(7)); 1.84 (ddd, J(7',6) 3.3, H'ÀC(7)). 13C-NMR
(75.4 MHz, CDCl3): 138.2, 137.9, 137.6 (3 C(1) of Ph), 128.3 127.3 (Ph); 88.9 (C(1)); 85.3 (C(2)); 73.8 (C(6));
73.1, 72.2, 71.8 (3 PhCH2); 71.7 (CH2ÀC(3)), 70.0 (C(3)); 67.6 (C(7a)); 63.4 (C(5)); 40.1(C(7)). FAB-MS: 460
(100, [M H] ), 482 (50, [M Na] ). HR-FAB-MS: 482.2334 ([C29H33NO4 Na] ; calc. 482.2307), 460.2492
([C29H34NO4 H] ; calc. 460.2489).
(1R,2R,3R,6R,7aR)-Hexahydro-3-(hydroxymethyl-1H-pyrrolizine-1,2,6-triol ( 7-Deoxycasuarine; 7). A
soln. of 16 (23 mg, 0.052 mmol) in 1% HCl/MeOH (2.5 ml) was hydrogenated at 1 atom over (10% Pd/C 12 mg)
for 16 h. The mixture was diluted with MeOH, filtered through Celite, and evaporated. The residue was then
redissolved in H2O (2 ml) and stirred with Dowex 1 Â 8-OH resin (40 mg) for 30 min. Filtration and evaporation
gave 7 (5.8 mg, 60%). White solid. [a]D25 23 (c 0.3, MeOH). 1H-NMR (300 MHz, CD3OD): 4.35
(m, HÀC(6)); 4.01( t, J(1,2) J(1,7a) 7.8, HÀC(1)); 3.72 (dd, J(CH2,3) 3.3, 2J 11.1, 1 H, CH2ÀC(3)); 3.70
(dd, J(2,3) 9.3, HÀC(2)); 3.53 (dd, J(CH2,3) 6.2, 1H, CH 2ÀC(3)); 3.22 (td, J(7a,7') 4.4, J(7a,7) 8.4,
HÀC(7a)); 3.04 (ddd, HÀC(3)); 3.03 (dd, J(5a,6) 4.3, 2J(5a,5b) 11.7, HaÀC(5)); 2.88 (ddd, J(5b,6) 3.4,
4J(5b',7') 1.4, HbÀC(5)); 2.09 (ddd, J(7,6) 5.1, 2J(7,7') 13.4, HÀC(7)); 1.89 (dddd, J(7',6) 3.9, H'ÀC(7)).
13C-NMR (125.7 MHz, CD3OD): 82.9 (C(1)); 79.0 (C(2)); 74.5 (C(6)); 72.8 (C(3)); 68.1 (C(7a)); 64.4 (C(8));
63.3 (C(5)); 39.4 (C(7)): CI-MS: 190 (100, [M H] ). HR-CI-MS: 190.1078 ([C8H15NO4 H] ; calc. 190.1079).
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