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F. Carrel, P. Vogel / Tetrahedron: Asymmetry 11 (2000) 4661–4680
trated. FC (silica gel, EtOAc/light petroleum ether (1:9)+1% NEt3) afforded (−)-16 (604 mg) and
a mixture of (−)-16 and (+)-17 (3.88 g). (Overall yield based on ( )-14: 77%.) Analytical samples
of (−)-16 and (+)-17 can be obtained by FC (silica gel, EtOAc/light petroleum ether (1:9)+1%
NEt3), Rf (EtOAc/light petroleum ether (1:3)) (−)-16=0.38, Rf (EtOAc/light petroleum ether
(1:3)) (+)-17=0.47: colorless oils.
Data for (−)-16. [h]52859=−30, [h]52757=−31, [h]52546=−35, [h]42535=−55, [h]42053=−63 (c=1.0,
CHCl3). UV (CH3CN): umax=213 nm (m=12700 [dm3 cm−1 mol−1]). IR (film): 2955, 2870, 2105,
1
1495, 1455, 1415, 1380, 1295, 1255, 1115, 1015, 885, 785, 735, 700 cm−1. H NMR (CDCl3, 400
2
MHz): 7.42–7.09 (m, 15H(Ph)); 4.82 (s, H-2); 4.59, 4.55 (2d, J=11.9 Hz, CH2(Bn)); 4.28, 4.14
2
3
(2d, J=9.3 Hz, CH2-C2%); 4.25 (d, J(H-4,H-5)=7.7 Hz, H-4); 4.20–4.16 (m, H-4%+H-5); 4.06
3
3
3
2
3
(ddd, J(H-6%,H-5%)=9.9 Hz, J=2.8 Hz, J=1.9 Hz, H-6%); 4.02 (dd, J=11.1 Hz, J=2.8 Hz,
2
3
3
H-C-C6%); 3.95 (dd, J=11.1 Hz, J=1.9 Hz, H%-C-C6%); 3.56 (dd, J(H-5%,H-6%)=9.9 Hz,
3J(H-5%,H-4%)=2.8 Hz, H-5%); 2.37 (dd, J=14.5 Hz, J(H-3%,H-4%)=3.1 Hz, H-3%); 2.18 (dd,
2
3
2J=14.5 Hz, J(H%-3%,H-4%)=3.7 Hz, H%-3%); 1.21–1.15 (m, 21H(TIPS)); 1.11 (t, J=7.7 Hz,
3
3
3Me(TES)); 0.76 (2q, J=7.7 Hz, 3CH2(TES)). 13C NMR (CDCl3, 100.6 MHz): 142.9, 141.6,
3
1
1
138.7 (3s, 3Car); 128.4–127.1 (9d, Jꢀ160 Hz, 15CHar); 78.6 (d, J=149 Hz, C2); 76.6 (s, C2%);
1
1
1
73.5 (t, J=141 Hz, CH2(Bn)); 71.1 (d, J=139 Hz, C5); 70.3 (t, J=145 Hz, CH2-C2%); 69.9 (d,
1J=143 Hz, C4); 69.2 (d, J=142 Hz, C6%); 68.4 (d, J=149 Hz, C4%); 64.2 (t, J=141 Hz,
1
1
1
1
1
1
CH2-C6%); 60.1 (d, J=142 Hz, C5%); 33.0 (t, J=128 Hz, C3%); 18.0 (q, J=126 Hz, 6Me(TIPS));
1
1
1
12.1 (d, J=118 Hz, 3CH(TIPS)); 6.95 (q, J=126 Hz, 3Me(TES)); 4.9 (d, J=117 Hz,
3CH2(TES)). CI-MS(NH3): m/z 786 (100, [M+H]+), 757 (4, [M−N2]+), 742 (2, [M−i-Pr]+), 681
(4), 636 (6), 609 (9),531(10), 223 (21).
Data for (+)-17. [h]25589=42, [h]52757=43, [h]25546=49, [h]24355=85, [h]24503=105 (c=1.0, CHCl3). UV
(CH3CN): umax=215 nm (m=13100 [dm3 cm−1 mol−1]). IR (film): 2865, 2105, 1495, 1455, 1415,
1365, 1255, 1120, 1015, 885, 745, 700 cm−1. H NMR (CDCl3, 400 MHz): 7.44–7.11 (m,
1
2
2
15H(Ph)); 4.84 (s, H-2); 4.62, 4.54 (2d, J=12.1 Hz, CH2(Bn)); 4.32, 4.04 (2d, J=9.8 Hz,
3
3
3
CH2-C2%); 4.26 (d, J(H-4,H-5)=7.8 Hz, H-4); 4.18 (ddde, J(H-4%,H-5%)=4.0 Hz, J(H-4%,H-
3%)=3.2 Hz, 3J(H-4%,H-3%)=2.9 Hz, H-4%); 4.26 (d, 3J(H-5,H-4)=7.8 Hz, H-5); 4.08 (dm,
3J(H-6%,H-5%)=9.8 Hz, H-6%); 4.01 (dd, J=10.9 Hz, J=3.5 Hz, H-C-C6%); 3.97 (dd, J=10.9
2
3
2
3
3
3
Hz, J=2.5 Hz, H-C-C6%); 3.43 (dd, J(H-5%,H-6%)=9.8 Hz, J(H-5%,H-4%)=2.9 Hz, H-5%); 2.50
2
3
2
(br.s, 2 NH); 2.23 (dd, J=14.4 Hz, J(H-3%,H-4%)=3.2 Hz, H-3%); 2.17 (dd, J=14.4 Hz,
3J(H%-3%,H-4%)=4.0 Hz, H%-3%); 1.21–1.15 (m, 21H(TIPS)); 1.13 (t, J=7.8 Hz, 3Me(TES));
3
0.78+0.77 (2q, J=7.8 Hz, 3CH2(TES)). 13C NMR (CDCl3, 100.6 MHz): 142.9, 141.4, 138.7 (3s,
3
1
3Car); 128.3, 128.2, 128.0, 127.7, 127.5, 127.5, 127.3, 127.3, 127.1 (9d, Jꢀ160 Hz, 15CHar);
78.0 (d, J=153 Hz, C2); 77.2 (s, C2%); 73.5 (t, J=141 Hz, CH2(Bn)); 70.9 (d, J=135 Hz, C5);
1
1
1
1
1
1
70.2 (t, J=145 Hz, CH2-C2%); 69.6 (d, J=138 Hz, C4); 69.4 (d, J=138 Hz, C6%); 68.5 (d,
1J=146 Hz, C4%); 64.3 (t, J=141 Hz, CH2-C6%); 60.3 (d, J=144 Hz, C5%); 32.9 (t, J=129 Hz,
1
1
1
1
1
1
C3%); 17.9 (q, J=126 Hz, 6Me(TIPS)); 12.0 (d, J=118 Hz, 3CH(TIPS)); 6.9 (q, J=126 Hz,
3Me(TES)); 4.9 (d, J=117 Hz, 3CH2(TES)). CI-MS(NH3): m/z 786 (100, [M+H]+), 758 (4,
1
[M+H−N2]+), 742 (3, [M−i-Pr]+), 635 (4, [M−CH2OBn−Et]+), 531 (6), 223 (42)).
4.15. (1R,2R,5R,6R,7R)-6-exo-Azido-1-[(benzyloxy)methyl]-3,9-dioxabicyclo[3.3.1]nonan-
2-exo,7-exo-diol (h-18) and (1R,2S,5R,6R,7R)-6-exo-azido-1-[(benzyloxy)methyl]-3,9-dioxa-
bicyclo[3.3.1]nonan-2-endo,7-exo-diol i-18
HF/pyr (7:3) (1.4 mL, 52.2 mmol) was added to a soln of pure (−)-16 (687 mg, 0.87 mmol)
in THF (15 mL) stirred at 0°C. After 30 min, the mixture was treated with EtOAc (10 mL) and