2552
P. Hutin et al. / Tetrahedron: Asymmetry 11 (2000) 2547±2553
separated and washed with brine (30 ml), dried (MgSO4), and the solvent was evaporated to give
the expected O-mesylated intermediate as a colourless oil which was used in the next step without
puri®cation. Thus, the crude product was diluted in THF (30 ml) in the presence of 10% HCl (20
ml) and re¯uxed for 12 h. After cooling to 0ꢀC, the solution was basi®ed (pH=10), and the
mixture was stirred for 2 h. The solution was extracted with CH2Cl2 (2Â40 ml) and the organic
extract dried (MgSO4) and evaporated in vacuo. The residue obtained was ®nally puri®ed by ¯ash
22
D
chromatography (CH2Cl2:MeOH, 90:10) to give a solid (1.25 g, 80%): ꢀ ^82.1 (c 1.13,
CH2Cl2); mp 81±82ꢀC (lit.11a mp 80±82ꢀC); H NMR (400 MHz, CDCl3) ꢂ 2.16 (dd, J=3.8 and
1
10.9 Hz, 1H, CH-N), 2.80±2.95 (m, 3H, CH-N and CH2-Ph), 3.35 and 4.12 (dd AB system,
J=12.9 Hz, 2H, CH2-Ph), 3.37 (dd, J=6.2 and 10.9 Hz, 1H, CH-N), 3.62±3.65 (m, 1H, CH-O),
3.78 (s, 3H, CH3-O), 4.05±4.09 (m, 1H, CH-O), 6.83 (d, J=8.7 Hz, 2H, Ph), 7.22 (d, J=8.7 Hz,
2H, Ph), 7.24±7.34 (m, 5H, Ph); 13C NMR (50 MHz, CDCl3) ꢂ 32.6, 55.10, 58.2, 59.8, 68.0, 75.6,
78.2, 113.8, 127.2, 128.3, 129.0, 130.1, 131.0, 137.9, 157.9; MS (CI, NH3) m/z 192 (14.8%), 314
(MH+, 100%); MS (EI) m/z 380 (5%), 338 (31%), 250 (100%), 239 (7%), 91 (13%), 77 (7%), 57
(8%), 43 (22%).
3.6. (2R,3S,4S)-3,4-Dihydroxy-2-(4-methoxybenzyl)pyrrolidine, (^)-deacetylanisomycin 2
The pyrrolidine 11 (625 mg, 2 mmol) was dissolved in absolute ethanol (30 ml) containing
palladium on activated carbon (10%) as catalyst (100 mg) and hydrogenated at atmospheric
pressure for 15 h. The catalyst was removed by ®ltration through Celite and the solvent was evap-
22
D
20
D
orated to dryness to give 2 as a solid (400 mg, 90%): ꢀ ^29 (c 1.25, EtOH), lit.21: ꢀ ^20 (c
1.0, EtOH); mp 173±174ꢀC (lit.11d mp 176±177ꢀC); H NMR (400 MHz, CD3OD) ꢂ 2.54 (dd,
J=1.8 and 12.3 Hz, 1H, CH-N), 2.72 (dd, J=6.6 and 13.5 Hz, 1H, CH-Ph), 2.89 (dd, J=8.2 and
13.5 Hz, 1H, CH-Ph), 3.18±3.22 (m, 1H, CH-N), 3.28 (dd, J=5.6 and 12.4 Hz, 1H, CH-N), 3.71
(d, J=2.8 Hz, 1H, CH-O), 3.75 (s, 3H, CH3-O), 4.07 (d, J=5.3 Hz, 1H, CH-O), 4.87 (s, 3H, NH,
OH), 6.73 (d, J=8.7 Hz, 2H, Ph), 7.10 (d, J=8.7 Hz, 2H, Ph); 13C NMR (50 MHz, CD3OD) ꢂ
34.4, 53.5, 55.6, 64.2, 78.0, 78.6, 114.8, 131.0, 132.9, 159.6; MS (CI, NH3) m/z 224 (MH+, 100%),
206 (12%), 188 (26%).
1
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