Iodine → HCID 15454939, compound

Participants

Reaction Steps

To a stirred mixture of (2S*,3S*,4S*,5S*)-1-benzyloxycarbonyl-4-benzyloxymethyl-3-[N-(t-butoxycarbonyl)amino]-5-hydroxymethyl-2-phenylpyrrolidine (9.00 g, 16.5 mmol), Ph3P (10.8 g, 41.3 mmol) and Im (2.81 g, 41.3 mmol) in dry PhMe (240 ml) was added I2 (8.38 g, 33.0 mmol) in one portion at room temperature. After stirring and heating at a gentle reflux for an hour, the dark brown mixture was allowed to cool to room temperature, and then sat. Na2SO3 aq. solution (70 ml) was added until the dark color due to the excess I2 was discharged. The layers were separated, and the organic layer was washed with sat. NaCl aq. solution (×1), dried (MgSO4), and concentrated in vacuo to give a deep red oil (22.9 g). This was chromatographed over SiO2 (Merck Kieselgel 60, 230 g). Elution with n-hexane-AcOEt (30:1→10:1→6:1) gave the title compound (9.95 g, 92%) as a white solid. A portion of it (105 mg) was recrystallized from isopropyl ether (IPE) to afford an analytical sample of the title compound as white powders (mp 107.5-108.5 C.); IRmax (nujol): 3440(s), 1705(vs), 1500(s), 1165(s), 780(m), 770(m), 755(m), 740(m), 707(s), 695(s) cm-1 ; 1H-NMR δ: 7.60-7.15(m, 14H), 7.09(br.s, 2H), 5.19(d, J=8.8 Hz, 1H), 5.03(br.s, 2H), 2H), 4.44(ddd, J=9.0, 9.0, 9.0 Hz, 1H), 4.15-3.97(m, 1H), 3.97-3.75(m, 2H), 3.71(dd, J=9.7, 5.3 Hz, 1H), 3.64(dd, J=9.7, 5.3 Hz, 1H), 2.34-2.18(m, 1H), 1.36(br.s, 9H) ppm.

Provenance & Evidence