Iodine → HCID 15454939, compound

HRID 2287510Notes

Reaction equation

HRID 2287510 reaction equation
[CH2:1]([O:8][C:9]([N:11]1[C@H:15]([CH2:16]O)[C@@H:14]([CH2:18][O:19][CH2:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[C@H:13]([NH:27][C:28]([O:30][C:31]([CH3:34])([CH3:33])[CH3:32])=[O:29])[C@@H:12]1[C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[I:60]I.[O-]S([O-])=O.[Na+].[Na+]>C1(C)C=CC=CC=1>[CH2:1]([O:8][C:9]([N:11]1[C@H:15]([CH2:16][I:60])[C@@H:14]([CH2:18][O:19][CH2:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[C@H:13]([NH:27][C:28]([O:30][C:31]([CH3:34])([CH3:33])[CH3:32])=[O:29])[C@@H:12]1[C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 807Iodine2×HCID 11776TriphenylphosphineHCID 24437Sodium SulfiteHCID 15454938HCID 15454938, compound

Product 1

HCID 15454939HCID 15454939, compoundYield 211.4%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

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.

Workup

  1. temperatureheating at
  2. temperaturea gentle reflux for an hour
  3. customThe layers were separated
  4. washthe organic layer was washed with sat. NaCl aq. solution (×1)
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-c41a9687eb444037a661367f079bb0e6
Source dataset
uspto-grants-2000_07
Patent number
US06083943

Reaction notes

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