Acetic Acid → HCID 15454938, compound

HRID 2287509Notes

Reaction equation

HRID 2287509 reaction equation
[CH2:1]([O:8][C:9]([N:11]1[C@H:15]([CH2:16][O:17][Si](C(C)(C)C)(C)C)[C@@H:14]([CH2:25][O:26][CH2:27][C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[C@H:13]([NH:34][C:35]([O:37][C:38]([CH3:41])([CH3:40])[CH3:39])=[O:36])[C@@H:12]1[C:42]1[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CC(O)=O.[N+](CCCC)(CCCC)(CCCC)CCCC.[F-].C([O-])(O)=O.[Na+]>C1COCC1>[CH2:1]([O:8][C:9]([N:11]1[C@H:15]([CH2:16][OH:17])[C@@H:14]([CH2:25][O:26][CH2:27][C:28]2[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=2)[C@H:13]([NH:34][C:35]([O:37][C:38]([CH3:40])([CH3:41])[CH3:39])=[O:36])[C@@H:12]1[C:42]1[CH:43]=[CH:44][CH:45]=[CH:46][CH:47]=1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 516892Sodium BicarbonateHCID 2724141Tetrabutylammonium Fluoride2×HCID 15454937HCID 15454937, compound

Product 1

HCID 15454938HCID 15454938, compoundYield 119.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

To a stirred and ice-cooled solution of (2S*,3S*,4S*,5S*)-1-benzyloxycarbonyl-4-benzyloxymethyl-3-[N-(t-butoxycarbonyl)amino]-5-(t-butyldimethylsilyloxy)methyl-2-phenylpyrrolidine (14.5 g, ca.21.3 mmol) in dry THF (20 ml) was added a mixture of glacial AcOH (1.59 ml, d1.049, 27.7 mmol) and a 1.0M solution of (n-Bu)4NF in THF (Aldrich, 32.0 ml, 32.0 mmol) dropwise. After stirring at room temperature for 6 hours, a further amount of a 1.0M solution of (n-Bu)4NF in THF (15.0 ml, 15.0 mmol) was added dropwise at room temperature. After the stirring was continued for 2 days, the resultant orange mixture was neutralized with sat. NaHCO3 aq. solution, and concentrated in vacuo at a bath temperature of 40 C. The residue was diluted with AcOEt (200 ml), washed with H2O (×2), sat. NaHCO3 aq. solution (×1), and sat. NaCl aq. solution (×1), dried (MgSO4), and concentrated in vacuo to give a dark red viscous oil (13.9 g). This was chromatographed over SiO2 (Merck Kieselgel 60, 130 g). Elution with n-hexane-AcOEt (20:1→10:1→5:1→4:1→2:1) gave a red solid (10.6 g). This was recrystallized from AcOEt-n-hexane; the crystals were filtered off, washed with AcOEt-n-hexane (1:4, ×1), and dried in vacuo to give the title compound (9.0 g, 78%) as a slightly purple crystals. A portion of it was recrystallized from AcOEt-n-hexane to afford an analytical sample of the title compound: mp 126.5-129.5 C. (white fine needles); IRmax (nujol): 3430(s), 3380(s), 1690(vs), 1518(s), 1498(m), 1100(s), 785(m), 770(s), 747(s), 740(s), 715(s), 695(s) cm-1 ; 1H-NMR δ: 7.45-7.15(m, 17H), 6.94(br.s, 1H), 5.22(d, J=8.1 Hz, 1H), 5.02(br.s, 2H), 4.87(br.s, 1H) 4.52(s), 2H), 4.30(dd, J=19.0, 9.0 Hz, 1H), 4.2-4.00(m, 2H), 4.03-3.90(m, 1H), 3.68-3.50(m, 2H), 2.10-1.85(m, 1H), 1.37(br.s, 9H) ppm.

Workup

  1. additionwas added
  2. stirringAfter stirring at room temperature for 6 hours
  3. concentrationconcentrated in vacuo at a bath temperature of 40 C
  4. additionThe residue was diluted with AcOEt (200 ml)
  5. washwashed with H2O (×2), sat. NaHCO3 aq. solution (×1), and sat. NaCl aq. solution (×1)
  6. dry with materialdried (MgSO4)
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-327418b017954ea5953dd864b3f44471
Source dataset
uspto-grants-2000_07
Patent number
US06083943

Reaction notes

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