Hydroxylamine → Allyl Fmoc Alcohol

HRID 396938Notes

Reaction equation

HRID 396938 reaction equation
Cl[C:2]([O:4][CH2:5][CH:6]1[C:18]2[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=2[C:12]2[C:7]1=[CH:8][CH:9]=[CH:10][CH:11]=2)=[O:3].N[OH:20].C([O-])([O-])=O.[Na+].[Na+].[CH2:27]1[CH2:31]OC[CH2:28]1>O.O>[CH2:31]([CH:5]([CH:6]1[C:18]2[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=2)[C:12]2[C:7]1=[CH:8][CH:9]=[CH:10][CH:11]=2)[O:4][C:2]([OH:20])=[O:3])[CH:27]=[CH2:28]

Participants

6

Reactant 4

HCID 787HydroxylamineHCID 8028TetrahydrofuranHCID 10340Sodium CarbonateHCID 343679-Fluorenylmethyl chloroformate

Product 1

HCID 86759120Allyl Fmoc AlcoholYield 68%

Reagents, catalysts & solvents 1

HCID 447138Water dimerSolvent

Procedure

9-Fluorenylmethyl chloroformate (5.65 g, 0.022 mol) was added portionwise to a stirred solution of the amino alcohol 4 (7.5 g, 0.02 mol) and Na2CO3 (5.26 g, 0.05 mol) in a mixture of THF (150 ml) and water H2O (150 ml) at 0° C. The reaction mixture was allowed to return to room temperature, stirred for a further 2 h, and then extracted with EtOAc (3×50 ml). The combined organic phase was washed with H2O (3×50 ml) and brine (3×25 ml), dried over magnesium sulphate and evaporated in vacuo to give a dark red oil. This was purified by flash column chromatography (petroleum ether 40-60/EtOAc, 1:1) to afford 5b as a pale yellow oil (8.11 g, 68%): 1H NMR (270 MHZ, CDCl3): δ1.72-2.18 (m, 6H); 2.9 (t, J=6.4, 2H); 3.43-3.91 (m, 3H); 3.81 (s, 3H); 4.25-4.54 (m, 5H); 4.61-4.65 (m, 2H); 5.21-5.37 (m, 2H); 5.85-6.0 (m, 1H); 6.85 (s, 1H); 7.31-7.79 (m, 9H); 8.77 (br s, 1H); 13C NMR (67.8 MHZ, CDCl3): δ25.1, 28.4, 35.3, 47.0, 56.7, 60.9, 64.3, 65.4, 66.3, 67.1, 106.4, 111.7, 118.3, 120.0, 125.2, 127.1, 127.2, 127.8, 131.5, 131.9, 141.3, 143.7, 144.4, 150.2, 153.8, 170.3; MS (FAB): 601 (M+•1); HRMS: calcd for C34H36N2O8 600.667, found 600.2175. IR (film): ν 3315, 2952, 1727, 1597, 1522, 1452, 1392, 1322, 1174, 1117, 1017.

Workup

  1. customto return to room temperature
  2. extractionextracted with EtOAc (3×50 ml)
  3. washThe combined organic phase was washed with H2O (3×50 ml) and brine (3×25 ml)
  4. dry with materialdried over magnesium sulphate
  5. customevaporated in vacuo
  6. customto give a dark red oil
  7. customThis was purified by flash column chromatography (petroleum ether 40-60/EtOAc, 1:1)

Sources & evidence

ORD record
ord-7927db43c5e74d8888ee9a7e12f35ffd
Source dataset
uspto-grants-2003_08
Patent number
US06608192B1

Reaction notes

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