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Chemical Structure| 101408-94-0 Chemical Structure| 101408-94-0

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Chemical Structure| 101408-94-0

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Product Details of [ 101408-94-0 ]

CAS No. :101408-94-0
Formula : C11H19NO4
M.W : 229.27
SMILES Code : O=C(N1C[C@H](OC(C)=O)CC1)OC(C)(C)C

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* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 101408-94-0 ]

[ 101408-94-0 ] Synthesis Path-Downstream   1~1

  • 1
  • [ 108-24-7 ]
  • [ 109431-87-0 ]
  • [ 101408-94-0 ]
YieldReaction ConditionsOperation in experiment
0.87 g With pyridine; dmap; In dichloromethane; at 20℃; for 4h; Crude tert-butyl (R)-3-hydoxypyrrolidine-1-carboxylate, prepared from (R)-3-hydroxylpyrrolidine hydrochloride (R)-2a·HCl (0.50 g, 4.1 mmol) by the above-described procedure, was dissolved in anhydrous CH2Cl2 (20 mL). Pyridine (0.98 mL, 12.1 mmol), Ac2O (0.77 mL, 8.1 mmol) and DMAP (25 mg, 0.20 mmol) were added, and the reaction mixture was stirred at rt for 4 h before being quenched with water. The layers were separated, and the aqueous layer was extracted three times with CH2Cl2. The combined organic layer was dried over Na2SO4, filtered, and concentrated in vacuo. The residue was purified by flash column chromatography (hexane-EtOAc, 3:1) to give 0.87 g of tert-butyl (R)-3-acetoxypyrrolidine-1-carboxylate [93% from (R)-2a·HCl]. A colorless oil, -16.1 (c=0.90, CHCl3). 1H NMR (500 MHz, CDCl3) δ: 1.44 (9H, s), 1.94-2.05 (5H, m), 3.33-3.56 (4H, m), 5.24 (1H, br). 13C NMR (125 MHz, CDCl3) δ: 21.1, 28.4, 30.7, 31.5, 43.6, 43.9, 51.4, 51.8, 72.9, 73.8, 79.5, 154.3, 154.4, 170.5, 170.6. IR (CHCl3): 1735, 1689, 1685 cm-1. HRMS Calcd for C11H19NNaO4 [(M+Na)+] m/z: 252.1206, found: 252.1183.Similarly to the preparation of (R)-1d, 230 mg of (R)-1e (74%, 99% ee) and 76 mg of (R)-4-acetoxy-1-pyrroline N-oxide (R)-4e (24%) were obtained from tert-butyl (R)-3-acetoxypyrrolidine-1-carboxylate (500 mg, 2.2 mmol). The optical purity of (R)-1e was determined by Daicel CHIRALCEL OZ-3 [hexane-iPrOH, 80:20, 2.0 mL/min; retention times 34.5 (R), 41.4 min (S)].(R)-1e. A pale yellow oil, +215 (c=0.42, CHCl3). 1H NMR (500 MHz, CDCl3) δ: 2.08 (3H, s), 2.25 (1H, dddd, J=2.0, 4.0, 8.0, 14.5 Hz), 2.64-2.73 (1H, m), 3.93 (1H, dddd, J=2.0, 4.0, 9.0, 14.0 Hz), 4.15-4.24 (1H, m), 5.72-5.77 (1H, m), 6.99 (1H, q, J=2.0 Hz). 13C NMR (125 MHz, CDCl3) δ: 20.8, 26.8, 61.3, 73.8, 132.2, 170.4. IR (CHCl3): 1744, 1582, 1242 cm-1. HRMS Calcd for C6H9NNaO3 [(M+Na)+] m/z: 166.0475, found: 166.0493.(R)-4-Acetoxy-1-pyrroline N-oxide [(R)-4e]. A pale yellow oil, -23.7 (c=0.35, CHCl3). 1H NMR (500 MHz, CDCl3) δ: 2.08 (3H, s), 2.78 (1H, d, J=22.0 Hz), 3.17 (1H, ddd, J=1.5, 7.0, 22.0 Hz), 3.92 (1H, d, J=15.0 Hz), 4.30 (1H, ddd, J=1.5, 7.0, 15.0 Hz), 5.42 (1H, t, J=7.0 Hz), 6.87 (1H, t, J=1.5 Hz). 13C NMR (125 MHz, CDCl3) δ: 20.8, 36.3, 67.4, 67.6, 134.2, 170.2. IR (CHCl3): 1743, 1595, 1238 cm-1. HRMS Calcd for C6H9NNaO3 [(M+Na)+] m/z: 166.0475, found: 166.0480.
 

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