2,2,2-Trifluoroethanol → HCID 86665795, compound

HRID 590757Notes

Reaction equation

HRID 590757 reaction equation
[CH2:1]([CH:4]1[C:8](=O)[CH2:7][CH:6]([NH:10][C:11](=[O:17])[O:12][C:13]([CH3:16])([CH3:15])[CH3:14])[CH2:5]1)[CH:2]=[CH2:3].[C:18]([O-:21])(=O)[CH3:19].[NH4+:22].[C:23]([N+:27]#[C-])([CH3:26])([CH3:25])[CH3:24].FC(F)(F)[CH2:31][OH:32]>>[C:18]([NH:22][C@:8]1([C:31](=[O:32])[NH:27][C:23]([CH3:26])([CH3:25])[CH3:24])[C@@H:4]([CH2:1][CH:2]=[CH2:3])[CH2:5][C@H:6]([NH:10][C:11](=[O:17])[O:12][C:13]([CH3:16])([CH3:15])[CH3:14])[CH2:7]1)(=[O:21])[CH3:19]

Participants

5

Reactant 4

HCID 64092,2,2-TrifluoroethanolHCID 23577Tert-Butyl isocyanideHCID 517165Ammonium AcetateHCID 67513641Tert-butyl 3-allyl-4-oxocyclopentylcarbamate

Product 1

HCID 86665795HCID 86665795, compoundYield 58%

Procedure

While under nitrogen, a mixture of tert-butyl 3-allyl-4-oxocyclopentylcarbamate, mixture of isomers (1.08 g, 4.5 mmol) and ammonium acetate (1.39 g, 18 mmol) in 2,2,2-trifluoroethanol (5 mL) was treated with t-butylisonitrile (1.53 mL, 13.5 mmol) and stirred at room temperature for 3 days. The reaction mixture was concentrated in vacuo and dissolved in dichloromethane (50 mL). The solution was washed with water (25 mL), dried (Na2SO4), and added to a silica gel column (˜250 cc). This was eluted successively with 50%, 65%, 70%, and 75% ethyl acetate in heptane to afford tert-butyl (1S,3S,4S)-3-acetamido-4-allyl-3-(tert-butylcarbamoyl)cyclopentylcarbamate (0.99 g, 58%) as a white solid. NMR (CDCl3): δ 7.72 and 7.04 (br s, 1 H combined), 7.27 and 6.35 (br s, 1 H combined), 5.84 and 5.06 (br s, 1 H combined), 5.55-5.70 (m, 1 H), 4.85-4.95 (m, 2 H), 3.90-4.15 (m, 1 H), 2.10-2.90 (m, 4 H), 1.70-2.00 (m, 6 H), 1.20-1.40 (m, 18 H). MS (M+1): 382.2.

Workup

  1. concentrationThe reaction mixture was concentrated in vacuo
  2. dissolutiondissolved in dichloromethane (50 mL)
  3. washThe solution was washed with water (25 mL)
  4. dry with materialdried (Na2SO4)
  5. additionadded to a silica gel column (˜250 cc)
  6. washThis was eluted successively with 50%, 65%, 70%, and 75% ethyl acetate in heptane

Sources & evidence

ORD record
ord-04bf80ad2a66402a9607b37cd81dabc9
Source dataset
uspto-grants-2016_01
Patent number
US09233985B2

Reaction notes

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