Trifluoroacetic acid → (2S,5R)-5-(allyloxyamino)-4-(methoxymethyl)-1,2,5,6-tetrahydropyridine-2-carboxamide

HRID 627122Notes

Reaction equation

HRID 627122 reaction equation
[CH2:1]([O:4][N:5](C(OC(C)(C)C)=O)[C@H:6]1[CH2:11][N:10](C(OC(C)(C)C)=O)[C@H:9]([C:19](=[O:21])[NH2:20])[CH:8]=[C:7]1[CH2:22][O:23][CH3:24])[CH:2]=[CH2:3].C(O)(C(F)(F)F)=O>C(Cl)Cl>[CH2:1]([O:4][NH:5][C@H:6]1[CH2:11][NH:10][C@H:9]([C:19]([NH2:20])=[O:21])[CH:8]=[C:7]1[CH2:22][O:23][CH3:24])[CH:2]=[CH2:3]

Participants

4

Reactant 2

HCID 6422Trifluoroacetic acidHCID 89852023(2S,5R)-tert-butyl 5-(allyloxy(tert-butoxycarbonyl)amino)-2-carbamoyl-4-(methoxymethyl)-5,6-dihydropyridine-1(2H)-carboxylate2×

Product 1

HCID 89851857(2S,5R)-5-(allyloxyamino)-4-(methoxymethyl)-1,2,5,6-tetrahydropyridine-2-carboxamideYield 66.8%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

(2S,5R)-tert-butyl 5-(allyloxy(tert-butoxycarbonyl)amino)-2-carbamoyl-4-(methoxymethyl)-5,6-dihydropyridine-1(2H)-carboxylate (Intermediate 73, 3.07 g, 6.95 mmol) was dissolved in 20 mL DCM. Then 5.36 mL TFA was added dropwise at 0° C. The mixture was stirred at rt for 3 h. The solvent was removed in vacuo and co-evaporated twice with 5 mL MeOH. The residue was dissolved in MeOH (10 mL) and ammonium hydroxide (30% in water) was added until it was basic. The mixture was rotovapored at rt and the residue was freeze-dried over night to give a solid. It was dissolved in DCM and purified on silica gel eluting with 0-100% MeOH/DCM to give a off-white solid (1.12 g, 66.8%).

Workup

  1. customThe solvent was removed in vacuo
  2. dissolutionThe residue was dissolved in MeOH (10 mL)
  3. additionammonium hydroxide (30% in water) was added until it
  4. customwas rotovapored at rt
  5. customthe residue was freeze-dried over night
  6. customto give a solid
  7. custompurified on silica gel eluting with 0-100% MeOH/DCM

Sources & evidence

ORD record
ord-266274aa726e415592f06b933944ab86
Source dataset
uspto-grants-2016_04
Patent number
US09309245B2

Reaction notes

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