Hydrochloric Acid → (R)-5-(allyloxyamino)-4-(2-amino-2-oxoethyl)-1,2,5,6-tetrahydropyridine-2-carboxamide

HRID 627199Notes

Reaction equation

HRID 627199 reaction equation
[CH2:1]([O:4][NH:5][CH: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][C:23]([NH2:25])=[O:24])[CH:2]=[CH2:3].Cl.C([O-])([O-])=O.[K+].[K+]>C(Cl)Cl>[CH2:1]([O:4][NH:5][CH:6]1[CH2:11][NH:10][C@@H:9]([C:19]([NH2:20])=[O:21])[CH:8]=[C:7]1[CH2:22][C:23]([NH2:25])=[O:24])[CH:2]=[CH2:3]

Participants

5

Reactant 3

HCID 313Hydrochloric Acid2×HCID 11430Potassium CarbonateHCID 89851408(2S)-tert-butyl 5-((allyloxy)amino)-4-(2-amino-2-oxoethyl)-2-carbamoyl-5,6-dihydropyridine-1(2H)-carboxylate2×

Product 1

HCID 89852066(R)-5-(allyloxyamino)-4-(2-amino-2-oxoethyl)-1,2,5,6-tetrahydropyridine-2-carboxamideYield 56%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of (2S)-tert-butyl 5-((allyloxy)amino)-4-(2-amino-2-oxoethyl)-2-carbamoyl-5,6-dihydropyridine-1(2H)-carboxylate (Intermediate 176, crude, 330 mg, 0.93 mmol) in DCM (5.0 mL) at 0° C. was added HCl (4.0M in dioxane, 0.233 mL, 0.93 mmol). The mixture was stirred from 0° C. to room temperature for 2 h. Then 0.233 mL more HCl was added to the mixture and stirred for 2 h. It was neutralized by K2CO3 and TEA, filtered and the solvent was removed under vacuum. The crude was subjected to silica column eluting with 0-50% MeOH/DCM to give the desired diastereomeric products as white solids. 100 mg, diastereomer 1. 32 mg, diastereomer 2. 56% yield.

Workup

  1. stirringstirred for 2 h
  2. filtrationfiltered
  3. customthe solvent was removed under vacuum
  4. washeluting with 0-50% MeOH/DCM

Sources & evidence

ORD record
ord-34fde70e49784faeafa4e6839a290e22
Source dataset
uspto-grants-2016_04
Patent number
US09309245B2

Reaction notes

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