Diisopropylamine → Tert-butyl 3-amino-3-[5-(benzyloxy)pyridin-3-yl]prop-2-enoate

HRID 526373Notes

Reaction equation

HRID 526373 reaction equation
C(NC(C)C)(C)C.C([Mg]Br)C.[C:12]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])(=[O:14])[CH3:13].[CH2:20]([O:27][C:28]1[CH:29]=[C:30]([C:34]#[N:35])[CH:31]=[N:32][CH:33]=1)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.[Cl-].[NH4+]>C(OCC)C>[NH2:35][C:34]([C:30]1[CH:31]=[N:32][CH:33]=[C:28]([O:27][CH2:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[CH:29]=1)=[CH:13][C:12]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14]

Participants

7

Reactant 5

HCID 7912DiisopropylamineHCID 10908tert-Butyl acetateHCID 25517Ammonium ChlorideHCID 538508325-(Benzyloxy)nicotinonitrileHCID 178418443HCID 178418443, compound

Product 1

HCID 71259023Tert-butyl 3-amino-3-[5-(benzyloxy)pyridin-3-yl]prop-2-enoate

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent3×

Procedure

Diisopropylamine (12.8 mL, 91 mmol) was added at 0° C. to a 3M solution of ethyl magnesium bromide in diethyl ether (15 mL, 45 mmol) and additional diethyl ether (40 mL). After one hour at 0° C. t-butyl acetate was added and stirring was continued for 30 minutes. 5-(benzyloxy)pyridine-3-carbonitrile (2.9 g, 13.8 mmol) in diethyl ether (40 mL) was added at 0° C. After 2.5 hours at 0° C. saturated aqueous ammonium chloride solution was added. Phases were separated and the aqueous phase was extracted with diethyl ether. The combined extracts were washed with brine and dried over sodium sulfate. The solution was concentrated under reduced pressure and the residue was purified by chromatography on silica gel (ethyl acetate in hexane, 0 to 45%) to yield 1.95 g tert-butyl 3-amino-3-[5-(benzyloxy)pyridin-3-yl]prop-2-enoate.

Workup

  1. customPhases were separated
  2. extractionthe aqueous phase was extracted with diethyl ether
  3. washThe combined extracts were washed with brine
  4. dry with materialdried over sodium sulfate
  5. concentrationThe solution was concentrated under reduced pressure
  6. customthe residue was purified by chromatography on silica gel (ethyl acetate in hexane, 0 to 45%)

Sources & evidence

ORD record
ord-e2ab0374c9ce4f81bf4e79872eb769f3
Source dataset
uspto-grants-2016_05
Patent number
US09345793B2

Reaction notes

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