Hydrochloric Acid → (S)-N-(1-Ethoxycarbonyl-2-methyl-prop-1-yl)-N-(6-bromopyridin-3-ylmethyl)-amine

HRID 233741Notes

Reaction equation

HRID 233741 reaction equation
[Br:1][C:2]1[N:7]=[CH:6][C:5]([CH:8]=O)=[CH:4][CH:3]=1.Cl.[CH2:11]([O:13][C:14](=[O:20])[C@H:15]([CH:17]([CH3:19])[CH3:18])[NH2:16])[CH3:12].C([O-])(=O)C.[Na+].C([BH3-])#N.[Na+].Cl.C(=O)([O-])[O-].[Na+].[Na+]>CO>[CH2:11]([O:13][C:14]([C@@H:15]([NH:16][CH2:8][C:5]1[CH:6]=[N:7][C:2]([Br:1])=[CH:3][CH:4]=1)[CH:17]([CH3:19])[CH3:18])=[O:20])[CH3:12]

Participants

8

Reactant 6

HCID 313Hydrochloric AcidHCID 10340Sodium CarbonateHCID 87181Ethyl L-valinate hydrochlorideHCID 517045Sodium AcetateHCID 5003444Sodium cyanoborohydrideHCID 117692346-Bromo-3-pyridinecarboxaldehyde

Product 1

HCID 54400421(S)-N-(1-Ethoxycarbonyl-2-methyl-prop-1-yl)-N-(6-bromopyridin-3-ylmethyl)-amineYield 24.5%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A solution of 4.77 g (25.65 mmol) of 6-bromo-3-pyridinecarboxaldehyde, 4.66 g (25.65 mmol) of L-valine ethyl ester hydrochloride and 4.24 g (51.3 mmol) of sodium acetate in 400 ml of methanol is stirred for 30 min together with 25 g of 4A molecular sieve. After adding 3.22 g (51.3 mmol) of sodium cyanoborohydride, the mixture is stirred at room temperature overnight, adjusted to pH=2 with dilute hydrochloric acid, then adjusted to pH 10 with sodium carbonate and filtered with suction through kieselguhr. The solution is diluted with water and washed three times with ethyl acetate; the combined organic phases are washed with sodium chloride solution, and then dried over sodium sulphate and chromatographed on 350 g of silica gel using ethyl acetate/toluene mixtures (1:20→1:10) to give 1.98 g of the title compound.

Workup

  1. filtrationfiltered with suction through kieselguhr
  2. additionThe solution is diluted with water
  3. washwashed three times with ethyl acetate
  4. washthe combined organic phases are washed with sodium chloride solution
  5. dry with materialdried over sodium sulphate
  6. customchromatographed on 350 g of silica gel

Sources & evidence

ORD record
ord-71ac617c7358417cb43746d12cd73a64
Source dataset
uspto-grants-1997_01
Patent number
US05594010

Reaction notes

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