Formaldehyde → Ethyl 3-t-butyldimethylsilyloxy-3-(2-chloropyridin-3-yl)-2-methylaminopropionate

HRID 1599315Notes

Reaction equation

HRID 1599315 reaction equation
C=O.[C:3]([BH3-])#N.[Na+].[NH2:7][CH:8]([CH:14]([O:22][Si:23]([C:26]([CH3:29])([CH3:28])[CH3:27])([CH3:25])[CH3:24])[C:15]1[C:16]([Cl:21])=[N:17][CH:18]=[CH:19][CH:20]=1)[C:9]([O:11][CH2:12][CH3:13])=[O:10].C(=O)([O-])O.[Na+]>O.C(Cl)Cl.C(O)(=O)C>[Si:23]([O:22][CH:14]([C:15]1[C:16]([Cl:21])=[N:17][CH:18]=[CH:19][CH:20]=1)[CH:8]([NH:7][CH3:3])[C:9]([O:11][CH2:12][CH3:13])=[O:10])([C:26]([CH3:28])([CH3:27])[CH3:29])([CH3:25])[CH3:24]

Participants

8

Reactant 4

HCID 712FormaldehydeHCID 516892Sodium BicarbonateHCID 5003444Sodium cyanoborohydrideHCID 23298326Ethyl 2-amino-3-t-butyldimethylsilyloxy-3-(2-chloropyridin-3-yl)propionate

Product 1

HCID 23298295Ethyl 3-t-butyldimethylsilyloxy-3-(2-chloropyridin-3-yl)-2-methylaminopropionateYield 27.9%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

182 mg of 35% formalin, 0.1 ml of acetic acid and 121 mg of sodium cyanoborohydride were added to a solution of 0.7 g of ethyl 2-amino-3-t-butyldimethylsilyloxy-3-(2-chloropyridin-3-yl)propionate (prepared as described in Preparation 78) in 4 ml of a 3:2 by volume mixture of methylene chloride and water at 0° C., and the resulting mixture was stirred at 0° C. for 15 minutes. At the end of this time, a saturated aqueous solution of sodium hydrogencarbonate was added to the reaction mixture, after Which it was extracted with ethyl acetate. The extract was washed with an aqueous solution of sodium chloride and dried over anhydrous sodium sulfate, after which the solvent was removed by distillation under reduced pressure. The residue was purified by column chromatography through silica gel, using a gradient elution method, with mixtures of hexane and ethyl acetate in ratios ranging from 8:1 to 1:1 by volume as the eluent, to give 200 mg of the title compound having Rf=0.38 (on silica gel thin layer chromatography using a 3:1 by volume mixture of hexane and ethyl acetate as the developing solvent).

Workup

  1. extractionafter Which it was extracted with ethyl acetate
  2. washThe extract was washed with an aqueous solution of sodium chloride
  3. dry with materialdried over anhydrous sodium sulfate
  4. customafter which the solvent was removed by distillation under reduced pressure
  5. customThe residue was purified by column chromatography through silica gel
  6. washa gradient elution method

Sources & evidence

ORD record
ord-a814c893582e490995abc7bba1f543b9
Source dataset
uspto-grants-1998_04
Patent number
US05739345

Reaction notes

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