Sodium borohydride → Methyl 1-(aminomethyl)spiro[2.4]heptane-1-carboxylate

HRID 1297218Notes

Reaction equation

HRID 1297218 reaction equation
[CH3:1][O:2][C:3]([C:5]1([C:12]#[N:13])[C:7]2([CH2:11][CH2:10][CH2:9][CH2:8]2)[CH2:6]1)=[O:4].[BH4-].[Na+].[H][H]>CO>[CH3:1][O:2][C:3]([C:5]1([CH2:12][NH2:13])[C:7]2([CH2:8][CH2:9][CH2:10][CH2:11]2)[CH2:6]1)=[O:4]

Participants

5

Reactant 3

HCID 4311764Sodium borohydrideHCID 11412713HCID 11412713, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 11298342Methyl 1-(aminomethyl)spiro[2.4]heptane-1-carboxylateYield 87%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a solution of 1-cyano-spiro[2.4]heptane-1-carboxylic acid methyl ester (3.45 g, 19.3 mmol) in methanol (240 mL) was added CoCl2-6H2O (9.16 g, 38.5 mmol) to give a deep purple colored solution. Sodium borohydride (7.30 g, 193 mmol) was added portionwise over 10 minutes with caution to control the evolution of hydrogen and the exothermic reaction that ensued to give a black solution. The reaction mixture was stirred for 30 minutes under nitrogen after the addition was completed. The reaction was quenched carefully by the addition of 0.5N HCl (1.3 L). The solution was made alkaline (pH˜9) by the addition of concentrated ammonium hydroxide. The mixture was extracted with ethyl acetate (4×400 mL). The combined organic layers were dried over sodium sulfate, filtered and evaporated to afford 3.07 g (87%) of 1-aminomethyl-spiro[2.4]heptane-1-carboxylic acid methyl ester as a yellow oil: 1H NMR (300 MHz, CDCl3) δ 0.74 (br d, 1H), 1.4-1.7 (m, 10H), 1.9 (m, 1H), 2.58 (d, J=13.8 Hz, 1H), 3.16 (d, J=13.8 Hz, 1H), 3.48 (s, 3H); MS (APCI) m/z 184 [M+H]+.

Workup

  1. customto give a deep purple colored solution
  2. customthe exothermic reaction that
  3. customto give a black solution
  4. additionafter the addition
  5. customThe reaction was quenched carefully by the addition of 0.5N HCl (1.3 L)
  6. additionby the addition of concentrated ammonium hydroxide
  7. extractionThe mixture was extracted with ethyl acetate (4×400 mL)
  8. dry with materialThe combined organic layers were dried over sodium sulfate
  9. filtrationfiltered
  10. customevaporated

Sources & evidence

ORD record
ord-dc5532fbbd1243a39a8b3bb2db374648
Source dataset
uspto-grants-2007_07
Patent number
US07250433B2

Reaction notes

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