Sodium Bromide → (S)-2-Boc-aminobutyraldehyde

HRID 9925

Reaction equation

HRID 9925 reaction equation
[C:1]([CH:8]([CH2:12][CH3:13])[C@@H:9](N)[OH:10])([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].CC1(C)[N:20]([O])C(C)(C)CCC1.[Br-].[Na+].C(=O)([O-])O.[Na+]>ClCCl.O>[C:4]([O:3][C:1]([C@:8]([NH2:20])([CH2:12][CH3:13])[CH:9]=[O:10])=[O:2])([CH3:7])([CH3:6])[CH3:5]

Participants

7

Reactant 4

HCID 253881Sodium BromideHCID 516892Sodium BicarbonateHCID 2724126TempoHCID 86590936(S)-2-Boc-aminobutanol

Product 1

HCID 86590935(S)-2-Boc-aminobutyraldehydeYield 77%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of (S)-2-Boc-aminobutanol (50 g; 264 mmol) in dichloromethane (500 mL) and water (350 mL) were added at 20° C. TEMPO (0.01 eq), sodium bromide (1 eq) and sodium hydrogencarbonate (3 eq). The reaction mixture was stirred at 0° C. and diluted bleach (1.3 eq, 450 mL) was added over 40 min. The reaction mixture was stirred for 30 min. at 0° C. and then quenched with aq. thiosulfate. After decantation and extractions (dichloromethane), the organic phase was washed with brine, dried and concentrated in vacuo to dryness, giving (S)-2-(tert-butoxycarbonyl)-amino-butyraldehyde as a low-melting solid (38.1 g; yield: 77%). C9H17NO3; MW=187.2; Tmelt=44° C.; NMR (CDCl3, ppm): 0.97 (t, J=7 Hz, 3H), 1.45 (s, 9H), 1.68 (m, 1H), 1.91 (m, 1H), 4.20 (lq, J=6.5 Hz, 1H), 5.09 (1s, 1H (mobile)) and 9.59 (s, 1H); SM (EI; m/z): 158 (M+—CHO), 102, 57.

Workup

  1. additiondiluted bleach (1.3 eq, 450 mL)
  2. additionwas added over 40 min
  3. stirringThe reaction mixture was stirred for 30 min. at 0° C.
  4. customquenched with aq. thiosulfate
  5. extractionAfter decantation and extractions (dichloromethane)
  6. washthe organic phase was washed with brine
  7. customdried
  8. concentrationconcentrated in vacuo to dryness

Sources & evidence

ORD record
ord-3478ddd948db4d8dac58867c45716e85
Source dataset
uspto-grants-2006_08
Patent number
US07091360B2

Linked notes

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