Sodium Thiosulfate → tert-Butyl N-(3-oxopropyl)carbamate

HRID 386799Notes

Reaction equation

HRID 386799 reaction equation
[C:1]([NH:8][CH2:9][CH2:10][CH2:11][OH:12])([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O.[O-]S([O-])(=S)=O.[Na+].[Na+]>O.CCOCC.C([O-])(O)=O.[Na+]>[C:1]([NH:8][CH2:9][CH2:10][CH:11]=[O:12])([O:3][C:4]([CH3:5])([CH3:6])[CH3:7])=[O:2]

Participants

7

Reactant 3

HCID 24477Sodium ThiosulfateHCID 159087TriacetoxyperiodinaneHCID 3838134tert-butyl N-(3-hydroxypropyl)carbamate

Product 1

HCID 10910051tert-Butyl N-(3-oxopropyl)carbamateYield 86.8%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 516892Sodium BicarbonateSolvent

Procedure

To a stirring solution of 3-(Boc-amino)-1-propanol (25 mL, 0.144 mol) in water saturated DCM (1.0 L) was added Dess-Martin reagent (99.2 g, 233.9 mmol) and the reaction mixture was stirred for 1 hour. The reaction was then diluted with ether (1.0 L), followed by a solution of Na2S2O3 (250 g) in 80% NaHCO3 (450 g in 1.0 L H2O). The reaction was stirred vigorously for 30 minutes until two layers formed, the top layer was clear. The reaction was filtered to remove the precipitated solids and the aqueous layer was extracted with ether (1.0 L). The organic layer was washed with sat. NaHCO3 (1.0 L), H2O (1.0 L), and brine (1 L), dried over Na2SO4 and concentrated to a clear oil. The crude oil was dissolved in EtOAc:hexanes (1:1 v/v, 1.0 L) and filtered through a short silica gel column to yield the desired N-Boc-3-amino-propanal (21.7 g, 0.125 mol, 85.6% yield): 1H NMR (400 MHz, CDCl3) δ 9.77 (s, 1 H, CHO), 4.85 (bs, 1 H, NH), 3.36-3.42 (m, 2 H, CH2), 2.67 (t, 2 H, CH2), 1.39 (s, 9 H, (CH3)3).

Workup

  1. stirringThe reaction was stirred vigorously for 30 minutes until two layers
  2. customformed
  3. filtrationThe reaction was filtered
  4. customto remove the precipitated solids
  5. extractionthe aqueous layer was extracted with ether (1.0 L)
  6. washThe organic layer was washed with sat. NaHCO3 (1.0 L), H2O (1.0 L), and brine (1 L)
  7. dry with materialdried over Na2SO4
  8. concentrationconcentrated to a clear oil
  9. dissolutionThe crude oil was dissolved in EtOAc:hexanes (1:1 v/v, 1.0 L)
  10. filtrationfiltered through a short silica gel column

Sources & evidence

ORD record
ord-6c1e067d8b564c7594a60dca89345b36
Source dataset
uspto-grants-2013_02
Patent number
US08372813B2

Reaction notes

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