Sodium Bicarbonate → Methyl 6-{[(benzyloxy)carbonyl]amino}-2-diazohexanoate

HRID 541009Notes

Reaction equation

HRID 541009 reaction equation
[N:1]([CH:4]([CH2:9][CH2:10][CH2:11][CH2:12][NH:13][C:14]([O:16][CH2:17][C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)=[O:15])[C:5]([O:7][CH3:8])=[O:6])=[N+:2]=[N-].C1(P(C2C=CC=CC=2)CCC(ON2C(=O)CCC2=O)=O)C=CC=CC=1.C([O-])(O)=O.[Na+]>C1COCC1.O.[Na+].[Cl-]>[CH2:17]([O:16][C:14]([NH:13][CH2:12][CH2:11][CH2:10][CH2:9][C:4](=[N+:1]=[N-:2])[C:5]([O:7][CH3:8])=[O:6])=[O:15])[C:18]1[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=1

Participants

6

Reactant 3

HCID 516892Sodium BicarbonateHCID 426043111-((3-(Diphenylphosphanyl)propanoyl)oxy)pyrrolidine-2,5-dioneHCID 72256677Methyl 2-azido-6-{[(benzyloxy)carbonyl]amino}hexanoate

Product 1

HCID 73111538Methyl 6-{[(benzyloxy)carbonyl]amino}-2-diazohexanoateYield 76%

Reagents, catalysts & solvents 2

HCID 5234Sodium ChlorideSolventHCID 21881883Oxolane--water (1/1)Solvent

Procedure

Methyl 2-azido-6-{[(benzyloxy)carbonyl]amino}hexanoate 2f (88 mg, 0.275 mmol) was dissolved in THF/H2O (2 mL/300 μL). To this solution was added phosphine 1e (102 mg, 0.288 mmol), and the resulting solution was stirred for 5 h under Ar(g). Sat. aq. NaHCO3 (2 mL) was then added, and the mixture was stirred vigorously overnight. The mixture was then diluted with sat. aq. NaCl (15 mL) and extracted with CH2Cl2 (2×15 mL). The organic layers were combined, dried over Na2SO4(s), filtered, and evaporated under reduced pressure. The residue was purified by silica gel flash chromatography, eluting with 20% EtOAc/hexanes, to give the diazo-compound 5f as a yellow oil (64 mg, 0.209 mmol, 76% yield).

Workup

  1. extractionextracted with CH2Cl2 (2×15 mL)
  2. dry with materialdried over Na2SO4(s)
  3. filtrationfiltered
  4. customevaporated under reduced pressure
  5. customThe residue was purified by silica gel flash chromatography
  6. washeluting with 20% EtOAc/hexanes

Sources & evidence

ORD record
ord-b04501f49e97414fbef9ddac822a89d4
Source dataset
uspto-grants-2014_10
Patent number
US08871916B2

Reaction notes

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