Potassium Persulfate → HCID 118379429, compound

HRID 708541Notes

Reaction equation

HRID 708541 reaction equation
[CH2:1]([O:8][C:9]([NH:11][C@@H:12]1[C:15](=[O:16])[N:14](CC2C=CC(OC)=CC=2OC)[C@@H:13]1[CH2:28][N:29]1[N:33]=[C:32]2[CH2:34][N:35]([C:37]([O:39][C:40]([CH3:43])([CH3:42])[CH3:41])=[O:38])[CH2:36][C:31]2=[N:30]1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.S(OOS([O-])(=O)=O)([O-])(=O)=O.[K+].[K+].P([O-])([O-])([O-])=O.[K+].[K+].[K+]>C(#N)C.O>[CH2:1]([O:8][C:9]([NH:11][C@@H:12]1[C:15](=[O:16])[NH:14][C@@H:13]1[CH2:28][N:29]1[N:30]=[C:31]2[CH2:36][N:35]([C:37]([O:39][C:40]([CH3:43])([CH3:42])[CH3:41])=[O:38])[CH2:34][C:32]2=[N:33]1)=[O:10])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 24412Potassium Persulfate3×HCID 62657Potassium Phosphate, TribasicHCID 118380176HCID 118380176, compound

Product 1

HCID 118379429HCID 118379429, compoundYield 51.8%

Reagents, catalysts & solvents 1

HCID 18373917Acetonitrile--water (1/1)Solvent

Conditions

Temperature
90 °C

Procedure

Slurried tert-butyl 2-(((2R,3S)-3-(((benzyloxy)carbonyl)amino)-1-(2,4-dimethoxybenzyl)-4-oxoazetidin-2-yl)methyl)-4,6-dihydropyrrolo[3,4-d][1,2,3]triazole-5(2H)-carboxylate (85.5 mg, 0.144 mmol), potassium peroxydisulfate (51.8 mg, 0.186 mmol) and potassium phosphate, dibasic (57 mg, 0.33 mmol) in ACN/water (2 mL, 2:1) for 5 min, then heated to 90° C. for 1.5 h. More potassium peroxydisulfate (13.9 mg, 0.050 mmol) was added and it was heated for an additional hour. More potassium peroxydisulfate (12.1 mg, 0.043 mmol) was added and it was heated an additional hour, whereupon the slurry was partially concentrated in vacuo then partitioned between saturated NaHCO3 (aq) and EtOAc. After separating the layers, the aqueous was extracted with EtOAc (3×). The combined organic layers were washed with brine, dried over Na2SO4 and concentrated in vacuo. The crude residue was purified via silica gel chromatography (EtOAc-Heptane, 0-100%) to afford contaminated product (33 mg), which was repurified by reverse phase HPLC (XSELECT CSH, C18, 5μ, 30×100 mm, ACN/H2O with 0.1% formic acid buffer, 60 mL/min). The title compound (12.1 mg, 19%) was obtained as a white solid. Rt=0.78 min, m/z=433.2 (M+1) Method 2m_acidic. 1H NMR (500 MHz, DMSO-d6) δ 8.40 (s, 1H), 8.17 (d, J=9.7 Hz, 1H), 7.42-7.26 (m, 5H), 5.05 (s, 2H), 5.04-4.99 (m, 1H), 4.58 (d, J=6.6 Hz, 2H), 4.40 (d, J=4.7 Hz, 4H), 4.22 (q, J=6.5 Hz, 1H), 1.45 (s, 9H).

Workup

  1. temperatureit was heated for an additional hour
  2. temperatureit was heated an additional hour, whereupon the slurry
  3. concentrationwas partially concentrated in vacuo
  4. customthen partitioned between saturated NaHCO3 (aq) and EtOAc
  5. customAfter separating the layers
  6. extractionthe aqueous was extracted with EtOAc (3×)
  7. washThe combined organic layers were washed with brine
  8. dry with materialdried over Na2SO4
  9. concentrationconcentrated in vacuo
  10. customThe crude residue was purified via silica gel chromatography (EtOAc-Heptane, 0-100%)

Sources & evidence

ORD record
ord-b14f9b907b854597bbdf4d995cb49d5b
Source dataset
uspto-grants-2015_11
Patent number
US09174978B2

Reaction notes

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