Sodium Thiosulfate → (4R,7S)-4-azido-7-(2-methyl-4-nitro-pyrazol-3-yl)oxepan-3-one

HRID 521883Notes

Reaction equation

HRID 521883 reaction equation
[N:1]([C@@H:4]1[CH2:10][CH2:9][C@@H:8]([C:11]2[N:15]([CH3:16])[N:14]=[CH:13][C:12]=2[N+:17]([O-:19])=[O:18])[O:7][CH2:6][C@H:5]1[OH:20])=[N+:2]=[N-:3].CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O.C([O-])(O)=O.[Na+].S([O-])([O-])(=O)=S.[Na+].[Na+]>C(Cl)Cl>[N:1]([C@@H:4]1[CH2:10][CH2:9][C@@H:8]([C:11]2[N:15]([CH3:16])[N:14]=[CH:13][C:12]=2[N+:17]([O-:19])=[O:18])[O:7][CH2:6][C:5]1=[O:20])=[N+:2]=[N-:3]

Participants

6

Reactant 4

HCID 24477Sodium ThiosulfateHCID 159087TriacetoxyperiodinaneHCID 516892Sodium BicarbonateHCID 86713832(3S,4R,7S)-4-azido-7-(1-methyl-4-nitro-1H-pyrazol-5-yl)oxepan-3-ol2×

Product 1

HCID 86713834(4R,7S)-4-azido-7-(2-methyl-4-nitro-pyrazol-3-yl)oxepan-3-oneYield 82%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of (3S,4R,7S)-4-azido-7-(1-methyl-4-nitro-1H-pyrazol-5-yl)oxepan-3-ol (1.4 g, 4.96 mmol, intermediate 90) in DCM (35 mL) was added Dess-Martin peridionane (2.52 g, 5.96 mmol) and the mixture stirred at room temperature for 2 hr. Aqueous saturated NaHCO3 (60 mL) and 20% sodium thiosulfate solution (50 mL) were added and the reaction mixture was stirred for 30 min until full dissolution of salts was observed. The organic layer was separated, dried over MgSO4 and solvents removed under reduced pressure. Purification via silica gel column chromatography (0-40% EtOAc/isoHexane) gave (4R,7S)-4-azido-7-(2-methyl-4-nitro-pyrazol-3-yl)oxepan-3-one as an off-white solid (1.1 g, 82%). 1H NMR (400 MHz, CDCl3) δ 8.05 (s, 1H), 5.38 (dd, J=10.2, 2.7 Hz, 1H), 4.62-4.49 (m, 2H), 4.31-4.22 (m, 1H), 4.08 (s, 3H), 2.31-2.17 (m, 3H), 2.15-2.04 (m, 1H).

Workup

  1. stirringthe reaction mixture was stirred for 30 min until full dissolution of salts
  2. customThe organic layer was separated
  3. dry with materialdried over MgSO4 and solvents
  4. customremoved under reduced pressure
  5. customPurification via silica gel column chromatography (0-40% EtOAc/isoHexane)

Sources & evidence

ORD record
ord-601b8b93fbd94f61a1c5df1d5375c2ea
Source dataset
uspto-grants-2016_05
Patent number
US09328106B2

Reaction notes

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