m-Chloroperbenzoic acid → (S)-2-(5-chloro-4-methylpyridin-2-ylamino)-4H-1'-azaspiro[oxazole-5,3'-bicyclo[2.2.2]octane]1'-oxide

HRID 447271Notes

Reaction equation

HRID 447271 reaction equation
[Cl:1][C:2]1[C:3]([CH3:21])=[CH:4][C:5]([NH:8][C:9]2[O:10][C@:11]3([CH2:19][N:20]=2)[CH:16]2[CH2:17][CH2:18][N:13]([CH2:14][CH2:15]2)[CH2:12]3)=[N:6][CH:7]=1.C1C=C(Cl)C=C(C(OO)=[O:30])C=1>C1COCC1>[Cl:1][C:2]1[C:3]([CH3:21])=[CH:4][C:5]([NH:8][C:9]2[O:10][C@:11]3([CH2:19][N:20]=2)[CH:16]2[CH2:17][CH2:18][N+:13]([O-:30])([CH2:14][CH2:15]2)[CH2:12]3)=[N:6][CH:7]=1

Participants

4

Reactant 2

HCID 70297m-Chloroperbenzoic acidHCID 58088234(R)-N-(5-chloro-4-methylpyridin-2-yl)-4H-1'-azaspiro[oxazole-5,3'-bicyclo[2.2.2]octan]-2-amine

Product 1

HCID 54588417(S)-2-(5-chloro-4-methylpyridin-2-ylamino)-4H-1'-azaspiro[oxazole-5,3'-bicyclo[2.2.2]octane]1'-oxideYield 46.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To (R)—N-(5-Chloro-4-methylpyridin-2-yl)-4H-1′-azaspiro[oxazole-5,3′-bicyclo[2.2.2]octan]-2-amine (0.04 g, 0.13 mmol) in THF (10 mL) was added m-CPBA (0.025 g, 0.14 mmol). The reaction stirred at room temperature for 2 hours and was then concentrated to a crude powder. The product was purified by chromatography (Biotage: 85% CHCl3, 14% MeOH, 1% NH4OH) to yield (S)-2-(5-chloro-4-methylpyridin-2-ylamino)-4H-1′-azaspiro[oxazole-5,3′-bicyclo[2.2.2]octane]1′-oxide (0.019 g, 0.06 mmol, 44% yield) as a white powder. 1H NMR (500 MHz, MeOD) δ ppm 8.18 (s, 1H), 6.75-7.09 (m, 1H), 4.00 (d, J=10.4 Hz, 1H), 3.84 (d, J=10.4 Hz, 1H), 3.61-3.78 (m, 2H), 3.41-3.54 (m, 3H), 3.23-3.38 (m, 3H), 2.45 (br. s., 1H), 2.25-2.38 (m, 4H), 1.88-2.22 (m, 1H). MS (LC/MS) R.T.=0.91; [M+H]+=323.11.

Workup

  1. concentrationwas then concentrated to a crude powder
  2. customThe product was purified by chromatography (Biotage: 85% CHCl3, 14% MeOH, 1% NH4OH)

Sources & evidence

ORD record
ord-c29c7e9ce39343d5a82c05aa48250a3f
Source dataset
uspto-grants-2013_07
Patent number
US08481555B2

Reaction notes

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