m-Chloroperbenzoic acid → HCID 54588501, compound

HRID 447277Notes

Reaction equation

HRID 447277 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([NH:9][C:10]2[O:11][C@:12]3([CH2:20][N:21]=2)[CH:17]2[CH2:18][CH2:19][N:14]([CH2:15][CH2:16]2)[CH2:13]3)=[N:6][C:7]=1[F:8].C1C=C(Cl)C=C(C(OO)=[O:30])C=1>C(Cl)(Cl)Cl>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([NH:9][C:10]2[O:11][C@:12]3([CH2:20][N:21]=2)[CH:17]2[CH2:18][CH2:19][N+:14]([O-:30])([CH2:15][CH2:16]2)[CH2:13]3)=[N:6][C:7]=1[F:8]

Participants

4

Reactant 2

HCID 70297m-Chloroperbenzoic acidHCID 67504443HCID 67504443, compound

Product 1

HCID 54588501HCID 54588501, compoundYield 66.1%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

To (R)—N-(5-bromo-6-fluoropyridin-2-yl)-4H-1′-azaspiro[oxazole-5,3′-bicyclo[2.2.2]octan]-2-amine (0.064 g, 0.180 mmol) in CHCl3 (15 mL) was added m-CPBA (0.032 g, 0.186 mmol) at room temperature. The reaction stirred at room temperature for 3 hours. TLC showed lower spot and no starting material. The mixture was purified by chromatography (Biotage: 15-20% of 9:1 MeOH:NH4OH in CHCl3; ˜1.1 L) to yield the pure fractions. The fractions were combined and the solvent was removed to yield (S)-2-(5-bromo-6-fluoropyridin-2-ylamino)-4H-1′-azaspiro[oxazole-5,3′-bicyclo[2.2.2]octane]1′-oxide (0.045 g, 0.119 mmol, 65.9% yield) as a yellow powder. 1H NMR (500 MHz, DMSO-d6) δ ppm 8.31-8.76 (m, 1H), 8.00 (br. s., 1H), 6.46-6.96 (m, 1H), 3.73 (d, J=11.0 Hz, 2H), 3.56 (br. s., 1H), 3.37 (br. s., 3H), 2.98-3.27 (m, 2H), 2.11 (br. s., 2H), 1.73-2.00 (m, 3H).

Workup

  1. customThe mixture was purified by chromatography (Biotage: 15-20% of 9:1 MeOH:NH4OH in CHCl3; ˜1.1 L)
  2. customto yield the pure fractions
  3. customthe solvent was removed

Sources & evidence

ORD record
ord-e223095fed4b4eb79068ec2e2c285aa5
Source dataset
uspto-grants-2013_07
Patent number
US08481555B2

Reaction notes

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