tert-butyl 4-(4-(3-(tert-butoxycarbonylamino)-5-cyano-6-(2-fluoro-4-methoxyphenyl)-4,7-dihydro-1H-pyrazolo[3,4-b]pyridine-4-yl)phenyl)piperazine-1-carboxylate → tert-butyl 4-(4-(3-(tert-butoxycarbonylamino)-5-cyano-6-(2-fluoro-4-methoxyphenyl)-1H-pyrazolo[3,4-b]pyridin-4-yl)phenyl)piperazine-1-carboxylate

HRID 336843Notes

Reaction equation

HRID 336843 reaction equation
[C:1]([O:5][C:6]([NH:8][C:9]1[C:17]2[CH:16]([C:18]3[CH:23]=[CH:22][C:21]([N:24]4[CH2:29][CH2:28][N:27]([C:30]([O:32][C:33]([CH3:36])([CH3:35])[CH3:34])=[O:31])[CH2:26][CH2:25]4)=[CH:20][CH:19]=3)[C:15]([C:37]#[N:38])=[C:14]([C:39]3[CH:44]=[CH:43][C:42]([O:45][CH3:46])=[CH:41][C:40]=3[F:47])[NH:13][C:12]=2[NH:11][N:10]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2]>ClCCl.[O-2].[Mn+2]>[C:1]([O:5][C:6]([NH:8][C:9]1[C:17]2[C:12](=[N:13][C:14]([C:39]3[CH:44]=[CH:43][C:42]([O:45][CH3:46])=[CH:41][C:40]=3[F:47])=[C:15]([C:37]#[N:38])[C:16]=2[C:18]2[CH:19]=[CH:20][C:21]([N:24]3[CH2:29][CH2:28][N:27]([C:30]([O:32][C:33]([CH3:36])([CH3:35])[CH3:34])=[O:31])[CH2:26][CH2:25]3)=[CH:22][CH:23]=2)[NH:11][N:10]=1)=[O:7])([CH3:2])([CH3:3])[CH3:4]

Participants

4

Reactant 1

HCID 136352994tert-butyl 4-(4-(3-(tert-butoxycarbonylamino)-5-cyano-6-(2-fluoro-4-methoxyphenyl)-4,7-dihydro-1H-pyrazolo[3,4-b]pyridine-4-yl)phenyl)piperazine-1-carboxylate

Product 1

HCID 67074067tert-butyl 4-(4-(3-(tert-butoxycarbonylamino)-5-cyano-6-(2-fluoro-4-methoxyphenyl)-1H-pyrazolo[3,4-b]pyridin-4-yl)phenyl)piperazine-1-carboxylateYield 97.5%

Reagents, catalysts & solvents 2

HCID 160959Manganese oxideCatalystHCID 6344DichloromethaneSolvent

Procedure

To 2.22 g (3.44 mmol) of tert-butyl 4-(4-(3(tert-butoxycarbonylamino)-5-cyano-6-(2-fluoro-4-methoxyphenyl)-4,7-dihydro-1H-pyrazolo[3,4-b]pyridin-4-yl)phenyl)piperazine-1-carboxylate in solution in 20 ml of dichloromethane are added 1.49 g (17.19 mmol) of manganese oxide. The reaction mixture is sonicated for 5 min then stirred at room temperature for 20 h. It is filtered on silica (cyclohexane/ethyl acetate eluent: 5:5) to yield 2.16 g (97%) of tert-butyl 4-(4-(3-(tert-butoxycarbonylamino)-5-cyano-6-(2-fluoro-4-methoxyphenyl)-1H-pyrazolo[3,4-b]pyridin-4-yl)phenyl)piperazine-1-carboxylate in the form of a yellow solid.

Workup

  1. customThe reaction mixture is sonicated for 5 min
  2. filtrationIt is filtered on silica (cyclohexane/ethyl acetate eluent: 5:5)

Sources & evidence

ORD record
ord-610fb6bc11254ebfad96906dacb47dfb
Source dataset
uspto-grants-2014_11
Patent number
US08889711B2

Reaction notes

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