Formaldehyde → HCID 71256048, compound

HRID 920205Notes

Reaction equation

[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([N:8]2[C:12]3=[N:13][CH:14]=[N:15][C:16]([NH:17][C:18](=[O:24])[O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[C:11]3[C:10]([I:25])=[N:9]2)=[CH:4][CH:3]=1.C=O.[BH3-][C:29]#N.[Na+].[BH-](OC(C)=O)(OC(C)=O)OC(C)=O.[Na+]>C1COCC1>[I:25][C:10]1[C:11]2[C:12](=[N:13][CH:14]=[N:15][C:16]=2[NH:17][C:18](=[O:24])[O:19][C:20]([CH3:21])([CH3:22])[CH3:23])[N:8]([C:5]2[CH:6]=[CH:7][C:2]([NH:1][CH3:29])=[CH:3][CH:4]=2)[N:9]=1

Participants

Conditions

Temperature: 30 °C

Procedure

To a solution of tert-butyl 1-(4-aminophenyl)-3-iodo-1H-pyrazolo[3,4-d]pyrimidin-4-ylcarbamate (29) (500 mg, 1.11 mmol) in THF (15 mL) was added HCHO solution (135 mg, 1.66 mmol, 37% solution in water) under N2. The reaction was warmed to 30° C. for 4 h and then NaBH3CN (70 mg, 1.11 mmol) was added. The reaction mixture was stirred for 1 h at 30° C. followed by the addition of NaBH(OAc)3 (235 mg, 1.11 mmol). The reaction mixture was stirred overnight at 30° C. The reaction mixture was quenched with sat. aqueous NaHCO3 and extracted with 85% DCM/IPA (15 mL×3). The organic solution was dried and concentrated. The residue was purified by flash chromatography to provide tert-butyl 3-iodo-1-(4-(methylamino)phenyl)-1H-pyrazolo[3,4-d]pyrimidin-4-ylcarbamate (30) (170 mg, 33%) as a yellow solid. LC-MS (ESI): m/z (M+1) 467.0.

Workup

stirringThe reaction mixture was stirred overnight at 30° C
customThe reaction mixture was quenched with sat. aqueous NaHCO3
extractionextracted with 85% DCM/IPA (15 mL×3)
customThe organic solution was dried
concentrationconcentrated
customThe residue was purified by flash chromatography

Sources & evidence

ORD record: ord-a00f9c03133b45629aa7c1a857b883c5
Source dataset: uspto-grants-2016_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09273051B2

Reaction notes

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