Dichloromethane → 1-(2,3,5,6-tetrafluorophenyl)-1H-pyrazolo[3,4-b]pyridin-4-ylboronic acid

HRID 1186809Notes

Reaction equation

I[C:2]1[CH:7]=[CH:6][N:5]=[C:4]2[N:8]([C:11]3[C:16]([F:17])=[C:15]([F:18])[CH:14]=[C:13]([F:19])[C:12]=3[F:20])[N:9]=[CH:10][C:3]=12.[O:21]1CC[O:23][BH:22]1.C([O-])(=O)C.[K+].C(Cl)Cl>CS(C)=O>[F:20][C:12]1[C:13]([F:19])=[CH:14][C:15]([F:18])=[C:16]([F:17])[C:11]=1[N:8]1[C:4]2=[N:5][CH:6]=[CH:7][C:2]([B:22]([OH:23])[OH:21])=[C:3]2[CH:10]=[N:9]1

Participants

Conditions

Temperature: 105 °C

Procedure

To a 48 mL pressure bottle under N2 was added the compound from Intermediate 69A (1.1 g, 2.8 mmol), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane (1.17 g, 4.61 mmol), potassium acetate (1.15 g, 11.72 mmol), and anhydrous DMSO (8 mL). Argon was bubbled into the reaction mixture for 5 min and then PdCl2(dppf).CH2Cl2 (71 mg, 0.097 mmol) was added. The reaction mixture was flushed with argon, securely capped, and heated at 105° C. for 75 min. After adding 30 mg more palladium catalyst and 60 mg more 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane, the reaction mixture was heated at 115° C. in an oil bath for an additional 75 min to give the desired intermediate. LC/MS (Condition B): ret. T=3.2 min, (M+H)+ 312.03.

Workup

customArgon was bubbled into the reaction mixture for 5 min
customThe reaction mixture was flushed with argon
customsecurely capped
additionAfter adding 30 mg more palladium catalyst and 60 mg more 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane
temperaturethe reaction mixture was heated at 115° C. in an oil bath for an additional 75 min

Sources & evidence

ORD record: ord-0998d283ed3e4398a6e7588eebe85e0c
Source dataset: uspto-grants-2014_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08673922B2

Reaction notes

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