Triisopropyl borate → 3-cyano-1-cyclobutyl-6-(difluoromethoxy)-1H-indol-2-ylboronic acid

HRID 1027991Notes

Reaction equation

HRID 1027991 reaction equation
[CH:1]1([N:5]2[C:13]3[C:8](=[CH:9][CH:10]=[C:11]([O:14][CH:15]([F:17])[F:16])[CH:12]=3)[C:7]([C:18]#[N:19])=[CH:6]2)[CH2:4][CH2:3][CH2:2]1.[B:20](OC(C)C)([O:25]C(C)C)[O:21]C(C)C.[Li+].CC([N-]C(C)C)C>C1COCC1>[C:18]([C:7]1[C:8]2[C:13](=[CH:12][C:11]([O:14][CH:15]([F:16])[F:17])=[CH:10][CH:9]=2)[N:5]([CH:1]2[CH2:2][CH2:3][CH2:4]2)[C:6]=1[B:20]([OH:25])[OH:21])#[N:19]

Participants

5

Conditions

Temperature
-78 °C

Procedure

Into a solution of 1-cyclobutyl-6-(difluoromethoxy)-1H-indole-3-carbonitrile (1.5 g, 5.7 mmol) and triisopropyl borate (2.4 mL, 10.3 mmol) in THF (25 mL) at −78° C. was added LDA (1.5 M in cyclohexane, 5.0 mL, 7.5 mmol). The mixture was stirred at −78° C. for 30 min and then quenched with ice water (60 mL) and stirred for 15 min without cooling. The mixture was extracted with ethyl acetate 1:1 in hexane (20 mL). The aqueous layer was acidified with 2 N aq. HCl to pH 5 and extracted with CH2Cl2 (60 mL). The organic layer was dried over Na2SO4 and concentrated to give 3-cyano-1-cyclobutyl-6-(difluoromethoxy)-1H-indol-2-ylboronic acid as a solid (1.8 g, 60% pure by LCMS) that was used in the next step without further purification.

Workup

  1. customquenched with ice water (60 mL)
  2. stirringstirred for 15 min
  3. temperaturewithout cooling
  4. extractionThe mixture was extracted with ethyl acetate 1:1 in hexane (20 mL)
  5. extractionextracted with CH2Cl2 (60 mL)
  6. dry with materialThe organic layer was dried over Na2SO4
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-db858bfe152d4ebb8df9ce785d809e38
Source dataset
uspto-grants-2014_05
Patent number
US08735414B2

Reaction notes

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