9-Borabicyclo(3.3.1)nonane → HCID 86722068, compound

HRID 1507766Notes

Reaction equation

HRID 1507766 reaction equation
[CH2:1]([O:8][C:9](=[O:15])[NH:10][CH2:11][CH2:12][CH:13]=[CH2:14])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.B1C2CCC[CH:17]1CCC2.[OH-].[Na+].O.Br[C:29]1[CH:34]=[C:33]([C:35]([F:38])([F:37])[F:36])[CH:32]=[CH:31][N:30]=1>C1(C)C=CC=CC=1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:1]([O:8][C:9](=[O:15])[NH:10][CH:11]([CH3:17])[CH2:12][CH2:13][CH2:14][C:29]1[CH:34]=[C:33]([C:35]([F:38])([F:37])[F:36])[CH:32]=[CH:31][N:30]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

7

Reactant 4

HCID 789669-Borabicyclo(3.3.1)nonaneHCID 27815432-Bromo-4-(trifluoromethyl)pyridineHCID 14688338Benzyl but-3-en-1-ylcarbamateHCID 23719242Sodium hydroxide--water (1/1/1)

Product 1

HCID 86722068HCID 86722068, compoundYield 99.4%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent2×

Procedure

A solution of but-3-enyl-carbamic acid benzyl ester (3.06 g, 14.0 mmol, 1 eq) in anhydrous toluene (40 mL) was cooled under argon to 0-5° C. 9-BBN (0.50 M, solution in THF; 30.8 mL, 1504 mmol, 1.1 eq.) was added dropwise, the mixture was stirred and allowed to reach room temperature. After 24 h, 1N NaOH/H2O (23.8 mL, 23.8 mmol, 1.7 eq.) was added, followed by 2-bromo-4-trifluoromethyl-pyridine (3.16 g, 14.0 mmol, 1 eq.) and toluene (25 mL). The resulting mixture was degassed and Pd(PPh3)4 (0.89 g, 0.70 mmol, 0.05 eq.) was added. The mixture was rapidly stirred under argon at 60° C. for 24 h, and then it was cooled to room temperature. Afterwards, the mixture was partitioned between EtOAc (100 mL) and brine (100 mL). The organic phase was washed with brine (100 mL), dried over Na2SO4, filtered and concentrated. The crude product was purified by flash chromatography on silica gel (0-50% EtOAc in Heptane) to afford 2 as colorless oil (5.1 g, 99%).

Workup

  1. customto reach room temperature
  2. customThe resulting mixture was degassed
  3. stirringThe mixture was rapidly stirred under argon at 60° C. for 24 h
  4. customAfterwards, the mixture was partitioned between EtOAc (100 mL) and brine (100 mL)
  5. washThe organic phase was washed with brine (100 mL)
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe crude product was purified by flash chromatography on silica gel (0-50% EtOAc in Heptane)

Sources & evidence

ORD record
ord-80ee0e8ecea6453ab78169caa620f466
Source dataset
uspto-grants-2015_12
Patent number
US09221827B2

Reaction notes

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