9-Borabicyclo(3.3.1)nonane → HCID 71116558, compound

HRID 1507763Notes

Reaction equation

HRID 1507763 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.B1C2CCCC1CCC2.[Br:25][C:26]1[CH:31]=[C:30](Br)[CH:29]=[C:28]([F:33])[C:27]=1[Cl:34].[OH-].[Na+].O>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][CH2:11][CH2:12][CH2:13][CH2:14][C:30]1[CH:29]=[C:28]([F:33])[C:27]([Cl:34])=[C:26]([Br:25])[CH:31]=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 27249061,5-Dibromo-2-chloro-3-fluorobenzeneHCID 14688338Benzyl but-3-en-1-ylcarbamateHCID 23719242Sodium hydroxide--water (1/1/1)

Product 1

HCID 71116558HCID 71116558, compoundYield 35%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent2×

Conditions

Temperature
60 °C

Procedure

A solution of but-3-enyl-carbamic acid benzyl ester (5.00 g, 24.36 mmol, 1 eq) in anhydrous toluene (60 mL) was cooled under argon to 0-5° C. 9-BBN (0.50 M, solution in THF; 54.6 mL, 26.80 mmol, 1.1 eq.) was added dropwise, and the mixture was allowed to reach room temperature. After 24 h, the resulting solution was added dropwise at room temperature to a mixture of 2a (7.03 g, 24.36 mmol, 1 eq.), 1N NaOH/H2O (40 mL, 40 mmol, 1.6 eq.), and toluene (20 mL). The mixture was then degassed with argon and Pd(PPh3)4 (1.13 g, 0.98 mmol, 0.04 eq.) was added. The mixture was rapidly stirred under argon at 60° C. for 24 h, before cooling to room temperature. The mixture was partitioned between EtOAc (150 mL) and brine (150 mL). The organic phase was washed with brine (200 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 3a as a colorless oil (3.54 g, 35%).

Workup

  1. customto reach room temperature
  2. additionwas added
  3. temperaturebefore cooling to room temperature
  4. customThe mixture was partitioned between EtOAc (150 mL) and brine (150 mL)
  5. washThe organic phase was washed with brine (200 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-968dff14440d4162af0a77f629495114
Source dataset
uspto-grants-2015_12
Patent number
US09221827B2

Reaction notes

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