Boron trifluoride etherate → HCID 68863714, compound

HRID 1725974Notes

Reaction equation

HRID 1725974 reaction equation
B(F)(F)F.CC[O:7]CC.[Br:10][C:11]1[C:20]2[C:19]([CH3:21])=[CH:18][CH2:17][CH2:16][C:15]=2[CH:14]=[CH:13][C:12]=1[NH:22][S:23]([C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][C:27]=1[F:32])(=[O:25])=[O:24]>C1COCC1>[Br:10][C:11]1[C:20]2[C@H:19]([CH3:21])[C@@H:18]([OH:7])[CH2:17][CH2:16][C:15]=2[CH:14]=[CH:13][C:12]=1[NH:22][S:23]([C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][C:27]=1[F:32])(=[O:25])=[O:24]

Participants

4

Reactant 2

HCID 8000Boron trifluoride etherateHCID 68863955HCID 68863955, compound

Product 1

HCID 68863714HCID 68863714, compoundYield 57%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A mixture of R-[N,N′-bis(monoisopinocampheylborane)-N,N,N′,N′-tetramethylethylenediamine] (1.25 g, 3.0 mmol) in THF (5 mL) was treated with boron trifluoride etherate, stirred at room temperature for 1.5 hours, and filtered. The filter cake was washed with THF (2.5 mL). Half of the solution containing the free isopinocamphenylborane (1.5 mmol) was cooled to −25° C., treated with a solution of Example 275D (500 mg, 1.25 mmol) in THF (3 mL), stirred at −20° C. for 48 hours, warmed to 0° C., and quenched with methanol (0.5 mL). The solution was treated with 3M NaOH (1.1 mL), followed by 30% H2O2 (0.9 mL) dropwise, stirred for 1 hour at 50° C., cooled to room temperature, extracted with diethyl ether, dried (Na2SO4), filtered, and concentrated. The concentrate was purified by flash column chromatography on silica gel with 30% acetone/hexanes to give 300 mg (57% yield). MS (ESI) m/e 412 (M−H)−; 1H NMR (300 MHz, DMSO-d6) δ 10.02 (s, 1H), 7.69 (m, 1H), 7.63 (dt, 1H), 7.42 (m, 1H), 7.30 (dt, 1H), 7.0 (d, 1H), 6.92 (d, 1H), 4.73 (d, 1H), 3.85 (m, 1H), 2.95 (m, 1H), 2.82 (m, 1H), 2.6 (m, 1H), 1.81 (m, 1H), 1.69 (m, 1H), 0.98 (d, 3H).

Workup

  1. filtrationfiltered
  2. washThe filter cake was washed with THF (2.5 mL)
  3. additionHalf of the solution containing the free isopinocamphenylborane (1.5 mmol)
  4. temperaturewas cooled to −25° C.
  5. stirringstirred at −20° C. for 48 hours
  6. temperaturewarmed to 0° C.
  7. customquenched with methanol (0.5 mL)
  8. additionThe solution was treated with 3M NaOH (1.1 mL)
  9. stirringstirred for 1 hour at 50° C.
  10. temperaturecooled to room temperature
  11. extractionextracted with diethyl ether
  12. dry with materialdried (Na2SO4)
  13. filtrationfiltered
  14. concentrationconcentrated
  15. customThe concentrate was purified by flash column chromatography on silica gel with 30% acetone/hexanes
  16. customto give 300 mg (57% yield)

Sources & evidence

ORD record
ord-16689a8909604b99b8465d08b4ff3df7
Source dataset
uspto-grants-2009_02
Patent number
US07491718B2

Reaction notes

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