Lithium tri-s-butylborohydride → HCID 58951276, compound

HRID 46155Notes

Reaction equation

HRID 46155 reaction equation
[Si:1]([O:18][C@H:19]1[CH2:24][C@H:23]2[CH2:25][C@@H:20]1[CH2:21][C:22]2=[O:26])([C:14]([CH3:17])([CH3:16])[CH3:15])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CCC(C)[BH-](C(C)CC)C(C)CC.[Li+]>C1COCC1>[Si:1]([O:18][C@H:19]1[CH2:24][C@H:23]2[CH2:25][C@@H:20]1[CH2:21][C@H:22]2[OH:26])([C:14]([CH3:17])([CH3:15])[CH3:16])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

4

Reactant 2

HCID 3611392Lithium tri-s-butylborohydrideHCID 58951272HCID 58951272, compound

Product 1

HCID 58951276HCID 58951276, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of (1R,4R,5S)-5-(tert-butyldiphenylsilyloxy)bicyclo[2.2.1]heptan-2-one (5.75 g, 15.8 mmol) in THF (15.0 mL) was added dropwise to L-Selectride (1.0 M solution in THF, 31.5 ml, 31.5 mmol) at −78° C. under nitrogen. The resulting mixture was stirred at −78° C. for 3 h, then quenched with tris-HCl (1M, PH 7.0 at 25° C.). The mixture was warmed to ambient temp. and partitioned between EtOAc and Tris-HCl. The combined organic portions were washed with brine, and conc. in vacuo. The residue was dissolved in MeOH (60 mL), stirred with NaOH (pellets, 3.2 g) at 60° C. overnight. After cooling to ambient temp., the solvent was removed in vacuo. The residue was partitioned between diethyl ether and water. The combined organic portions were washed with brine, dried with Na2SO4, filtered, and conc. in vacuo. The crude product was purified by flash column chromatography (0 to 30% of EtOAc in hexanes) to yield the title compound as a colorless oil.

Workup

  1. customquenched with tris-HCl (1M, PH 7.0 at 25° C.)
  2. temperatureThe mixture was warmed to ambient temp.
  3. custompartitioned between EtOAc and Tris-HCl
  4. washThe combined organic portions were washed with brine
  5. dissolutionThe residue was dissolved in MeOH (60 mL)
  6. stirringstirred with NaOH (pellets, 3.2 g) at 60° C. overnight
  7. temperatureAfter cooling to ambient temp.
  8. customthe solvent was removed in vacuo
  9. customThe residue was partitioned between diethyl ether and water
  10. washThe combined organic portions were washed with brine
  11. dry with materialdried with Na2SO4
  12. filtrationfiltered
  13. customThe crude product was purified by flash column chromatography (0 to 30% of EtOAc in hexanes)

Sources & evidence

ORD record
ord-f96481a6bfdd4e6da03296f877b54855
Source dataset
uspto-grants-2013_09
Patent number
US08541592B2

Reaction notes

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