Ammonium Chloride → HCID 86718972, compound

HRID 1842834Notes

Reaction equation

HRID 1842834 reaction equation
[Si:1]([O:8][CH2:9][C@@H:10]1[C@H:14]2[O:15][C:16]([CH3:19])([CH3:18])[O:17][C@H:13]2[C@H:12]([OH:20])[C:11]1=[CH2:21])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[BH4-].[Na+].[NH4+].[Cl-]>CO>[Si:1]([O:8][CH2:9][C@@H:10]1[C@H:14]2[O:15][C:16]([CH3:19])([CH3:18])[O:17][C@H:13]2[C@@H:12]([OH:20])[C:11]1=[CH2:21])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:2])[CH3:3]

Participants

5

Reactant 3

HCID 25517Ammonium ChlorideHCID 4311764Sodium borohydrideHCID 86693878HCID 86693878, compound

Product 1

HCID 86718972HCID 86718972, compoundYield 80.1%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a stirred solution of allylic alcohol 11 (4 g, 12.7 mmol) was added dess marline (8.1 g, 19.7 mmol) at 0° C. The mixture was warm to ambient temperature and stirred for 1 hr. The mixture was passed through celite bed and obtained filtrate was concentrated under reduced pressure to give crude allylic ketone, which was proceeded as such in next step without further purification. The crude allylic ketone (3.5 g, 11.1 mmol) was dissolved in anhydrous methanol, cooled the solution at −78° C. Added CeCl3.7H2O (5.8 g, 15.6 mmol) at −78° C. and after 10 minutes stirring NaBH4 (0.54 g, 14.5 mmol) was added at one portion. After 15 min stirring at −78° C., the reaction mixture was allowed to 0° C. then saturated NH4Cl (30 mL) was added and the mixture was allowed to stir for 1 hr. Solvent was removed under reduced temperature and pressure and the residue was extracted with DCM (200 mL×2). The combined DCM extracts were washed with brine (40 mL×2), dried over anhydrous Na2SO4, filtered and concentrated under vacuum. The residue was purified by flash silica gel column chromatography (5% EtOAc/hexane) to give compound 12 (3.2 g, 80%) as oil. [α]22D −96.878° (c 2.01, CHCl3); 1H NMR (500 MHz, CDCl3) δ 5.26(s, 1H), 5.10 (s, 1H), 4.52 (m, 2, 3- H's, 2H), 4.4 (m, 1H, 1-H′), 3.71 (dd, J=4 & 10 Hz, 1H, 5- Ha), 3.53 (dd, J=4 & 10 Hz, 5- Hb, 1H), 2.57 (br, 1H), 2.29 (d, J=10.5 Hz, D2O exchange, OH), 1.38 (s, 3H), 1.30 (s, 3H), 0.85 (m, 9H), 0.013-0.006 (m, 6H). 13C NMR(125 MHz, CDCl3) 159.01, 115.9, 115.4, 86.85, 84.85, 79.48, 71.63, 57.21, 32.13, 31.54, 30.33, 23.83, 0.015; HR-MS Calcd. For (C16H30O4Si+H)+ 315.1913, found 315.1987.

Workup

  1. customobtained filtrate
  2. concentrationwas concentrated under reduced pressure
  3. customto give crude allylic ketone, which
  4. customwithout further purification
  5. temperaturecooled the solution at −78° C
  6. additionwas added at one portion
  7. stirringAfter 15 min stirring at −78° C.
  8. customwas allowed to 0° C.
  9. stirringto stir for 1 hr
  10. customSolvent was removed
  11. extractionthe residue was extracted with DCM (200 mL×2)
  12. washThe combined DCM extracts were washed with brine (40 mL×2)
  13. dry with materialdried over anhydrous Na2SO4
  14. filtrationfiltered
  15. concentrationconcentrated under vacuum
  16. customThe residue was purified by flash silica gel column chromatography (5% EtOAc/hexane)

Sources & evidence

ORD record
ord-679c4f3151ff41b7a57606c5b90028bd
Source dataset
uspto-grants-2015_02
Patent number
US08946242B2

Reaction notes

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