(5R,6R,6aR)-5-((tert-butyldiphenylsilyloxy)methyl)-2,2,6a-trimethyl-tetrahydrofuro[3,2-d][1,3]dioxol-6-yl 4-methylbenzenesulfonate → (5R,6R,6aR)-5-((tert-butyldiphenylsilyloxy)methyl)-2,2,6a-trimethyl-tetrahydrofuro[3,2-d][1,3]dioxol-6-ol

HRID 409006Notes

Reaction equation

HRID 409006 reaction equation
CC1C=CC(S([O:11][C@H:12]2[C@@:16]3([CH3:22])[O:17][C:18]([CH3:21])([CH3:20])[O:19][CH:15]3[O:14][C@@H:13]2[CH2:23][O:24][Si:25]([C:38]([CH3:41])([CH3:40])[CH3:39])([C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)[C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)(=O)=O)=CC=1>C1COCC1>[Si:25]([O:24][CH2:23][C@H:13]1[O:14][CH:15]2[C@:16]([CH3:22])([O:17][C:18]([CH3:21])([CH3:20])[O:19]2)[C@@H:12]1[OH:11])([C:38]([CH3:41])([CH3:40])[CH3:39])([C:32]1[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=1)[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1

Participants

3

Reactant 1

HCID 86662593(5R,6R,6aR)-5-((tert-butyldiphenylsilyloxy)methyl)-2,2,6a-trimethyl-tetrahydrofuro[3,2-d][1,3]dioxol-6-yl 4-methylbenzenesulfonate

Product 1

HCID 66780009(5R,6R,6aR)-5-((tert-butyldiphenylsilyloxy)methyl)-2,2,6a-trimethyl-tetrahydrofuro[3,2-d][1,3]dioxol-6-olYield 93%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

The mixture of (5R,6R,6aR)-5-((tert-butyldiphenylsilyloxy)methyl)-2,2,6a-trimethyl-tetrahydrofuro[3,2-d][1,3]dioxol-6-yl 4-methylbenzenesulfonate (from step 4) (56 g, 0.094 mol) and 1M solution of Li(Et)3BH (376.4 mL, 0.376 mol) in 800 mL of THF was refluxed for 12 h. The reaction mixture was cooled to room temperature and quenched carefully with 200 mL of saturated ammonium chloride solution. Diluted with 500 mL of ethyl acetate and washed with 1N HCl (500 mL) and brine (300 mL). The organic layers were dried over anhydrous Na2SO4, filtered and concentrated. The crude residue was dissolved in ethyl acetate and passed through a pad of celite to remove salts. Purified by column chromatography using hexane and ethyl acetate as a gradient mixture to give 38.4 g of the title compound (93% yield).

Workup

  1. temperaturewas refluxed for 12 h
  2. customquenched carefully with 200 mL of saturated ammonium chloride solution
  3. additionDiluted with 500 mL of ethyl acetate
  4. washwashed with 1N HCl (500 mL) and brine (300 mL)
  5. dry with materialThe organic layers were dried over anhydrous Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. dissolutionThe crude residue was dissolved in ethyl acetate
  9. customto remove salts
  10. customPurified by column chromatography

Sources & evidence

ORD record
ord-777921a7d5e74a7d95614d0c85a9ebf9
Source dataset
uspto-grants-2014_06
Patent number
US08759318B2

Reaction notes

Loading…