Sodium Sulfite → (1S,4S,6R)-4-benzhydryl-3,7-dioxa-bicyclo[4.1.0]-heptane

HRID 78924Notes

Reaction equation

HRID 78924 reaction equation
[CH:1]([C@@H:14]1[CH2:19][CH:18]=[CH:17][CH2:16][O:15]1)([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.C1C=C(Cl)C=C(C(OO)=[O:28])C=1.[O-]S([O-])=O.[Na+].[Na+]>C(Cl)Cl>[CH:1]([C@@H:14]1[CH2:19][C@@H:18]2[C@@H:17]([O:28]2)[CH2:16][O:15]1)([C:8]1[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 24437Sodium SulfiteHCID 70297m-Chloroperbenzoic acidHCID 54762285(2S)-2-benzhydryl-3,6-dihydro-2H-pyran

Product 1

HCID 54762329(1S,4S,6R)-4-benzhydryl-3,7-dioxa-bicyclo[4.1.0]-heptaneYield 50.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of (2S)-2-benzhydryl-3,6-dihydro-2H-pyran 27a (0.15 g, 0.6 mmol) in CH2Cl2 (20 ml) was added mCPBA (0.3 g, 70%, 1.2 mmol) in a portionwise manner at 0° C. The mixture was brought to room temperature and the reaction mixture was stirred for 20 h under N2. Na2SO3 (20 ml 1.0 M solution) was added to the reaction mixture at 0° C. to quench the reaction. The aqueous phase was extracted with CH2Cl2 (20 ml×2). The combined organic phase was washed in turn with saturated NaHCO3 and brine, then dried over anhydrous Na2SO4. Evaporation of the solvent gave light brown solid residue. The crude products were purified by flash chromatography on silica gel (hexane/ethyl ether=9:1) to give 0.08 g (1S,4S,6R)-4-benzhydryl-3,7-dioxa-bicyclo[4.1.0]-heptane 28a (50.3%, [α]D=(−)60, c=1, MeOH) and 0.065 g 28b (1R,4S,6S)-4-benzhydryl-3,7-dioxa-bicyclo[4.1.0]-heptane (41%, [α]D=(−) 76, c=1, MeOH).

Workup

  1. customwas brought to room temperature
  2. customto quench
  3. customthe reaction
  4. extractionThe aqueous phase was extracted with CH2Cl2 (20 ml×2)
  5. washThe combined organic phase was washed in turn with saturated NaHCO3 and brine
  6. dry with materialdried over anhydrous Na2SO4
  7. customEvaporation of the solvent
  8. customgave light brown solid residue
  9. customThe crude products were purified by flash chromatography on silica gel (hexane/ethyl ether=9:1)

Sources & evidence

ORD record
ord-632f632183384da3aee6972c4a64dcfa
Source dataset
uspto-grants-2014_09
Patent number
US08841464B2

Reaction notes

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