Methyl morpholine oxide → (R,R)-Hydrobenzoin

HRID 48541

Reaction equation

HRID 48541 reaction equation
C[N+]1([O-])CC[O:5]CC1.[C:9]1(/[CH:15]=[CH:16]/[C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.[OH2:23].CC(C)=O.C(#N)C>[O-][Os](=O)(=O)=O.O=[Os](=O)(=O)=O>[C:9]1([C@@H:15]([OH:5])[C@@H:16]([C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=2)[OH:23])[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1

Participants

6

Reactant 3

HCID 82029Methyl morpholine oxideHCID 638088trans-StilbeneHCID 18799168Acetonitrile acetone water

Product 1

HCID 853019(R,R)-HydrobenzoinYield 96%

Reagents, catalysts & solvents 2

HCID 30318Osmium TetroxideCatalystHCID 9543328OsmateCatalyst

Procedure

Resin-OsO4 (0.01 Eq. Wt.), Hydroquinidine 1,4-phthalazinediyl diether (DHQD)2PHAL (0.01 Eq. Wt.) and N-methylmorpholine-N-oxide (1.5 Eq. Wt.) were stirred in the mixed solvent of water/acetone/acetonitrile (in the volume ratio of 1:1:1). To this mixture was added trans-stilbene (1.0 Eq. Wt) and stirred at room temperature for 6 hours. After the reaction, supported osmate catalyst was filtered off and washed with methanol. The combined filtrates were concentrated under reduced pressure. The chiral ligand was recovered from the aqueous layer after acidification (1N HCl). The pure product was obtained by removing the solvent at reduced pressure followed by column chromatography. (R,R)-(+)-1,2-diphenyl-1,2-ethandiol of more than 99.0% of enantiomeric excess was obtained (yield 96%) [∝]D+92.44 (c 1.0, EtOH): e.e.=99.4%

Workup

  1. customAfter the reaction
  2. filtrationwas filtered off
  3. washwashed with methanol
  4. concentrationThe combined filtrates were concentrated under reduced pressure
  5. customThe chiral ligand was recovered from the aqueous layer after acidification (1N HCl)
  6. customThe pure product was obtained
  7. customby removing the solvent at reduced pressure

Sources & evidence

ORD record
ord-6e5cb2debfa449c8bffa435fc0c4b32b
Source dataset
uspto-grants-2004_03
Patent number
US06703531B2

Linked notes

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