Sodium Chloride → (2S,3R)-1,2-Epoxy-2-(2,4-difluorophenyl)butan-3-ol

HRID 368907

Reaction equation

C([C@@H:6]([C@H:8]([C:10]([O:12][CH2:13]C)=O)[OH:9])O)(OCC)=O.C(OO)(C)(C)C.[F:21][C:22]1[CH:27]=[C:26]([F:28])[CH:25]=[CH:24][C:23]=1C(=C)[C@H](O)C.[OH-].[Na+].[Na+].[Cl-].[O-]S([O-])(=O)=O.[Mg+2]>C(Cl)Cl.CC(C)[O-].[Ti+4].CC(C)[O-].CC(C)[O-].CC(C)[O-]>[F:21][C:22]1[CH:27]=[C:26]([F:28])[CH:25]=[CH:24][C:23]=1[C@@:10]1([O:12][CH2:13]1)[C@H:8]([OH:9])[CH3:6]

Participants

Conditions

Temperature: -5 °C

Procedure

To a solution of diethyl L(+)-tartrate (16 ml, 0.094 mole) in dry CH2Cl2 (2.4 L) is added activated 3A° molecular sieve powder (600 g) and cooled the mixture to -5° C. Added a solution of titanium (IV) isopropoxide (59 ml, 0.20 mole) followed by t-butyl hydroperoxide (156 ml of 5-6M solution in decane) and continue to stir at -5° C. for 25 minutes. To this mixture, a solution of crude 6b, in CH2Cl2 (200 ml) is added and stirred for 12 hours at 5° C. Cooled the reaction mixture to -40° C., added 140 ml of 30% aq. NaOH solution saturated with NaCl and the mixture is allowed to warm to 10 °C. Added 120 g of MgSO4, 40 g of celite and continued to stir at 10° C. for 30 minutes. The mixture is suction-filtered over celite. To the filtrate toluene (2 L), and 1.5 L of ether re added and insoluble material removed by filtration. The filtrate is evaporated under reduced pressure to give the crude 7c as a light brown oil.

Workup

stirringstirred for 12 hours at 5° C
temperatureCooled the reaction mixture to -40° C.
temperatureto warm to 10 °C
stirringto stir at 10° C. for 30 minutes
filtrationThe mixture is suction-filtered over celite
additionTo the filtrate toluene (2 L), and 1.5 L of ether re added
custominsoluble material removed by filtration
customThe filtrate is evaporated under reduced pressure

Sources & evidence

ORD record: ord-33a89d53e7354593a101f2053be7a240
Source dataset: uspto-grants-2000_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06133485

Linked notes

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