Potassium Carbonate → (2R,3R)-2-(benzyloxymethyl)-3-(2-chlorophenyl)oxirane

HRID 1506987Notes

Reaction equation

HRID 1506987 reaction equation
[CH2:1]([O:8][CH2:9]/[CH:10]=[CH:11]/[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[Cl:18])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CC1(C)O[C@@]2(OC[C@H]3OC(C)(C)O[C@H]3C2=O)C[O:21]1.C([O-])([O-])=O.[K+].[K+].CC(O)=O.OOS([O-])=O.[K+].C([O-])([O-])=O.[K+].[K+]>[N+](CCCC)(CCCC)(CCCC)CCCC.[O-]S(O)(=O)=O.C(N(CC(O)=O)CC(O)=O)CN(CC(O)=O)CC(O)=O>[CH2:1]([O:8][CH2:9][C@@H:10]1[C@@H:11]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=2[Cl:18])[O:21]1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

8

Reactant 5

HCID 11430Potassium CarbonateHCID 7275400D-EpoxoneHCID 23369868K2CO3 AcOHHCID 23707502Potassium hydroxy sulfiteHCID 90033540(E)-1-(3(benzyloxy)prop-1enyl)2-chlorobenzene

Product 1

HCID 118140949(2R,3R)-2-(benzyloxymethyl)-3-(2-chlorophenyl)oxiraneYield 56.8%

Reagents, catalysts & solvents 2

HCID 94433Tetrabutylammonium hydrogen sulfateCatalystHCID 6049Ethylenediaminetetraacetic AcidSolvent3×

Conditions

Temperature
0 °C

Procedure

To a solution of (E)-1-(3-(benzyloxy)prop-1-enyl)-2-chlorobenzene (Preparation example 367, 4.16 g, 18.58 mmole) and 1,2;4,5-di-O-isopropylidene-β-D-erythro-2,3-hexodiulo-2,6-pyranose (5.76 g, 22.30 mmole) in DME-DMM (3:1, v/v) (185 mL) was added buffer (0.2M K2CO3—AcOH in 4×10-4 aq. EDTA, buffer pH=8.0) (185 mL) and Bu4NHSO4 (0.26 g, 0.75 mmole). After the mixture was cooled to 0° C., a solution of Oxone (15.76 g, 25.64 mmole) in 4×10-4 aq. EDTA (100 mL) and a solution of K2CO3 (13.6 g, 98.47 mmole) in 4×10-4 aq. EDTA (100 mL) were added dropwise separately over a period of 3.5 hr via a syringe pump at 0° C. The reaction mixture was stirred for 14 hr at 0° C. The reaction mixture was quenched with H2O then extracted with EtOAc. The aqueous layer was extracted with EtOAc and separated. The combined organic layer was washed with H2O then dried over MgSO4 and evaporated under reduced pressure The crude compound was purified by silica ge column to produce the title compound (2.9 g, 56%).

Workup

  1. customThe reaction mixture was quenched with H2O
  2. extractionthen extracted with EtOAc
  3. extractionThe aqueous layer was extracted with EtOAc
  4. customseparated
  5. washThe combined organic layer was washed with H2O
  6. dry with materialthen dried over MgSO4
  7. customevaporated under reduced pressure The crude compound
  8. customwas purified by silica ge column

Sources & evidence

ORD record
ord-2ada8ef90ab34d6eaaa25800208f2898
Source dataset
uspto-grants-2015_12
Patent number
US09221783B2

Reaction notes

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