m-Chloroperbenzoic acid → HCID 70907159, compound

HRID 1914508Notes

Reaction equation

HRID 1914508 reaction equation
[O:1]1[C:6]2[CH:7]=[CH:8][C:9]([CH2:11][C:12]3[CH:13]=[C:14]([C@H:20]4[C@H:25]([OH:26])[C@@H:24]([OH:27])[C@H:23]([OH:28])[C@@H:22]([CH2:29][OH:30])[O:21]4)[CH:15]=[CH:16][C:17]=3[CH2:18][CH3:19])=[CH:10][C:5]=2[O:4][CH2:3][CH2:2]1.[C:31]([O:35][P:36](N(CC)CC)(=[O:42])[O:37][C:38]([CH3:41])([CH3:40])[CH3:39])([CH3:34])([CH3:33])[CH3:32].N1C=NN=N1.C1C=C(Cl)C=C(C(OO)=O)C=1>C1COCC1.C(Cl)Cl>[O:1]1[C:6]2[CH:7]=[CH:8][C:9]([CH2:11][C:12]3[CH:13]=[C:14]([C@@H:20]4[O:21][C@H:22]([CH2:29][O:30][P:36](=[O:42])([O:37][C:38]([CH3:41])([CH3:40])[CH3:39])[O:35][C:31]([CH3:33])([CH3:34])[CH3:32])[C@@H:23]([OH:28])[C@H:24]([OH:27])[C@H:25]4[OH:26])[CH:15]=[CH:16][C:17]=3[CH2:18][CH3:19])=[CH:10][C:5]=2[O:4][CH2:3][CH2:2]1

Participants

7

Reactant 4

HCID 70297m-Chloroperbenzoic acidHCID 14827533HCID 14827533, compoundHCID 52913524Licogliflozin2×HCID 178418441HCID 178418441, compound

Product 1

HCID 70907159HCID 70907159, compoundYield 47.9%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-40 °C

Procedure

To a stirred solution of (2S,3R,4R,5S,6R)-2-[3-(2,3-Dihydro-benzo[1,4]dioxin-6-ylmethyl)-4-ethyl-phenyl]-6-hydroxymethyl-tetrahydro-pyran-3,4,5-triol (Intermediate 2, 1.0 g, 2.4 mmol) in THF (15 ml) was added a solution of Diethyl-phosphoramidic acid di-tert-butyl ester (780 mg, 3.12 mmol) in THF (5 ml) at 0° C. followed by a solution of tetrazole (435 mg, 6.2 mmol) in DCM (12.5 ml). After stirring for 5 min at same temperature, it was stirred at room temperature for 20 min. Reaction mixture was cooled to −40° C. and added a solution of m-CPBA (830 mg, 4.8 mmol) in DCM (5 ml). The reaction mixture was stirred at same temperature for 5 min and then at room temperature for 2 h. Reaction mixture was cooled to 0° C. and quenched by the addition of 10% sodium bisulfite solution (5 ml). This was extracted with ether (3×10 ml). Combined organic layer was washed with brine (5 ml), dried over sodium sulfate and concentrated to give 700 mg of phosphoric acid di-tert-butyl ester (2R,3S,4R,5R,6S)-6-[3-(2,3-dihydro-benzo[1,4]dioxin-6-ylmethyl)-4-ethyl-phenyl]-3,4,5-trihydroxy-tetrahydro-pyran-2-ylmethyl ester.

Workup

  1. stirringwas stirred at room temperature for 20 min
  2. customReaction mixture
  3. stirringThe reaction mixture was stirred at same temperature for 5 min
  4. waitat room temperature for 2 h
  5. customReaction mixture
  6. temperaturewas cooled to 0° C.
  7. customquenched by the addition of 10% sodium bisulfite solution (5 ml)
  8. extractionThis was extracted with ether (3×10 ml)
  9. washCombined organic layer was washed with brine (5 ml)
  10. dry with materialdried over sodium sulfate
  11. concentrationconcentrated

Sources & evidence

ORD record
ord-7f07a0a4889b412b845f54ca34838d2e
Source dataset
uspto-grants-2013_12
Patent number
US08614195B2

Reaction notes

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