Cornforth reagent → HCID 11427434, compound

HRID 873282Notes

Reaction equation

HRID 873282 reaction equation
[OH:1][CH2:2][C:3]([CH3:22])([CH3:21])[CH2:4][CH2:5][CH2:6][C:7](=[O:20])[CH2:8][CH2:9][CH2:10][CH2:11][C:12]([CH3:19])([CH3:18])[C:13]([O:15][CH2:16][CH3:17])=[O:14].[Cr](O[Cr]([O-])(=O)=O)([O-])(=O)=[O:24].[NH+]1C=CC=CC=1.[NH+]1C=CC=CC=1>CN(C=O)C.OS(O)(=O)=O.O>[CH2:16]([O:15][C:13](=[O:14])[C:12]([CH3:19])([CH3:18])[CH2:11][CH2:10][CH2:9][CH2:8][C:7](=[O:20])[CH2:6][CH2:5][CH2:4][C:3]([CH3:21])([CH3:22])[C:2]([OH:24])=[O:1])[CH3:17]

Participants

6

Reactant 2

HCID 2724130Cornforth reagentHCID 11243945HCID 11243945, compound

Product 1

HCID 11427434HCID 11427434, compoundYield 79%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 1118Sulfuric AcidSolventHCID 6228DimethylformamideSolvent

Procedure

A mixture of 221 (3.26 g, 10.4 mmol) and pyridinium dichromate (14.0 g, 37.2 mmol) in DMF (45 mL) was stirred at room temperature for 46 h. The solution was diluted with 48% H2SO4 (30 mL) and water (300 mL) and extracted with ethyl acetate (5×100 mL). The combined organic layers were washed with saturated aqueous NaCl solution (5×100 mL), dried over anhydrous MgSO4, and concentrated in vacuo to give the crude product (3.19 g) as greenish oil. The crude product was subjected to column chromatography (silica gel; hexanes/ethyl acetate=3:1, 2:1), affording 223 (2.69 g, 79%) as a pale yellow oil. 1H NMR (CDCl3): δ 11.30 (br., 1H), 4.10 (q, 2H, J=7.2), 2.39 (t, 4H, J=7.2), 1.56-1.48 (m, 8H), 1.25-1.15 (m, 2H), 1.24 (t, 3H, J=7.2), 1.20 (s, 6H), 1.15 (s, 6H). 13C NMR (CDCl3): δ 210.9, 184.4, 178.1, 60.4, 43.1, 42.7, 42.2, 40.5, 39.8, 25.3, 25.0, 24.7, 24.3, 19.3, 14.4. HRMS (LSIMS, gly): Calcd for C18H33O5 (MH+): 329.2328, found: 329.2330.

Workup

  1. extractionextracted with ethyl acetate (5×100 mL)
  2. washThe combined organic layers were washed with saturated aqueous NaCl solution (5×100 mL)
  3. dry with materialdried over anhydrous MgSO4
  4. concentrationconcentrated in vacuo
  5. customto give the crude product (3.19 g) as greenish oil

Sources & evidence

ORD record
ord-954ad77a982b4d38bfb058c832803da2
Source dataset
uspto-grants-2015_03
Patent number
US08975300B2

Reaction notes

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