Lithium hydroxide, monohydrate → HCID 22794411, compound

HRID 1943068Notes

Reaction equation

HRID 1943068 reaction equation
[O:1]=[C:2]([CH2:10][CH2:11][CH2:12][CH2:13][CH3:14])[CH2:3]P(=O)(OC)OC.O.[OH-].[Li+].[C:18]([O:21][C@@H:22]1[C@H:26]([CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][C:33]([O:35][CH3:36])=[O:34])[C@@H:25]([CH:37]=O)[C@H:24]([O:39][CH:40]2[CH2:45][CH2:44][CH2:43][CH2:42][O:41]2)[CH2:23]1)(=[O:20])[CH3:19]>COC(C)(C)C.O>[C:18]([O:21][C@@H:22]1[C@H:26]([CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][C:33]([O:35][CH3:36])=[O:34])[C@@H:25](/[CH:37]=[CH:3]/[C:2](=[O:1])[CH2:10][CH2:11][CH2:12][CH2:13][CH3:14])[C@H:24]([O:39][CH:40]2[CH2:45][CH2:44][CH2:43][CH2:42][O:41]2)[CH2:23]1)(=[O:20])[CH3:19]

Participants

6

Reactant 3

HCID 168937Lithium hydroxide, monohydrateHCID 580181Dimethyl (2-oxoheptyl)phosphonateHCID 11729034methyl 7-[(1R,2R,3R,5S)-5-acetoxy-2-formyl-3-(2-tetrahydropyranyl-oxy)cyclopentyl]heptanate

Product 1

HCID 22794411HCID 22794411, compoundYield 96.4%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 15413tert-Butyl methyl etherSolvent2×

Procedure

To a solution of dimethyl (2-oxoheptyl)phosphonate (12) (0.178 g, 0.801 mmol) in t-butyl methyl ether (2 ml), lithium hydroxide monohydrate (32.5 mg, 0.775 mmol) was added and the mixture was stirred for two hours at room temperature. A solution of methyl 7-[(1R,2R,3R,5S)-5-acetoxy-2-formyl-3-(2-tetrahydropyranyl-oxy)cyclopentyl]heptanate (2) (0.213 g, 0.535 mmol) in t-butyl methyl ether (2 ml) and water (0.12 ml) were added thereto, and the mixed solution was stirred for one hour at room temperature. The reaction mixture was added to water and extracted twice with t-butyl methyl ether. The organic layers were combined, sequentially washed with saturated sodium bicarbonate water and saturated aqueous sodium chloride, and then dried with anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by silica gel column chromatography (Fuji Silysia BW-300: 100 g; ethyl acetate:hexane=3:7), to give methyl 7-[(1R,2R,3R,5S)-5-acetoxy-2-((E)-3-oxo-1-octenyl)-3-(2-tetrahydropyranyloxy)cyclopentyl]heptanate (13) (0.255 g; 0.516 mmol; yield: 96.4%) as a colorless oil.

Workup

  1. stirringthe mixed solution was stirred for one hour at room temperature
  2. extractionextracted twice with t-butyl methyl ether
  3. washsequentially washed with saturated sodium bicarbonate water and saturated aqueous sodium chloride
  4. dry with materialdried with anhydrous magnesium sulfate
  5. concentrationAfter concentration under reduced pressure
  6. customthe residue was purified by silica gel column chromatography (Fuji Silysia BW-300: 100 g; ethyl acetate:hexane=3:7)

Sources & evidence

ORD record
ord-558cac849cc84683a830bad036cfbd08
Source dataset
uspto-grants-2013_03
Patent number
US08389748B2

Reaction notes

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