Acetic Acid → 6-[(E)-3-hydroxy-4-phenoxybut-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one

HRID 462778Notes

Reaction equation

HRID 462778 reaction equation
[Si]([O:8][CH:9]([CH2:29][O:30][C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1)/[CH:10]=[CH:11]/[CH:12]1[CH2:19][CH2:18][CH:17]2[CH:13]1[CH2:14]/[C:15](=[CH:21]\[CH2:22][CH2:23][CH2:24][C:25]([O:27][CH3:28])=[O:26])/[C:16]2=[O:20])(C(C)(C)C)(C)C.COC(CCC/C=C1/C(=O)C2C(C/1)CCC2)=O.O.C(O)(=O)C>[Cl-].[Na+].O1CCCC1>[OH:8][CH:9]([CH2:29][O:30][C:31]1[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=1)/[CH:10]=[CH:11]/[CH:12]1[CH2:19][CH2:18][CH:17]2[CH:13]1[CH2:14]/[C:15](=[CH:21]\[CH2:22][CH2:23][CH2:24][C:25]([O:27][CH3:28])=[O:26])/[C:16]2=[O:20]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 962WaterHCID 203971906-[(E)-3-tert-Butyldimethylsilyloxy-4-phenoxybut-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-oneHCID 867400973-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one

Product 1

HCID 203971966-[(E)-3-hydroxy-4-phenoxybut-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-oneYield 28.2%

Reagents, catalysts & solvents 2

HCID 5234Sodium ChlorideSolventHCID 8028TetrahydrofuranSolvent

Procedure

6-[(E)-3-tert-Butyldimethylsilyloxy-4-phenoxybut-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one (4.1 mg), prepared as described in Reference Example 54, and in the form of (±)-6β-[(E)-(mixture of 3α and 3β)-tert-butyldimethylsilyloxy-4-phenoxybut-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one, otherwise known as (±)-methyl (5E,13E)-(9S), [mixture of (15R) and (15S)]-6a-oxo-6,9-methano-15-tert-butyldimethylsilyloxy-16-phenoxy-17,18,19,20-tetranorprosta-5,13-dienoate, and a solution of water, glacial acetic acid and tetrahydrofuran (1.0 ml; 7:13:2 by volume) were stirred together at 40° C. for 4 hours. After cooling, the mixture was diluted with saturated aqueous sodium chloride solution and extracted with diethyl ether. The extract was washed with aqueous sodium bicarbonate solution (1M) and then with saturated aqueous sodium chloride solution, dried over anhydrous sodium sulphate and concentrated under reduced pressure. The residue (3.0 mg) was subjected to preparative thin layer chromatography on silica gel, eluting with a mixture of ethyl acetate and hexane (3:2 v/v), to give 6-[(E)-3-hydroxy-4-phenoxybut-1-enyl] -3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one (0.9 mg), in the form of (±)-6β-[(E)-(mixture of 3α and 3β)-hydroxy-4-phenoxybut-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one, otherwise known as (±)-methyl (5E,13E)-(9S), [mixture of (15R) and (15S)]-6a-oxo-6,9-methano-15-hydroxy-16-phenoxy-17,18,19,20-tetranorprosta-5,13-dienoate.

Workup

  1. temperatureAfter cooling
  2. extractionextracted with diethyl ether
  3. washThe extract was washed with aqueous sodium bicarbonate solution (1M)
  4. dry with materialwith saturated aqueous sodium chloride solution, dried over anhydrous sodium sulphate
  5. concentrationconcentrated under reduced pressure
  6. washeluting with a mixture of ethyl acetate and hexane (3:2 v/v)

Sources & evidence

ORD record
ord-a9b6913a7d294618a054b26effe7121b
Source dataset
uspto-grants-1985_05
Patent number
US04517202

Reaction notes

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