3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one → 3-[(Z)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one

HRID 462772Notes

Reaction equation

HRID 462772 reaction equation
[CH3:1][O:2][C:3]([CH2:5][CH2:6][CH2:7]/[CH:8]=[C:9]1/[C:10](=[O:17])[CH:11]2[CH:15]([CH2:16]/1)[CH2:14][CH2:13][CH2:12]2)=[O:4]>CO.[Hg]>[CH3:1][O:2][C:3]([CH2:5][CH2:6][CH2:7]/[CH:8]=[C:9]1\[C:10](=[O:17])[CH:11]2[CH:15]([CH2:16]\1)[CH2:14][CH2:13][CH2:12]2)=[O:4]

Participants

4

Reactant 1

HCID 867400973-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one

Product 1

HCID 867400983-[(Z)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-oneYield 25%

Reagents, catalysts & solvents 2

HCID 23931MercuryCatalystHCID 887MethanolSolvent

Procedure

A solution of 6-[(E)-(mixture of 3α and 3β)-hydroxyoct-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one (20 mg), prepared as described in Example 4 and predominantly in the 6β-configuration, otherwise known as (±)-methyl(5E,13E)-(9S),[mixture of (15R) and (15S)]-6a-oxo-6,9-methano-15-hydroxyprosta-5,13-dienoate, in methanol (5 ml) was irradiated for 20 hours with ultra-violet rays of wavelength 254 nm, emitted by a low pressure mercury vapour lamp. The solution was carefully concentrated in vacuo and then subjected to preparative thin layer chromatography on silica gel, using a mixture of ethyl acetate and hexane (1:4 v/v) as eluant, to give 6-[(E)-(mixture of 3α and 3β)-hydroxyoct-1-enyl]-3-[(Z)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one (5.0 mg), predominantly in the 6β-configuration, otherwise known as (±)-methyl(5Z,13E)-(9S),[mixture of (15R) and (15S)]-6a-oxo-6,9-methano-15-hydroxyprosta-5,13-dienoate [NMR in deuterochloroform: multiplets at 5.9, 5.5., 4.1, 3.0-1.1, 1.1-0.7 p.p.m., singlet at 3.7 p.p.m.]; and recovered 6-[(E)-(mixture of 3α and 3β)-hydroxyoct-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]-bicyclo[3,3,0]octan-2-one (3.6 mg) [NMR in deuterochloroform: multiplets at 6.5, 5.5, 4.1, 3.0-1.1, 1.1-0.7 p.p.m., singlet at 3.7 p.p.m⟧

Workup

  1. concentrationThe solution was carefully concentrated in vacuo
  2. additiona mixture of ethyl acetate and hexane (1:4 v/v) as eluant

Sources & evidence

ORD record
ord-1078854332d546bebb4fa0001d3d6a61
Source dataset
uspto-grants-1985_05
Patent number
US04517202

Reaction notes

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