Triethylamine → 6-[(E)-3-tert-Butyldimethylsilyloxy-4-phenoxybut-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one

HRID 462802Notes

Reaction equation

HRID 462802 reaction equation
[Si:1]([O:8][CH:9]([CH2:30][O:31][C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1)/[CH:10]=[CH:11]/[CH:12]1[CH2:19][CH2:18][CH:17]2[CH:13]1[CH2:14][CH:15]([CH:21](O)[CH2:22][CH2:23][CH2:24][C:25]([O:27][CH3:28])=[O:26])[C:16]2=[O:20])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].CS(Cl)(=O)=O.C(N(CC)CC)C.N12CCCN=C1CCCCC2>C1C=CC=CC=1.O>[Si:1]([O:8][CH:9]([CH2:30][O:31][C:32]1[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=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:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

Participants

7

Reactant 4

HCID 8471TriethylamineHCID 31297Methanesulfonyl chlorideHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 203972146-[(E)-3-tert-butyldimethylsilyloxy-4-phenoxybut-1-enyl]-3-(1-hydroxy-4-methoxycarbonylbut-1-yl)bicyclo[3,3,0]octan-2-one

Product 1

HCID 203971906-[(E)-3-tert-Butyldimethylsilyloxy-4-phenoxybut-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-oneYield 65.4%

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 962WaterSolvent

Procedure

A stirred solution of 6-[(E)-3-tert-butyldimethylsilyloxy-4-phenoxybut-1-enyl]-3-(1-hydroxy-4-methoxycarbonylbut-1-yl)bicyclo[3,3,0]octan-2-one (38 mg), prepared as described in Reference Example 47 and in the form of (±)-6β-[(E)-3β-tert-butyldimethylsilyloxy-4-phenoxybut-1-enyl]-3-(1-hydroxy-4-methoxycarbonylbut-1-yl)bicyclo[3,3,0]octan-2-one, in dry benzene (0.28 ml) was treated with methanesulphonyl chloride (0.0072 ml) at the ambient temperature and then with triethylamine (0.012 ml) and stirred for 2 hours. It was then treated with 1,8-diazabicyclo[5,4,0]undec-7-ene (65 mg) and stirred for 150 minutes. The mixture was treated with water (15 ml) and extracted with ethyl acetate. The extract was washed with saturated aqueous sodium chloride solution, dried over anhydrous sodium sulphate, and concentrated under reduced pressure. The resulting residue was then subjected to medium pressure, short column chromatography on silica gel, eluting with a mixture of ethyl acetate and hexane (23:77 v/v), to give 6-[(E)-3-tert-butyldimethylsilyloxy-4-phenoxybut-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one (24 mg), in the form of (±)-6β-[(E)-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,15S)-6a-oxo-6,9-methano-15-tert-butyldimethylsilyloxy-16-phenoxy-17,18,19,20-tetranorprosta-5,13-dienoate.

Workup

  1. extractionextracted with ethyl acetate
  2. washThe extract was washed with saturated aqueous sodium chloride solution
  3. dry with materialdried over anhydrous sodium sulphate
  4. concentrationconcentrated under reduced pressure
  5. washeluting with a mixture of ethyl acetate and hexane (23:77 v/v)

Sources & evidence

ORD record
ord-68e26e550c544ab9a0f6700871975a9c
Source dataset
uspto-grants-1985_05
Patent number
US04517202

Reaction notes

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