Triethylamine → 3,3a,4,5,6,6a-hexahydro-2H-pentalen-1-one

HRID 462799Notes

Reaction equation

HRID 462799 reaction equation
[Si:1]([O:8][CH:9]([CH:32]1[CH2:37][CH2:36][CH2:35][CH2:34][CH2:33]1)/[CH:10]=[CH:11]/[CH:12]1[CH2:19][CH2:18][CH:17]2[CH:13]1[CH2:14][CH:15]([C:21]([OH:31])([CH2:23][CH2:24][CH2:25][C:26]([O:28][CH2:29][CH3:30])=[O:27])[CH3:22])[C:16]2=[O:20])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[CH3:38]S(Cl)(=O)=O.C(N(CC)CC)C.N12CCCN=C1CCCCC2>C1C=CC=CC=1.O>[Si:1]([O:8][CH:9]([CH:32]1[CH2:33][CH2:34][CH2:35][CH2:36][CH2:37]1)/[CH:10]=[CH:11]/[CH:12]1[CH2:19][CH2:18][CH:17]2[CH:13]1[CH2:14][CH:15]([C:21]1([OH:31])[CH2:22][CH2:38][CH:25]([C:26]([O:28][CH2:29][CH3:30])=[O:27])[CH2:24][CH2:23]1)[C:16]2=[O:20])([C:4]([CH3:5])([CH3:6])[CH3:7])([CH3:3])[CH3:2].[CH:17]12[CH2:18][CH2:19][CH2:12][CH:13]1[CH2:14][CH2:15][C:16]2=[O:20]

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 31297Methanesulfonyl chlorideHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 203972076-[(E)-3-tert-butyldimethylsilyloxy-3-cyclohexylprop-1-enyl]-3-(5-ethoxycarbonyl-2-hydroxypent-2-yl)bicyclo[3,3,0]octan-2-one

Product 2

HCID 1406313,3a,4,5,6,6a-hexahydro-2H-pentalen-1-oneHCID 13241022(E)-6-(3-tert-Butyldimethylsilyloxy-3-cyclohexylprop-1-enyl)-3-(4-ethoxycarbonyl-1-hydroxycyclohex-1-yl)bicyclo[3,3,0]octan-2-one

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 962WaterSolvent

Procedure

A stirred solution of 6-[(E)-3-tert-butyldimethylsilyloxy-3-cyclohexylprop-1-enyl]-3-(5-ethoxycarbonyl-2-hydroxypent-2-yl)bicyclo[3,3,0]octan-2-one (26 mg), prepared as described in Reference Example 39 and in the form of 6β-[(E)-3β-tert-butyldimethylsilyloxy-3-cyclohexylprop-1-enyl]-3-(5-ethoxycarbonyl-2-hydroxypent-2-yl)bicyclo[3,3,0]octan-2-one, otherwise known as (±)-ethyl(13E)-(9S,15R)-6a-oxo-6,9-methano-15-tert-butyldimethylsilyloxy-15-cyclohexyl-5-hydroxy-5-methyl-16,17,18,19,20-pentanorprost-13-enoate, in benzene (0.19 ml) was treated with methanesulphonyl chloride (0.0048 ml) at the ambient temperature, followed by triethylamine (0.008 ml) and the mixture was stirred for 2 hours. It was then treated with 1,8-diazabicyclo[5,4,0]undec-7-ene (0.0446 ml) and the mixture was stirred for 2 hours. It was then treated with water (10 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 subjected to medium pressure, short column chromatography on silica gel, using a mixture of ethyl acetate and hexane (1:8 v/v) as eluant, to give 6-[(E)-3-tert-butyldimethylsilyloxy-3-cyclohexylprop-1-enyl]-3-{[mixture of (E) and (Z)]-5-ethoxycarbonylpentylid-2-ene}bicyclo[3,3,0]octan-2-one (22 mg), in the form of (±)-6β-[(E)-3β-tert-butyldimethylsilyloxy-3-cyclohexylprop-1-enyl]-3-{[mixture of (E) and (Z)]-5-ethoxycarbonylpentylid-2-ene}bicyclo[3,3,0]octan-2-one, otherwise known as (±)-ethyl [mixture of (5E and (5Z)],(13E)-(9S,15R)-6a-oxo-6,9-methano-5-methyl-15-tert-butyldimethylsilyloxy-15-cyclohexyl-16,17,18,19,20-pentanorprosta-5,13-dienoate.

Workup

  1. stirringthe mixture was stirred for 2 hours
  2. extractionextracted with ethyl acetate
  3. washThe extract was washed with saturated aqueous sodium chloride solution
  4. dry with materialdried over anhydrous sodium sulphate
  5. concentrationconcentrated under reduced pressure
  6. additiona mixture of ethyl acetate and hexane (1:8 v/v) as eluant

Sources & evidence

ORD record
ord-3e219d7097b84d41874fe24592df190b
Source dataset
uspto-grants-1985_05
Patent number
US04517202

Reaction notes

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