Réaction #1162737

Équation de réaction

ethylacrylate

(1S,4aR,5R,8aR)-tert-Butyl[5-[(S)-2-iodo-1-methyl-ethyl]-4a-methyl-decahydronaphtalen-1-yloxy]-dimethylsilane

→

(R)-5-[(1R,4aR,5S,8aR)-5-(tert-Butyl-dimethyl-silanyloxy)-8a-methyl-decahydro-naphtalen-1-yl)-hexanoic acid ethyl ester

Rendement 44.0%

Solvants

tetrahydrofuran pyridine

tetrahydrofuran pyridine

Conditions de réaction

Traitement

1. 1
   TempératureThe reaction mixture is heated at 65° for 30 minutes
2. 2
   workup.ADDITIONare added
3. 3
   FiltrationFiltration through Speedex
4. 4
   Lavagewashing of the filter cake with ethylacetate
5. 5
   Autreis followed by evaporation in vacuo to 1/3 of the volume
6. 6
   workup.ADDITIONThe solution is diluted with ethylacetate
7. 7
   Lavagethe organic phase is washed 4 times with a disodium ethylene diamine tetraacetate dihydrate (EDTA) solution (8 g of EDTA and 8 g of NaHCO3 in 100 ml water)
8. 8
   SéchageThe organic phase is dried over Na2SO4
9. 9
   Filtrationfiltered
10. 10
    Autreevaporated in vacuo
11. 11
    AutreThe residue is chromatographed over 100 g of silicagel with hexane/ethylacetate 98/2

Mode opératoire

To 342.5 mg (5.24 mMol) of Zn powder are added 1.57 ml of tetrahydrofuran/pyridine 2/1. The reaction mixture is stirred under Argon, 247.2 mg (1.04 mMol) of NiCl2.6H2O and then 472.2 mg (4.72 mMol) of ethylacrylate are added. The reaction mixture is heated at 65° for 30 minutes, cooled to room temperature and 947 mg (2.10 mMol) of (1S,4aR,5R,8aR)-tert-Butyl[5-[(S)-2-iodo-1-methyl-ethyl]-4a-methyl-decahydronaphtalen-1-yloxy]-dimethylsilane dissolved in 1.57 ml of tetrahydrofuran pyridine 1/2 are added and the reaction mixture kept overnight at room temperature. Filtration through Speedex and washing of the filter cake with ethylacetate is followed by evaporation in vacuo to 1/3 of the volume. The solution is diluted with ethylacetate and the organic phase is washed 4 times with a disodium ethylene diamine tetraacetate dihydrate (EDTA) solution (8 g of EDTA and 8 g of NaHCO3 in 100 ml water) and twice with brine. The organic phase is dried over Na2SO4, filtered and evaporated in vacuo. The residue is chromatographed over 100 g of silicagel with hexane/ethylacetate 98/2 to yield 269 mg of starting material and 390 mg (44%) of (R)-5-[(1R,4aR,5S,8aR)-5-(tert-Butyl-dimethyl-silanyloxy)-8a-methyl-decahydro-naphtalen-1-yl)-hexanoic acid ethyl ester as an amorphous product.

Source