127744-13-2

Upstream product

• 127744-10-9 5-[(1R,3aS,5R,6S,6aS)-5-(tert-Butyl-dimethyl-silanyloxy)-6-cyano-1-hydroxy-hexahydro-pentalen-(2E)-ylidene]-pentanoic acid methyl ester 
• 127744-10-9 5-[(1S,3aS,5R,6S,6aS)-5-(tert-Butyl-dimethyl-silanyloxy)-6-cyano-1-hydroxy-hexahydro-pentalen-(2E)-ylidene]-pentanoic acid methyl ester 
• 72397-63-8 (5RS,7SR)-7-t-butyldimethylsilyloxybicyclo[3.3.0]oct-8-en-2-one 
• 127744-09-6 5-[(3aS,5R,6S,6aS)-5-(tert-Butyl-dimethyl-silanyloxy)-6-cyano-1-oxo-hexahydro-pentalen-(2E)-ylidene]-pentanoic acid methyl ester 
• 14273-92-8 methyl 5-hydroxypentanoate 
• 6026-86-4 methyl 4-formylbutanoate 
• 542-28-9 3,4,5,6-tetrahydro-2H-pyran-2-one 
• 127744-11-0 5-[(1R,3aR,5S,6R,6aR)-1-Acetoxy-5-(tert-butyl-dimethyl-silanyloxy)-6-cyano-hexahydro-pentalen-(2E)-ylidene]-pentanoic acid methyl ester 
• 127744-11-0 5-[(1S,3aR,5S,6R,6aR)-1-Acetoxy-5-(tert-butyl-dimethyl-silanyloxy)-6-cyano-hexahydro-pentalen-(2E)-ylidene]-pentanoic acid methyl ester 

Relevant academic research and scientific papers

Stereocontrol in organic synthesis using silicon-containing compounds. A synthesis of a (±)-carbacyclin analogue with the geometry of the exocyclic double bond controlled by the protodesilylation of an allylsilane

The known ketone, 7-tert-butyldimethylsilyloxybicyclo[3.3.0]oct-8-en-2-one 11, was converted in five steps into 3-(4′-methoxycarbonylbutylidene)-7-tert-butyldimethylsilyloxy-8- cyanobicyclo[3.3.0]octan-2-one 13. Reduction gave the diastereoisomeric pair of allylic alcohols 14 and 15, both of which were converted into the allylsilane, 3-(1′-dimethylphenylsilyl-4′-methoxycarbonyl)butyl-7-tert- butyldimethyl-silyloxy-8-cyanobicyclo[3.3.0]oct-2-ene 20. Protodesilylation of the allylsilane gave a high level of selectivity (>96:4) in favour of the carbacyclin analogue, 5-(4′-methoxycarbonyl)butylidene-3-tert-butyldimethylsilyloxy-2- cyanobicyclo[3.3.0]octane 22, having the exocyclic double bond with the E-configuration.