87828-10-2

Upstream product

• 70398-75-3 (3aα,6aα)-5β-(t-butyldimethylsilyloxy)-4α-<(E)-(3S*)-3-(t-butyldimethylsilyloxy)oct-1-enyl>perhydropentalen-2-one 
• 41723-91-5 4-carboxybutyliden triphenylphosphorane sodium 
• 69552-54-1 3α-hydroxy-2β-<3α-hydroxy-1(E)-octenyl>bicyclo<3.3.0>octan-7-one 
• 70871-23-7 5-[(3aR,4S,5S,6aR)-5-(Tetrahydro-pyran-2-yloxy)-4-[(E)-(R)-3-(tetrahydro-pyran-2-yloxy)-oct-1-enyl]-hexahydro-pentalen-(2Z)-ylidene]-pentanoic acid methyl ester 
• 92471-34-6 methyl 5-hydroxy-5-(8α-ethoxycarbonyl-1βH,6βH-bicyclo<4.3.0>non-3-en-8β-yl)pentanoate 
• 87751-98-2 methyl 5-oxo-5-(8α-ethoxycarbonyl-1βH,6βH-bicyclo<4.3.0>non-3-en-8β-yl)pentanoate 
• 87752-00-9 methyl 5-acetoxy-5-(8α-ethoxycarbonyl-1βH,6βH-bicyclo<4.3.0>non-3-en-8β-yl)pentanoate 
• 87752-01-0 methyl 5-acetoxy-5-<1α-ethoxycarbonyl-3α,4α-bis(formylmethyl)-1β-yl>pentanoate 
• 87752-02-1 methyl 5-acetoxy-5-(3α-ethoxycarbonyl-6β-formyl-7α-hydroxy-1βH,5βH-bicyclo<3.3.0>oct-3β-yl)pentanoate 
• 87752-03-2 methyl 5-acetoxy-5-(3α-ethoxycarbonyl-6β-<(E)-3-oxo-oct-1-enyl>-7α-hydroxy-1βH,5βH-bicyclo<3.3.0>oct-3β-yl)pentanoate 
• 87752-04-3 methyl 5-acetoxy-5-(3α-ethoxycarbonyl-6β-<(E)-3-oxo-oct-1-enyl>-7α-(tetrahydropyran-2-yl)oxy-1βH,5βH-bicyclo<3.3.0>oct-3β-yl)pentanoate 
• 87752-07-6 5-acetoxy-6α-ethoxycarbonyl-6a-carbaprostaglandin I₁ methyl ester 11,15-bis(tetrahydropyran-2-yl)ether 
• 87752-06-5 5-acetoxy-6α-ethoxycarbonyl-6a-carbaprostaglandin I₁ methyl ester 
• 87751-97-1 5(R^*)-hydroxy-6α-carboxy-6a-carbaprostaglandin I₁ 11,15-bis(tetrahydropyran-2-yl)ether 

Downstream Products

• 69552-46-1 (5E)-carba-PGI2 
• 102491-28-1 (-)-ent-9(O)-methanoprostacyclin 

Relevant academic research and scientific papers

PROSTANOIDS. LII. (+/-)-7,7-DICHLORO-4β-TRIMETHYLSILYLBICYCLOHEPT-3-EN-6-ONE IN THE SYNTHESIS OF PROSTANOIDS. RACEMIC CARBACYCLIN

The products from the Prins reaction of formaldehyde and (+/-)-7,7-dichloro-4β-trimethylsilylbicyclohept-3-en-6-one were isolated and characterized.The optimum conditions were found for the production of the isomeric 2β-acetoxy-6,6(7,7)-dichlorobicyclohept-3-en-7(6)-ones and 2β-acetoxymethyl-3α-acetoxy-6,6(7,7)-dichlorobicyclohept-3-en-7(6)-ones and also (1R,2S,5R,6S,10R)-3,3-dichloro-4-oxo-10-hydroxy(acetoxy)-8-oxatricyclo2,5>undecanes, suitable for the subsequent synthesis of modified prostanoids.An effective scheme for the synthesis of (+/-)-carbacyclin was worked out on the basis of the monoacetates of a series of bicycloheptenones through the corresponding 2β-acetoxymethyl-3α-acetoxybicyclooctan-7-ones.

Synthesis of Stable Prostacyclin Analogues from 2,3-Disubstituted Bicycloheptan-6-ones

A short synthesis of 9-deoxy-6-9α-methanoepoxy-Δ5-prostaglandin F1 (14) from bicycloheptan-6-one (3) is described.The ketone (3) can be converted by known methods into the vinyl ether (8).In the presence of mercury(II) acetate at 100 deg C, the 5-hydroxyalk-1-enyl methyl ether (8) undergoes a novel intramolecular vinyl transetherification reaction to give the Δ2-dihydropyran (9).Hydroboration-oxidation of the dihydropyran (9) furnished selectively the tetrahydropyran-3-ol (10).Subsequent elaboration via oxidation, Wittig olefination, and deprotection afforded 9-deoxy-6,9α-methanoepoxy-Δ5-prostaglandin F1 (14).The protected bicycloheptan-6-one (16) underwent a ring expansion with diazomethane, producing a 1:1 mixture of the two homologated ketones (17) and (18).Wittig olefination and deprotection of these ketones provided 15-epi-9-deoxy-6,9α-methano-Δ5-prostaglandin F1 (19) and its structural isomer (20).The two bicycloheptan-6-ones (3) and (4) also led directly to a series of 9-deoxy-6,9α-cycloprostaglandins F1 via Wittig reactions.