102491-28-1Relevant articles and documents
Shibasaki et al.
, p. 433 (1979)
PROSTANOIDS. LII. (+/-)-7,7-DICHLORO-4β-TRIMETHYLSILYLBICYCLOHEPT-3-EN-6-ONE IN THE SYNTHESIS OF PROSTANOIDS. RACEMIC CARBACYCLIN
Tolstikov, G. A.,Akhmetvaleev, R. R.,Zhurba, V. M.,Vasil'eva, M. S.,Miftakhov, M. S.
, p. 543 - 552 (2007/10/02)
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
Newton, Roger F.,Wadsworth, Alan H.
, p. 822 - 830 (2007/10/02)
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.