82978-04-9Relevant academic research and scientific papers
Photolytic Conversion of Some Bicycloheptanones into 3-Hydroxy- or 3-Methoxy-2-oxabicyclooctan-2-ones
Newton, Roger F.,Reynolds, Derek P.,Crossland, Noelle M.,Kelly, David R.,Roberts, Stanley M.
, p. 1583 - 1586 (2007/10/02)
The ketones (1) and (7)-(9) gave the corresponding cyclic acetals (3), (4), and (12)-(17), respectively, on photolysis in methanol.Concurrent production of the alkenes (6) and (18)-(20) detracted from the potential synthetic utility of this process.However, photolysis of the ketones (8), (10), and (11) in aqueous tetrahydrofuran or aqueous acetonitrile led to a highly selective ring-expansion process, and consequently high yields of the corresponding γ-lactols (21)-(23).
Total Synthesis of Prostaglandin-F2α involving Stereocontrolled and Photo-induced Reactions of Bicycloheptanones
Howard, Colin C.,Newton, Roger F.,Reynolds, Derek P.,Wardsworth, Alan H.,Kelly, David R.,Roberts, Stanley M.
, p. 852 - 857 (2007/10/02)
A short total synthesis of prostaglandin-F2α from cyclopentadiene is described.Acetalisation of bicyclohept-2-en-6-one (1) followed by formation of a singal bromohydrin gave on treatment with base the epoxyacetal (4).Reaction of (4) with the appropriate organocuprate reagent introduced both the 12β side-chain and 11α-hydroxy-group of the embryonic prostaglandin.The fused cyclobutane ring is important as it controls both the stereoselectivity of epoxide formation and the regioselectivity of the subsequent ring-opening reaction.Furthermore, the unusual photochemical behaviour of cyclobutanones was exploited in this synthesis.Irradiation of the bicycloheptan-6-one (9) in aqueous solution and subsequent Wittig olefination afforded prostaglandin-F2α.Baeyer-Villiger oxidation of the same ketone (9) furnished the lactone (16), a known precursor of prostaglandin-E.
