42586-67-4Relevant articles and documents
Prostaglandins and Prostaglandin Intermediates. Part 26 A Novel Route to PGF2α using Triisopropoxy-hept-1-ynyl-titanium as Precursor for the β-Side Chain
Mahrwald, Rainer,Schick, Hans,Pivnitsky, Kasimir K.,Schwarz, Sigfrid
, p. 403 - 413 (2007/10/02)
The benzoylated Corey aldehyde 1a can be alkynylated with hept-1-ynyl-triisopropoxytitanium in good chemical yield and high diastereoselectivity to the (R)-alcohol 3c admixed with about 10percent of the diastereomeric (S)-alcohol 2c.Without removal of thi
TOTAL SYNTHESIS AND PROPERTIES OF PROSTAGLANDINS. X. SYNTHESIS OF γ-KETO ESTERS AND THEIR REACTION WITH SOME ALUMINUM- AND BORON-CONTAINING REAGENTS
Kalnin'sh, A. P.,Dikovskaya, K. I.,Kuchin, A. V.,Kudryashova, V. V.,Korita, V. R.,et al.
, p. 667 - 678 (2007/10/02)
The cuprate synthesis of the monotetrahydrofuryl-γ-keto ester from 2-methoxycarbonyl-4-trimethylsilyloxy-2-cyclopenten-1-one and the active diastereomer (SS + RR) of 3-(2-tetrahydrofuryloxy)iodooctenol is described.The stereoselectivity of the reaction of the mono- and bistetrahydrofuryl-γ-keto esters with some aluminum- and boron-containing reagents was investigated, and the possibility of the production of the corresponding lactones with good yields was demonstrated.The reaction of the γ-keto esters and lactones with lithium selectride gave the corresponding γ-lactol, which together with the γ-lactones is the basic raw material for the synthesis of prostaglandins.
Regio- and Stereoselectivity of the Reaction between Cyanocuprates and Cyclopentene Epoxides. Application to the Total Synthesis of Prostaglandins
Marino, Joseph P.,Pradilla, Roberto F. de la,Laborde, Edgardo
, p. 4898 - 4913 (2007/10/02)
A systematic study of the reaction between cyclopentene epoxides and alkyl-, alkenyl-, and arylcyanocuprates is described.Alkylcyanocuprates react with complete regio- and stereoselectivity to provide trans-4-alkylcyclopent-2-enols in excellent yields.Vin
Stereocontrolled Synthesis of Prostaglandins from Cyclopentadiene Monoepoxide
Marino, Joseph P.,Pradilla, Roberto Fernandez de la,Laborde, Edgardo
, p. 5279 - 5280 (2007/10/02)
Two complementary syntheses of prostaglandins from the same key intermediate 3, available in four steps from cyclopentadiene monoepoxide, are described.In one approach, a saturated α-chain is introduced via a 1,4-addition of an appropriately functionalized cyanocuprate reagent onto silyl enol ether 3.The resulting prostanoid compound was converted into the bronchodilator 1-decarboxy-1-hydroxymethyl PGE1, PGE1, and PGF1α.The second approach involves the transformation of silyl enol ether 3 into the known prostanoid precursor 11 via selective addition of carbethoxycarbene and subsequent fluoride-induced ring opening of the resulting (silyloxy)cyclopropane carboxylate ester.
Total Synthesis of (+/-)-Prostaglandin E2 Methyl Ester from exo-2-Bromo-endo-3-hydroxybicycloheptan-6-one using Dimethyl-t-butylsilyl Protected Intermediates
Howard, Colin,Newton, Roger F.,Reynolds, Derek P.,Roberts, Stanley M.
, p. 2049 - 2054 (2007/10/02)
Peracetic acid oxidation at -78 deg C of the dihydroxybicyclohepten-6-one (23) afforded the dihydroxylactone (24) which was protected as its bisdimethyl-t-butylsilyl ether (26) and reduced to the corresponding lactol (27).A Wittig reaction on (27), carried out in benzene with a short reaction time, gave mainly the required 11α-silyl ether (28) together with a trace of the 9α-silyl ether (29) which results from 1,5-migration of the silyl group.Oxidation of (28) followed by quantitative deprotection using aqueous HF in acetonitrile afforded (+/-)-PGE2 methyl ester (20).This short stereo- and regioselective total synthesis proceeds in an overall yield of 10percent starting from cyclopentadiene.
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.
