FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2951657189> ?p ?o ?g. }

• W2951657189 abstract "Tedanolide (1), an 18-membered macrolide, was isolated by Schmitz et al. in 1984 from the Caribbean sponge Tedania ignis and structurally related 13-deoxytedanolide (2) was isolated from a Japanese sea sponge, Mycale adhaerens, by Fusetani et al. in 1991. Both tedanolide (1) and 13-deoxytedanolide (2) exhibit very potent biological activities against certain tumor cell lines. Their complex structures and distinctive biological properties make them extremely attractive targets for synthetic chemists. Recently Kalesse and Smith have reported successful total syntheses of tedanolide (1). As shown in Scheme 1, our retrosynthetic strategy for tedanolide (1) was the disconnection to two subunits 4 and 5 via cleavage at ester C-O bond and the aldol condensation transformation. The subunit 5 was envisioned to be obtained from the coupling between precursors 6 and 7. Herein we disclose our efforts in the construction of the C1-C7 fragment 6 of tedanolide (1). At first stage, we have utilized the Roush protocol as a key methodology toward fragment 6. The synthesis began with the known aldehyde 9. The Roush asymmetric crotylation upon 9 with 10 gave the desired product in 80% yield as a 92:8 mixture of two diastereomers, which was methylated to the methyl ether 11 in good yield. Ozonolysis of 11 furnished aldehyde 12. The second Roush crotylation on 12 did not yield the desired product. Instead we obtained a mixture of diastereomers (Scheme 2). Because of the observed lability of aldehyde 12 during the second crotylation, we considered the modification of the synthetic pathway. As a replacing measurement for the second Roush crotylation, we devised the combined application of Sharpless asymmetric epoxidation and Gilman cuprate reaction. As shown in Scheme 3, we established a highly stereoselective synthesis of precursor 6 via epoxide ring-opening and Mitsunobu reaction. The oxidative cleavage of the terminal vinyl group of 11 followed by immediate HornerWadsworth-Emmons reaction provided α,β-unsaturated ester 15 in 75% yield over two steps (trans:cis = 96:4). Subsequent reduction of ester 15 using DIBAL-H gave the intermediate allylic alcohol and Sharpless epoxidation upon this alcohol with Ti(OPr)4, L-DET and TBHP afforded stereoselectively epoxide 8 in nearly quantitative yield (β/α ≥ 30). Epoxide ring opening of 8 by the treatment with MeLi and CuI furnished the intermediate 1,3-diol (1,3-diol:1,2diol = 88:12) and the exposure of the resulting 1,3-diol to 16 with PPTS yielded p-methoxyphenyl acetal 17 in 70% yield. To introduce the requisite stereochemistry at C2, the" @default.
• W2951657189 created "2019-06-27" @default.
• W2951657189 creator A5000691411 @default.
• W2951657189 creator A5016438715 @default.
• W2951657189 creator A5065517188 @default.
• W2951657189 creator A5079168057 @default.
• W2951657189 date "2008-08-20" @default.
• W2951657189 modified "2023-09-24" @default.
• W2951657189 title "Synthetic Studies on Tedanolide: Stereoselective Synthesis of the C1-C7 Fragment" @default.
• W2951657189 cites W1964660658 @default.
• W2951657189 cites W1970225652 @default.
• W2951657189 cites W1973599436 @default.
• W2951657189 cites W1973651851 @default.
• W2951657189 cites W1981916475 @default.
• W2951657189 cites W1982013879 @default.
• W2951657189 cites W1996051767 @default.
• W2951657189 cites W2000694159 @default.
• W2951657189 cites W2007810628 @default.
• W2951657189 cites W2022287054 @default.
• W2951657189 cites W2027525636 @default.
• W2951657189 cites W2027738744 @default.
• W2951657189 cites W2032402698 @default.
• W2951657189 cites W2041908171 @default.
• W2951657189 cites W2052545303 @default.
• W2951657189 cites W2057186015 @default.
• W2951657189 cites W2058227642 @default.
• W2951657189 cites W2069297028 @default.
• W2951657189 cites W2092063918 @default.
• W2951657189 cites W2094244413 @default.
• W2951657189 cites W2137820971 @default.
• W2951657189 cites W2949551971 @default.
• W2951657189 cites W2949628168 @default.
• W2951657189 cites W2950470427 @default.
• W2951657189 cites W2951052181 @default.
• W2951657189 cites W2951402745 @default.
• W2951657189 cites W2952322301 @default.
• W2951657189 doi "https://doi.org/10.5012/bkcs.2008.29.8.1447" @default.
• W2951657189 hasPublicationYear "2008" @default.
• W2951657189 type Work @default.
• W2951657189 sameAs 2951657189 @default.
• W2951657189 citedByCount "4" @default.
• W2951657189 crossrefType "journal-article" @default.
• W2951657189 hasAuthorship W2951657189A5000691411 @default.
• W2951657189 hasAuthorship W2951657189A5016438715 @default.
• W2951657189 hasAuthorship W2951657189A5065517188 @default.
• W2951657189 hasAuthorship W2951657189A5079168057 @default.
• W2951657189 hasBestOaLocation W29516571891 @default.
• W2951657189 hasConcept C134121241 @default.
• W2951657189 hasConcept C134195300 @default.
• W2951657189 hasConcept C138716334 @default.
• W2951657189 hasConcept C146686406 @default.
• W2951657189 hasConcept C161790260 @default.
• W2951657189 hasConcept C178790620 @default.
• W2951657189 hasConcept C181647583 @default.
• W2951657189 hasConcept C185592680 @default.
• W2951657189 hasConcept C18616679 @default.
• W2951657189 hasConcept C191897082 @default.
• W2951657189 hasConcept C192562407 @default.
• W2951657189 hasConcept C2779825165 @default.
• W2951657189 hasConcept C2780407432 @default.
• W2951657189 hasConcept C61156836 @default.
• W2951657189 hasConcept C71240020 @default.
• W2951657189 hasConceptScore W2951657189C134121241 @default.
• W2951657189 hasConceptScore W2951657189C134195300 @default.
• W2951657189 hasConceptScore W2951657189C138716334 @default.
• W2951657189 hasConceptScore W2951657189C146686406 @default.
• W2951657189 hasConceptScore W2951657189C161790260 @default.
• W2951657189 hasConceptScore W2951657189C178790620 @default.
• W2951657189 hasConceptScore W2951657189C181647583 @default.
• W2951657189 hasConceptScore W2951657189C185592680 @default.
• W2951657189 hasConceptScore W2951657189C18616679 @default.
• W2951657189 hasConceptScore W2951657189C191897082 @default.
• W2951657189 hasConceptScore W2951657189C192562407 @default.
• W2951657189 hasConceptScore W2951657189C2779825165 @default.
• W2951657189 hasConceptScore W2951657189C2780407432 @default.
• W2951657189 hasConceptScore W2951657189C61156836 @default.
• W2951657189 hasConceptScore W2951657189C71240020 @default.
• W2951657189 hasLocation W29516571891 @default.
• W2951657189 hasOpenAccess W2951657189 @default.
• W2951657189 hasPrimaryLocation W29516571891 @default.
• W2951657189 hasRelatedWork W1985762981 @default.
• W2951657189 hasRelatedWork W2004214507 @default.
• W2951657189 hasRelatedWork W2016887597 @default.
• W2951657189 hasRelatedWork W2028166746 @default.
• W2951657189 hasRelatedWork W2031013585 @default.
• W2951657189 hasRelatedWork W2043429898 @default.
• W2951657189 hasRelatedWork W2046007812 @default.
• W2951657189 hasRelatedWork W2063308026 @default.
• W2951657189 hasRelatedWork W2077359941 @default.
• W2951657189 hasRelatedWork W2116111110 @default.
• W2951657189 hasRelatedWork W2157683827 @default.
• W2951657189 hasRelatedWork W2518935719 @default.
• W2951657189 hasRelatedWork W2949967888 @default.
• W2951657189 hasRelatedWork W2950054554 @default.
• W2951657189 hasRelatedWork W2950645361 @default.
• W2951657189 hasRelatedWork W2951352980 @default.
• W2951657189 hasRelatedWork W2951750039 @default.
• W2951657189 hasRelatedWork W2951869175 @default.
• W2951657189 hasRelatedWork W2952444396 @default.
• W2951657189 hasRelatedWork W47458658 @default.

• next