Guaianolides. 2. total synthesis of (±)-compressanolide and (±)-estafiatin

Devreese, A.; Demuynck, M.; Clercq, Pierre J. De; Vandewalle, M.

doi:10.1016/s0040-4020(01)91544-3

Cited by 30 publications

(10 citation statements)

References 15 publications

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“…[391] Weitere Pseudoguaianolide, die auf diese Weise synthetisiert wurden, sind (AE )-Neoambrosin, (AE )-Parthenin, (AE )-Hymenin, [392] (AE )-Carpesiolin [393] und (AE )-Hysterin. [394] Die analoge Reaktionssequenz ausgehend von 1,2-Bis(trimethylsilyloxy)cyclopenten und Cyclopentenon [390] eröffnete den Zugang zur Synthese der Guaianolide (AE )-Compressanolid [395,396] und (AE )-Estafiatin. [396,397] Eine ähnliche formale Totalsynthese von (AE )-Compressanolid nutzte eine oxidative Diolspaltung des [2+2]-Photocycloadditionsprodukts von 1,2-Diacetoxycyclopenten und 3-Methoxycarbonylcyclopent-2-enon nach Entfernung der Acetylgruppen.…”

Section: Sesquiterpens (Ae )-B-himachalen (263) (Abbildung 8)unclassified

“…[394] Die analoge Reaktionssequenz ausgehend von 1,2-Bis(trimethylsilyloxy)cyclopenten und Cyclopentenon [390] eröffnete den Zugang zur Synthese der Guaianolide (AE )-Compressanolid [395,396] und (AE )-Estafiatin. [396,397] Eine ähnliche formale Totalsynthese von (AE )-Compressanolid nutzte eine oxidative Diolspaltung des [2+2]-Photocycloadditionsprodukts von 1,2-Diacetoxycyclopenten und 3-Methoxycarbonylcyclopent-2-enon nach Entfernung der Acetylgruppen. [398] Die Spaltung beider Bindungen a und c (Schema 67) ergibt die formalen Produkte einer Kreuzmetathese.…”

Section: Sesquiterpens (Ae )-B-himachalen (263) (Abbildung 8)unclassified

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Photochemische Reaktionen als Schlüsselschritte in der Naturstoffsynthese

2011

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Photochemische Reaktionen bereichern in signifikanter Weise das Repertoire zur Knüpfung von Kohlenstoff‐Kohlenstoff‐Bindungen und machen ungewöhnliche, auf herkömmlichem Weg nicht erhältliche Molekülgerüste zugänglich. In diesem Aufsatz werden die wichtigsten Umsetzungen der Photochemie vorgestellt, die auf breiter Front Einzug in die Naturstoffsynthese gehalten haben. Beispielhaft werden einzelne Totalsynthesen diskutiert, wobei besonderes Augenmerk auf den photochemischen Schlüsselschritt sowie dessen Stereoselektivität gerichtet ist. Dabei wird das photochemisch erzeugte Molekül in Relation zur Struktur des Naturstoffs gebracht, und Folgereaktionen werden, wo notwendig, illustriert und klassifiziert.

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Section: Sesquiterpens (Ae )-B-himachalen (263) (Abbildung 8)unclassified

Photochemische Reaktionen als Schlüsselschritte in der Naturstoffsynthese

2011

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“…The 1983 publications by Vandewalle et al (described in the next section) [49] largely concern the first total synthesis of the guaianolides (Ϯ)-compressanolide and (Ϯ)-estafiatin. Nevertheless, to the best of our knowledge, the first synthesis of the 4,5-epoxyosmitopsin family, starting from cyclohexane-1,3-dione, was reported in 1980 by Posner.…”

Section: Hydroazulene Strategies By Ring Enlargement or Rearrangementmentioning

confidence: 99%

Trends in the Synthesis and Functionalization of Guaianolides

2015

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Guaianolides constitute a large and diverse group of biologically active sesquiterpenes. Guaianolide and seco‐guaianolides can also be used as, for example, scaffolds for the development of new active molecules that are readily accessible by synthetic methods. Nevertheless, these lactones often have complex structures that make their synthesis difficult. The aim of this microreview is to provide an overview of the developments in guaianolide synthesis by the two major synthetic strategies: semi‐synthesis and total synthesis. Partial and total syntheses of guaianolides are described, with particular emphasis placed on the methods reported in the last decade. The methods discussed include rearrangements, cycloadditions, ring‐closing metathesis, the use of transition‐metal catalysts, photochemical reactions, and other recently developed techniques as key steps.

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“…Folded molecules are epoxidized selectively from the less hindered convex side; m-CPBA epoxidation of the triene lactone (15) takes place from the α-face with 97% stereoselectivity. 20 The triepoxide (16) has been obtained in 74% yield by epoxidizing the corresponding triene; 21 in the epoxidation step, six new chiral centers are introduced stereoselectively as a result of steric effects. Epoxidation of Cyclic Alkenes having Directing Groups.…”

Section: %mentioning

confidence: 99%

“…Henbest showed that in the absence of severe steric interference, allylic cyclohexenols are epoxidized stereoselectively by organic peroxy acids to furnish cis-epoxy alcohols; 24a a large number of cis-epoxy alcohols have been prepared by epoxidizing allylic cyclohexenols. 7 A mixture (5:1) of labile bisallylic alcohols (19) and (20) was reacted with m-CPBA (eq 5); from the reaction mixture diepoxide (21) was isolated as a single isomer. 25 Epoxidation of (Z)-cyclooct-2-en-1-ol (22) Stereoselectivity has been observed during the peroxy acid epoxidation of some homoallylic and bishomoallylic alcohols, 28 and the epoxidation of the allylic carbamate (24) is syn stereoselective (eq 7).…”

Section: %mentioning

confidence: 99%