Synthesis of the four stereoisomers of enprostil

Cooper, Gary F.; Wren, D. L.; Jackson, David Y.; Beard, Colin C.; Galeazzi, E.; Horn, A. R. Van; Li, Tsung T.

doi:10.1021/jo00068a023

Cited by 16 publications

(3 citation statements)

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“…Chiral allenes gained significant importance as versatile intermediates for asymmetric synthesis via the axial to centered chirality transfer . Recently chiral allenes are explored as potential chiral synthons in the synthesis of bioactive molecules and natural products. 1n,s, The S N 2‘ addition of nucleophiles to suitably derivatized, optically active propargyl derivatives is one of the most widely used routes for the asymmetric synthesis of chiral allenes. 1e,, In conjunction with our program to develop a general, simple and efficient means of synthesizing chiral allenes for further usage in organic synthesis, we report herein a substrate-controlled asymmetric synthesis of camphor-derived chiral allenes and the stereochemical course of their hydroboration−oxidation reactions.…”

Section: Introductionmentioning

confidence: 99%

A Highly Diastereoselective Synthesis of (1R)-(+)-Camphor-Based Chiral Allenes and Their Asymmetric Hydroboration−Oxidation Reactions

et al. 2002

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Synthesis of camphor derived chiral allenes and their hydroboration-oxidation reactions are described. Reaction of (1R)-(+)-camphor with alkynyllithium followed by the reduction of the resulted propargyl alcohol derivatives using AlH3 furnished chiral allenes 2a-g in excellent yields with high diastereoselectivity. Reduction of the propargyl alcohols with aluminum hydride proceeded through selective intermolecular anti-addition of hydride ion. The stereochemistry of the chiral allenes 2 was assigned based on lanthanide shift studies and chemical correlations. Diastereoselectivity was observed in the hydroboration-oxidation of 2 which produced a mixture of (E,R) and (E,S) stereoisomers in a ratio of 6:1 to 18:1.

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Section: Introductionmentioning

confidence: 99%

A Highly Diastereoselective Synthesis of (1R)-(+)-Camphor-Based Chiral Allenes and Their Asymmetric Hydroboration−Oxidation Reactions

et al. 2002

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“…The proposed catalytic cycle of the enantioselective synthesis of allenes are presented in Scheme 9. The S N 2' addition of nucleophiles to suitably derivatized, optically active propargylic ethers is among the most direct route to the enantiomerically enriched allenes required for asymmetric synthesis [70]. Alkyne-substituted -lactones were subject to S N 2' nucleophilic addition analogous to that observed for activated propargylic alcohols, rendering these lactones as complimentary precursors to allene derivatives.…”

Section: Ir (Cm-1) C=c=cmentioning

confidence: 99%

Recent Progress in the Chemistry of Allenes

Hassan

2007

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Allenes are important compounds in organic and synthetic organic chemistry and therefore a large number of studies on their synthesis and reactions have been reported so far. We report the most recent methods for the synthesis of allenes, including optically active forms and fluorinated and gem-difluorinated allenes, in this paper. Reactions such as nucleophilic addition of allenes were classified and discussed in details according to the nature of the nucleophile either oxygen, nitrogen, carbon or sulfur, whereas, inter-and intra-molecular cycloadditions reactions with a variety of unsaturated functionality were separately discussed. A collection of some useful reactions such as coupling reactions of allenes mediated by organometallic reagents, intramolecular cyclization of allenes with tethered amines, asymmetric dihydroxylation, and epoxidation of allenes are also included.

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“…Die selektive Synthese der vier Stereoisomere von Enprostil gelang schließlich Cooper und Mitarbeitern125a mithilfe einer Orthoester‐Claisen‐Umlagerung (Schema ): Durch Acetylidaddition an den Aldehyd 112 erhielten sie ein 3:2‐Gemisch der epimeren Propargylalkohole 113 a und 113 b , die chromatographisch voneinander getrennt und durch syn ‐stereoselektive Claisen‐Umlagerung in 114 a bzw. 114 b umgewandelt wurden.…”

Section: Pharmakologisch Aktive Alleneunclassified

Synthese und Eigenschaften allenischer Natur‐ und Wirkstoffe

2004

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Heute sind etwa 150 Naturstoffe mit Allen‐ oder Cumulen‐Struktur bekannt. Die Chemie dieser Verbindungen hat sich als ein reizvolles und fruchtbares Gebiet erwiesen: Fortschritte in der Isolierung und Charakterisierung neuer allenischer Naturstoffe haben zur Etablierung effizienter Syntheseverfahren geführt, die häufig einen Zugang zu enantiomerenreinen Produkten eröffneten. Wegen der oftmals beeindruckenden biologischen Eigenschaften allenischer Naturstoffe sind Allengruppierungen mittlerweile systematisch in pharmakologisch aktive Verbindungsklassen (Steroide, Prostaglandine, Aminosäuren, Nucleoside) eingebaut worden. Diese funktionalisierten Allene weisen in vielen Fällen interessante Aktivitäten auf, beispielsweise als Mechanismus‐inhärente Enzyminhibitoren, Cytostatika oder antivirale Wirkstoffe. Eine grundlegende Voraussetzung für weitere Entwicklungen auf diesem Gebiet ist die effiziente stereoselektive Synthese von Allenderivaten.

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Synthesis of the four stereoisomers of enprostil

Cited by 16 publications

References 0 publications

A Highly Diastereoselective Synthesis of (1R)-(+)-Camphor-Based Chiral Allenes and Their Asymmetric Hydroboration−Oxidation Reactions

A Highly Diastereoselective Synthesis of (1R)-(+)-Camphor-Based Chiral Allenes and Their Asymmetric Hydroboration−Oxidation Reactions

Recent Progress in the Chemistry of Allenes

Synthese und Eigenschaften allenischer Natur‐ und Wirkstoffe

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