An Enantiospecific Synthesis of Jiadifenolide

Siler, David A.; Mighion, Jeffrey D.; Sorensen, Erik J.

doi:10.1002/anie.201402335

Cited by 82 publications

(47 citation statements)

References 38 publications

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“…The addition of the stabilized enolate to MVK and annulation under either basic or acidic conditions yields the chiral hydrindenone 71 with a yield ranging from 55 to 82%, depending on the conditions. [77,78] This compound has been used as intermediate for the synthesis of jiadifenolide or (-)-prezizaene which is obtained upon dehydration of (-)-prezizanol. Scheme 24.…”

Section: Pulegonementioning

confidence: 99%

Enantioselective Access to Robinson Annulation Products and Michael Adducts as Precursors

2017

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The Robinson annulation is a reaction that has been useful for numerous syntheses since its discovery in 1935, especially in the field of steroid synthesis. The products are usually obtained after three consecutive steps: the formation of an enolate (or derivative), a conjugate addition, and an aldol reaction. Over the years, several methodological improvements have been made for each individual step or alternative routes have been devised to access the Robinson annulation products. The first part of this Review outlines the most relevant developments towards the formation of monocarbonyl-derived Robinson annulation products (MRA products, MRAPs) and activated monocarbonyl-derived Robinson annulation products (AMRA products, AMRAPs). The following sections are then devoted to the diastereoselective and enantioselective synthesis of these products, while the last section describes the enantiomeric resolution of racemic mixtures.

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Section: Pulegonementioning

confidence: 99%

Enantioselective Access to Robinson Annulation Products and Michael Adducts as Precursors

2017

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“…During their synthesis of jiadifenolide ( 14 ), the Sorensen group arrived at intermediate 12 . [5] Their synthetic approach to fashion the all-carbon quaternary center at C5 was to use diastereotopic group discrimination (Scheme 3). By utilizing a C–H activation protocol developed by Sanford and coworkers, [6] they were able to achieve directed oxidation of the unactivated diastereotopic methyl groups at C5.…”

Section: Simple Diastereotopic Group Selectionmentioning

confidence: 99%

“…In 2015, the Johnson group described a total synthesis of the indole diterpenoid paspaline ( 17 ) which merged local and global desymmetrization strategies (Scheme 4). [7] In the course of the synthesis, intermediate 15 was synthesized by a route that took advantage of enantiotopic group discrimination via a biocatalytic reduction.…”

Section: Simple Diastereotopic Group Selectionmentioning

confidence: 99%

Local Desymmetrization through Diastereotopic Group Selection: An Enabling Strategy for Natural Product Synthesis

Horwitz

Johnson

2017

Eur J Org Chem

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The application of desymmetrization strategies in chemical synthesis has allowed fundamentally new synthetic sequences that efficiently create dense and polyfunctional stereochemical arrays. Enantiotopic group discrimination has become a well-established method of global desymmetrization, while the conceptually unique strategy of local desymmetrization by diastereotopic group discrimination has its own advantages. This microreview focuses on the application of local desymmetrization in natural product synthesis and places a particular emphasis on the efficiency engendered by diastereotopic group discrimination. Local desymmetrization is subdivided into three distinct manifolds; examples under each paradigm are presented and compared.

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“…[77,78] Diese Verbindung wurde als Zwischenprodukt fürd ie Synthese von Jiadifenolid oder (À)-Prezizaen verwendet, das nach Dehydratisierung aus (À)-Prezizanol entstand. Addition des stabilisierten Enolats an MVK und Anellierung unter basischen oder sauren Bedingungen führten zum chiralen Hydrindenon 71 in Ausbeuten von 55 bis 82 %, je nach den Bedingungen.…”

Section: Pulegonunclassified

Enantioselektive Synthese von Robinson‐Anellierungsprodukten und Michael‐Addukten als Vorstufen

Gallier

Martel²,

Dujardin³

2017

Angewandte Chemie

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Die Robinson‐Anellierung hat seit ihrer Entdeckung 1935 in zahlreichen Synthesen Anwendung gefunden, besonders auf dem Gebiet der Steroidsynthese. Die Produkte werden gewöhnlich nach drei aufeinanderfolgenden Stufen erhalten: der Bildung eines Enolats (oder Derivats davon), einer konjugierten Addition und einer Aldolreaktion. Im Laufe der Jahre wurden mehrere methodische Verbesserungen für jede einzelne Stufe vorgenommen oder alternative Synthesewege hin zu Robinson‐Anellierungsprodukten entwickelt. Im ersten Teil dieses Aufsatzes werden die wichtigsten Entwicklungen für die Bildung Monocarbonyl‐abgeleiteter Robinson‐Anellierungsprodukte (MRA‐Produkten, MRAPs) und von einer aktivierten Monocarbonylverbindung abgeleiteter Robinson‐Anellierungsprodukte (AMRA‐Produkten, AMRAPs) erläutert. In den folgenden Abschnitten werden diastereoselektive und enantioselektive Synthesen dieser Produkte beschrieben, und im letzten Abschnitt wird die Racematspaltung von Enantiomerenmischungen dargelegt.

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An Enantiospecific Synthesis of Jiadifenolide

Cited by 82 publications

References 38 publications

Enantioselective Access to Robinson Annulation Products and Michael Adducts as Precursors

Enantioselective Access to Robinson Annulation Products and Michael Adducts as Precursors

Local Desymmetrization through Diastereotopic Group Selection: An Enabling Strategy for Natural Product Synthesis

Enantioselektive Synthese von Robinson‐Anellierungsprodukten und Michael‐Addukten als Vorstufen

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