Die Totalsynthese von <i>Isodon</i>‐Diterpenen

Lazarski, Kiel E.; Moritz, Benjamin J.; Thomson, Regan J.

doi:10.1002/ange.201404482

Angewandte Chemie

2014

DOI: 10.1002/ange.201404482

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Die Totalsynthese von Isodon‐Diterpenen

Kiel E. Lazarski

Benjamin J. Moritz

Regan J. Thomson

Abstract: Familien strukturell verwandter Verbindungen sind oft interessante Syntheseziele für organische Chemiker, die mit der Entwicklung neuer Methoden und Strategien für die Naturstoffsynthese befasst sind. Diese Synthesearbeiten richten sich zwar normalerweise auf spezifische Verbindungen, führen aber oft auch zu verallgemeinerbaren Konzepten. Historisch gut untersuchte Naturstoffklassen wie die Prostanoide, Indolalkaloide und Makrolidantibiotika bieten ausreichenden Beleg für den bleibenden Wert dieser kollektiven… Show more

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Cited by 30 publications

(1 citation statement)

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“…Not surprisingly, the intriguing architectures of these diterpenoids as well as their potential biological activities have attracted considerable attention from the synthetic community, culminating in many elegant synthetic approaches to these target molecules (see the Supporting Information). [3][4][5][6][7] Despite the significant advances, interconversions of the bicyclooctane subunit of these diterpenoids with satisfactory selectivity and yield are highly sought after. [4d,s] In the course of our ongoing investigations on the biological activities of these molecules, [8] we sought to develop a divergent protocol for the synthesis of these biogenetically related diterpenoids.…”

mentioning

confidence: 99%

Divergent Total Synthesis of Euphoranginol C, Euphoranginone D, ent‐Trachyloban‐3β‐ol, ent‐Trachyloban‐3‐one, Excoecarin E, and ent‐16α‐Hydroxy‐atisane‐3‐one

Zong

Qiao

et al. 2020

Angew Chem Int Ed

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A divergent synthetic approach to biogenetically related diterpenoids such as ent-kauranes, ent-trachylobanes, ent-beyerane, and ent-atisane has been developed. The unified synthetic route involves the De Mayo reaction to rapidly generate the bicyclo[3.2.1]-octane moiety of ent-kaurane. The key reactions also include bioinspired nucleophilic cyclopropanation generating the [3.2.1.0 2,7 ]-tricyclic core of ent-trachylobane and regioselective cyclopropane fragmentation furnishing ent-beyerane and ent-atisane through the nucleophilic attack and protonation of the cyclopropane ring. This strategy enables the asymmetric total syntheses of six diterpenoids from the commercially available geraniol.

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mentioning

confidence: 99%

Divergent Total Synthesis of Euphoranginol C, Euphoranginone D, ent‐Trachyloban‐3β‐ol, ent‐Trachyloban‐3‐one, Excoecarin E, and ent‐16α‐Hydroxy‐atisane‐3‐one

Zong

Qiao

et al. 2020

Angew Chem Int Ed

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Metathesis Reactions in Natural Product Fragments and Total Syntheses

et al. 2022

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The passion of total‐ and fragments syntheses of natural products always remained one of the top priorities among the synthetic chemists worldwide. Due their curiosity toward the complexity of molecules of living nature and their endeavour to imitate them in laboratory; limitless arrays of natural products have been extracted, architecturally‐elucidated, synthesized, and chronicled by utilizing various synthetic methodologies in different fashions. Frequently, the synthesis of complex natural products proceed with inscrutable synthetic challenges, which can be circumvented either by modification of previously developed synthetic methods or by formulating a new one. In this way, a myriad of powerful synthetic reactions have been developed since the genesis of the logic of chemical synthesis. Amongst them, metathesis tactics discovered unexpectedly in the 1950s (Nobel Prize in 2005), have incredibly influenced and changed the landscape of the art of the total and formal synthesis in the last three A. H. Hoveyda, A. R. Zhugralin, me abruptly as compared to other developed transformations or their modified forms. In this particular review article, we envisioned to report a comprehensive detail of the metathetic tools involved in both total and fragments synthesis of natural products in the years 2018 and 2019 along with an overview of 2017.

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Enantioselective Palladium‐Catalyzed Dearomative Cyclization for the Efficient Synthesis of Terpenes and Steroids

Guo

Chen

et al. 2015

Angewandte Chemie

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A novel enantioselective palladium-catalyzed dearomative cyclization has been developed for the efficient construction of a series of chiral phenanthrenone derivatives bearing an all-carbon quaternary center. The effectiveness of this method in the synthesis of terpenes and steroids was demonstrated by a highly efficient synthesis of a kaurene intermediate, the facile construction of the skeleton of the anabolic steroid boldenone, and the enantioselective total synthesis of the antimicrobial diterpene natural product (À)-totaradiol.Tricyclic skeletons bearing chiral all-carbon quaternary centers, such as chiral phenanthrenone derivatives, exist in numerous complex terpenes and steroids with interesting biological activities ( Figure 1). [1] For example, kaurene [2] is the biosynthetic precursor of the plant hormones gibberellins, boldenone [3] is an anabolic steroid, totaradiol [4a-d] is a diterpene natural product that exhibits good antimicrobial properties, and triptoquinone B exhibits a remarkable inhibitory activity against interleukin-1 release. [4e-f] Their syntheses have attracted a great deal of attention with the emergence of various excellent methods. [5] Among them, the asymmetric intramolecular Heck reaction [6] has become a powerful method for constructing chiral polycyclic skeletons bearing all-carbon quaternary centers ( Figure 2). However, a number of synthetic steps are often required either in constructing the olefin moiety necessary for the Heck cyclization or for the post-modification of the Heck product to the target molecule. Alternatively, asymmetric intramolecular dearomative cyclizations [7,8] between two aryl systems can offer better synthetic efficiency owing to the availability of aryl systems as well as the convenience in the post-modification of the cyclization product. Herein, we present a powerful asymmetric palladium-catalyzed dearomative cyclization that has led to a series of chiral phenanthrenone derivatives bearing an allcarbon quaternary center in excellent enantioselectivities. The new method has been successfully applied in the highly efficient synthesis of a chiral kaurene intermediate, the facile construction of the skeleton of the anabolic steroid boldenone, and an enantioselective total synthesis of the diterpene natural product (À)-totaradiol.Although dearomative cyclizations have been frequently applied in natural product synthesis, the asymmetric transition-metal-catalyzed dearomative cyclization has remained underdeveloped, and only a few examples of efficient intramolecular dearomative arylations have been reported thanks to the pioneering work from the Buchwald, [9] Bedford, [10] and You [11] groups. Buchwald [9] and co-workers developed efficient dearomative cyclizations to form chiral benzocarbazole derivatives and spirocyclohexadienones bearing all-carbon quaternary centers. You [11e] et al. recently reported an interesting dearomative cyclization to form a tetracyclic spiroamine framework. However, to the best of our knowledge, enantioselective dearomative...

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Die Totalsynthese von Isodon‐Diterpenen

Cited by 30 publications

References 50 publications

Divergent Total Synthesis of Euphoranginol C, Euphoranginone D, ent‐Trachyloban‐3β‐ol, ent‐Trachyloban‐3‐one, Excoecarin E, and ent‐16α‐Hydroxy‐atisane‐3‐one

Divergent Total Synthesis of Euphoranginol C, Euphoranginone D, ent‐Trachyloban‐3β‐ol, ent‐Trachyloban‐3‐one, Excoecarin E, and ent‐16α‐Hydroxy‐atisane‐3‐one

Metathesis Reactions in Natural Product Fragments and Total Syntheses

Enantioselective Palladium‐Catalyzed Dearomative Cyclization for the Efficient Synthesis of Terpenes and Steroids

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