Concise Asymmetric Synthesis of Kweichowenol A

Konrad, David; Kicin, Bilal; Trauner, Dirk

doi:10.1055/s-0037-1610390

Cited by 7 publications

(7 citation statements)

References 19 publications

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“…We have previously developed an asymmetric synthesis of unsaturated aldehydes similar to 3 via a Kiyooka aldol reaction and used it toward kweichowenol A, a polyoxygenated cyclohexene isolated from the plant Uvaria kweichowensis. 34 Although an analogous route gave the aldehyde 3 in sufficient quantities to procced with the synthesis of TTX, we found it more practical and economical to start from the glucose-derived building block 4. All the carbons of glucose and two of its stereocenters would be retained over the course of the synthesis, making this an attractive starting material.…”

Section: Synthetic Designmentioning

confidence: 92%

An Efficient Synthesis of Tetrodotoxin

Konrad

Ruehmann

Ando

et al. 2021

Preprint

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Tetrodotoxin (TTX) is an indispensable probe in neuroscience, a biosynthetic and ecological enigma, and one of the most celebrated targets of synthetic chemistry. Here, we present a stereoselective synthesis of TTX that proceeds in 22 steps starting from a readily available glucose derivative. The central cyclohexane ring of TTX and its α-tertiary amine moiety was established via the intramolecular 1,3-dipolar cycloaddition of a nitrile oxide, followed by alkynyl addition to the resultant isoxazoline. After some carefully chosen protecting group manipulations, a ruthenium-catalyzed hydroxylactonization set the stage for the formation of its dioxa-adamantane core. Installation of the guanidine, oxidation of a primary alcohol, and late-stage epimerization of the resultant aldehyde gave a mixture of TTX and anhydro TTX. Our synthesis represents one of the most effective of TTX reported to date and could give ready access to biologically active derivatives.

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Section: Synthetic Designmentioning

confidence: 92%

An Efficient Synthesis of Tetrodotoxin

Konrad

Ruehmann

Ando

et al. 2021

Preprint

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“…Trauner and co‐workers presented the asymmetric synthesis of kweichowenol A 287 (Scheme 31), [212] a polyoxygenated cyclohexene, extracted from the Chinese medicinal herb Uvaria Kweichowesis . In this synthetic strategy, RCM was one of the key steps and was employed to forge highly oxygenated core.…”

Section: Ring‐closing Metathesis (Rcm)mentioning

confidence: 99%

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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“…2b,10 An alternative way of purification was reported by Trauner and coworker, who performed multiple washing and drying (high vacuum) cycles leading to ketene acetal 8 in a sufficient purity and excellent yield (97%). 12 Scheme 2 Different conditions for the synthesis of ketene acetal 8.…”

Section: Scope Of the Reactionmentioning

confidence: 99%

Chiral Polyoxygenated Tertiary Alcohols through Kiyooka Aldol Reaction

Kalesse

Lücke

2022

Synlett

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Here we present our work on a Kiyooka aldol protocol for the stereoselective synthesis of tertiary alcohols. In the obtained products, three oxygenated carbon atoms that could further be differentiated flank the chiral tertiary alcohol. This methodology can be applied to simple aromatic or aliphatic aldehydes and more complex substrates bearing a chiral center in the α and/or β-position. For complex substrates, an unexpected dependency between stereoselectivity and double bond geometry of the ketene acetal was observed. Furthermore, applications in or towards the synthesis of natural products are presented. 1 Introduction 2 Scope of the reaction 3 Synthetic applications 4 Conclusion

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Concise Asymmetric Synthesis of Kweichowenol A

Cited by 7 publications

References 19 publications

An Efficient Synthesis of Tetrodotoxin

An Efficient Synthesis of Tetrodotoxin

Metathesis Reactions in Natural Product Fragments and Total Syntheses

Chiral Polyoxygenated Tertiary Alcohols through Kiyooka Aldol Reaction

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