Advances in the Total Synthesis of Xanthanolide‐Type Sesquiterpenoids

Lei, Xiaoqiang; Feng, Juan; Liu, Jingchun; Tang, Yefeng

doi:10.1002/asia.201900040

Cited by 6 publications

(5 citation statements)

References 54 publications

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“…Since the total syntheses of xanthanolides have been summarized elsewhere recently, 20 this account will mainly concentrate on some key elements related with the biomimetic Diels-Alder reactions. Initially, we chose to investigate the biomimetic synthesis of 35 through the proposed tandem reaction.…”

Section: Biomimetic Synthesis Of Polycyclic and Dimeric Xanthanolidesmentioning

confidence: 99%

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Biomimetic Diels–Alder Reactions in Natural Product Synthesis: A Personal Retrospect

Tang

Liu

2022

Synlett

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Nature has been recognized for her super capability of constructing complex molecules with remarkable efficiency and elegancy. Among nature’s versatile synthetic toolkits, Diels-Alder reaction is particularly attractive since it allows for rapid generation of molecular complexity from simple precursors. For natural products biosynthetically formed through Diels-Alder reactions, the most straightforward way to access them should build on biomimetic Diels-Alder reactions. However, the implementation of biomimetic Diels-Alder reactions in a laboratory setting may encounter considerable challenges, particularly for those suffering from complicated reactivity and selectivity issues. Indeed, the translation of a biosynthetic hypothesis into a real biomimetic synthesis entails the orchestrated combination of nature’s inspiration and chemist’s rational design. In this account, we will briefly summarize our recent progress on the application of biomimetic Diels-Alder reactions in natural product synthesis. As shown in the discussed stories, rational manipulation of the structures of biosynthetic precursors plays a crucial role for the successful implementation of biomimetic Diels-Alder reactions. 1 Introduction 2 Biomimetic Synthesis of Rossinone B 3 Biomimetic Synthesis of Homodimericin A 4 Biomimetic Synthesis of Polycyclic and Dimeric Xanthanolides 5 Biomimetic Synthesis of Periconiasins and Pericoannosins 6 Biomimetic Synthesis of Merocyctochalasans 7 Conclusion and outlook

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Section: Biomimetic Synthesis Of Polycyclic and Dimeric Xanthanolidesmentioning

confidence: 99%

“…Since the total syntheses of xanthanolides have been summarized elsewhere recently, 20 this Account will mainly concentrate on some key elements related with the biomi-J. Liu et al…”

Section: Biomimetic Synthesis Of Polycyclic and Dimeric Xanthanolidesmentioning

confidence: 99%

Biomimetic Diels–Alder Reactions in Natural Product Synthesis: A Personal Retrospect

Tang

Liu

2022

Synlett

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“…However, the more challenging targets 3−10 had not yet succumbed to total synthesis before we initiated our study. 10 From a synthetic perspective, the most straightforward approach to access 3−10 should build on their biosynthetic pathways. Thus, at the beginning of this study, our major task was to acquire the requisite biosynthetic precursors 1 and 2.…”

Section: ■ Total Synthesis Of Xanthanolidesmentioning

confidence: 99%

“…With 15 as precursor, an array of xanthanolide dimers including pungiolides A, B, E, and L (5−8) were accessed through latestage functionality elaborations. In parallel, 15 readily underwent C-3′ epimerization to give compound 34, which then converted to pungiolides D (9), M (10), and N (35) through intramolecular ene cyclization followed by regioselective oxidation or reduction. Of note, the transformations from 2 to 9 could also be realized in a one-pot fashion (EtOH, 180 °C) in 40% overall yield.…”

Section: ■ Total Synthesis Of Xanthanolidesmentioning

confidence: 99%

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Biomimetic Synthesis of Natural Products: A Journey To Learn, To Mimic, and To Be Better

2021

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Conspectus Total synthesis of natural products has been one of the most exciting and dynamic areas in synthetic organic chemistry. Nowadays, the major challenge in this field is not whether a given target of interest can be synthesized but how to make it with commendable efficiency and practicality. To meet this grand challenge, a wise way is to learn from Mother Nature who is recognized for her superb capability of forging complicated and sometimes beyond-imagination molecules in her own delicate way. Indeed, since Sir Robert Robinson published his groundbreaking synthesis of tropinone in 1917, biomimetic synthesis of natural products, a process of imitating nature’s way to make molecules, has evolved into one of the most popular research directions in organic synthesis. Our group has been engaging in biomimetic synthesis of natural products in the past decade. During this time, we have come to realize that the successful implementation of a biomimetic synthesis entails the orchestrated combination of bioinspiration and rational design. On the one hand, we prefer to utilize some elegant bioinspired transformations (e.g., Diels–Alder dimerization, 6π-electrocyclization, and [2 + 2]-photocycloaddition) as the key steps of our synthesis, which enable rapid construction of the core skeletons of the chased targets with high efficiency; on the other hand, various powerful reactions (e.g., dyotropic rearrangement of β-lactone, tandem aldol condensation/Grob fragmentation reaction, and organocatalytic asymmetric Mukaiyama–Michael addition) are rationally designed by us, which allow for facile access to the requisite precursors for attempting biomimetic transformations. In some cases, the proposed biomimetic transformation may fail to give a satisfactory result in practice, and thus we opt to develop creative tactics (e.g., hydrogen atom transfer-triggered vinyl cyclobutane ring opening/oxygen insertion/cyclization cascade) that can meet the challenge. Guided by this synthesis concept, we have achieved the total syntheses of multiple families of natural products of great importance in both chemistry and biology, representatives of which include xanthanolides, cytochalasans, and plakortin-type polyketides. Of note, most of these targets could be accessed in a concise, efficient, and scalable manner, which paves the way for further exploration of their biological functions and medicinal potential. Moreover, owing to their biomimetic nature, our syntheses provide valuable information for deciphering the underlying biosynthetic pathways of the chased targets, which could not be attained by other synthetic modes.

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Naturally occurring [4 + 2] type terpenoid dimers: sources, bioactivities and total syntheses

Liu

Zhou

2020

Nat. Prod. Rep.

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Advances in the Total Synthesis of Xanthanolide‐Type Sesquiterpenoids

Cited by 6 publications

References 54 publications

Biomimetic Diels–Alder Reactions in Natural Product Synthesis: A Personal Retrospect

Biomimetic Diels–Alder Reactions in Natural Product Synthesis: A Personal Retrospect

Biomimetic Synthesis of Natural Products: A Journey To Learn, To Mimic, and To Be Better

Naturally occurring [4 + 2] type terpenoid dimers: sources, bioactivities and total syntheses

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