Concise gram-scale synthesis of Euphorikanin A skeleton through a domino ring-closing metathesis strategy

Shi, Linlin; He, Yingdong; Gong, Jianxian; Yang, Zhen

doi:10.1039/c9cc08830j

Cited by 18 publications

(12 citation statements)

References 49 publications

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“…The intriguing and complex molecular scaffold as well as potential bioactivities of 1 make it an attractive target for total synthesis. In 2020, Yang, Gong and co‐workers reported the synthesis of the 5/6/7/3‐fused tetracyclic skeleton through a domino ring‐closing metathesis strategy [5] . In 2021, Carreira's group reported the first, and thus far, the only total synthesis of 1 via a key SmI 2 ‐mediated ketyl‐enoate reaction [6] .…”

Section: Methodsmentioning

confidence: 99%

“…In 2020, Yang, Gong and co-workers reported the synthesis of the 5/6/7/3-fused tetracyclic skeleton through a domino ring-closing metathesis strategy. [5] In 2021, Carreira's group reported the first, and thus far, the only total synthesis of 1 via a key SmI 2 -mediated ketylenoate reaction. [6] In connection with our ongoing studies towards the total synthesis of structurally complex natural products, we have achieve the total synthesis of some natural products by employing biomimetic synthetic strategy.…”

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confidence: 99%

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Bioinspired Total Synthesis of (+)‐Euphorikanin A

2022

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We have achieved a bioinspired total synthesis of (+)-euphorikanin A, which possesses an intriguing and complex 5/6/7/3-fused tetracyclic skeleton bearing a bridged [3.2.1]-γ-lactone moiety. Key transformations include stereoselective alkylation and aldol condensation to install the main stereocenters, an intramolecular nucleophile-catalyzed aldol lactonization of carboxylic acid-ketone to assemble the five-membered ring, a McMurry coupling to construct the seven-membered ring, and a biomimetic benzilic acid type rearrangement to form the bridged [3.2.1]-γ-lactone moiety.

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Section: Methodsmentioning

confidence: 99%

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confidence: 99%

Bioinspired Total Synthesis of (+)‐Euphorikanin A

2022

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“…Also, direct transformation of this tetracyclic product to the final target is failed, as the double bond in the seven-membered ring is more reactive, which needs additional steps for protection and deprotection. Very recently, the group of Gong and Yang (Shi et al, 2020) employed a similar strategy for rapid construction of tricyclic scaffold up to gram scale ( Figure 2B). The 5/6/7/3-fused tetracyclic ring skeleton of euphorikanin A can be built by further elaboration, but the final total synthesis is impeded during the final lactone formation step.…”

Section: Construction Of Polycyclic Carbocyclesmentioning

confidence: 99%

Recent Advances in Construction of Polycyclic Natural Product Scaffolds via One-Pot Reactions Involving Alkyne Annulation

Zheng

Hua

2020

Front. Chem.

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Polycyclic scaffolds are omnipresent in natural products and drugs, and the synthetic strategies and methods toward construction of these scaffolds are of particular importance. Compared to simple cyclic ring systems, polycyclic scaffolds have higher structure complexity and diversity, making them suitable for charting broader chemical space, yet bringing challenges for the syntheses. In this review, we surveyed progress in the past decade on synthetic methods for polycyclic natural product scaffolds, in which the key steps are one-pot reactions involving intermolecular or intramolecular alkyne annulation. Synthetic strategies of selected polycyclic carbocycles and heterocycles with at least three fused, bridged, or spiro rings are discussed with emphasis on the synthetic efficiency and product diversity. Recent examples containing newly developed synthetic concepts or toolkits such as collective and divergent total synthesis, gold catalysis, C-H functionalization, and dearomative cyclization are highlighted. Finally, several "privileged synthetic strategies" for "privileged polycyclic scaffolds" are summarized, with discussion of remained challenges and future perspectives.

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“…In very recent work, Yang and co-workers envisioned the synthesis of its core skeleton 105 by performing a RCDEYM reaction of dienyne 104 (Scheme 23, B). 62 This compound, carrying the required stereogenic center on its 7,3-ring, was stereoselectively prepared in seven steps and 13% overall yield starting from commercially available (+)-3-carene. The domino ring-closing metathesis process on 104 by employing G2 (7.5 mol%) in DCM gave the desired tetracyclic derivative 105 in 88% yield.…”

Section: Review Synthesismentioning

confidence: 99%

Recent Advances in One-Pot Enyne Metathesis Processes for the Preparation of Biologically and Medicinally Relevant Compounds

Bernardi

Colombo²,

Serra³

2020

Synthesis

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Enyne metathesis reactions are powerful tools for the preparation of a wide range of synthetic and natural chemical substances with increasing efficiency and environmental sustainability. The driving force of the reaction is the formation of a stable conjugated system, i.e., a diene, which through further functionalization steps can be used for the construction of skeletally complex molecular architectures. These concepts are exploited to design cascade reaction sequences, where multiple rings can be formed in a one-pot fashion by combining metathetic protocols with various chemical transformations. The strong correlation between synthetic organic chemistry and medicinal chemistry prompted us to review the most notable approaches for the synthesis of biologically relevant compounds via enyne metathesis-based one-pot processes. With the aim to provide a modern and practical overview, by taking into consideration the scientific literature on this topic, we have focused the majority of our attention on the research performed in the last decade. This review covers the literature from 2003 to 2020.1 Introduction2 Ethylene-Mediated Processes3 RCEYM/CM and CEYM/RCM Processes4 Enyne Metathesis/Diels–Alder-Based Processes5 RCM of Dienynes6 RCM of Tethered Dienynes7 Relay Metathesis8 Ring-Rearrangement Metathesis9 RCEYM/Transition-Metal-Catalyzed C–C Bond-Forming Processes10 Conclusions11 List of Acronyms

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Concise gram-scale synthesis of Euphorikanin A skeleton through a domino ring-closing metathesis strategy

Abstract: Euphorikanin A is a diterpenoid possessing a highly congested and unprecedented 5/6/7/3-fused tetracyclic ring skeleton.

Cited by 18 publications

References 49 publications

Bioinspired Total Synthesis of (+)‐Euphorikanin A

Bioinspired Total Synthesis of (+)‐Euphorikanin A

Recent Advances in Construction of Polycyclic Natural Product Scaffolds via One-Pot Reactions Involving Alkyne Annulation

Recent Advances in One-Pot Enyne Metathesis Processes for the Preparation of Biologically and Medicinally Relevant Compounds

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