Study of Cascade Ring-Closing Metathesis Reactions en Route to an Advanced Intermediate of Taxol

Letort, Aurélien; Long, De‐Liang; Prunet, Joëlle

doi:10.1021/acs.joc.6b02264

Cited by 22 publications

(8 citation statements)

References 36 publications

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“…In contrast, the RCM of terminal olefins with alkenes that are geminally disubstituted at their terminus (e.g., the prenyl group) in ruthenium benzylidene catalyzed RCM reactions have limited literature precedent. − While these examples have shown that such olefin combinations are possible in RCM reactions, the prenyl grouping is most often employed as a matter of synthetic expediency to derive the RCM substrate from readily available terpene building blocks , or in RCM reactions demonstrated directly on monoterpenes . It has also been employed as a rational design feature to direct initiation to another olefin, ,, and it has certainly been noted that the prenyl group functions surprisingly well in selected RCM reactions. ,, However, to the best of our knowledge, there have been no direct kinetic comparison of RCM reactions using acyclic dienes with terminal alkenes versus an acyclic diene where one of the alkenes is now geminally disubstituted at its terminus. Herein, we report on such activities, and experimentally demonstrate that prenyl groups are excellent acceptor olefins in ring-closing metatheses.…”

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confidence: 99%

Kinetic Benchmarking Reveals the Competence of Prenyl Groups in Ring-Closing Metathesis

et al. 2017

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A series of prenyl-containing malonates are kinetically benchmarked against the standard allyl-containing congeners using a ruthenium benzylidene precatalyst for ring-closing metatheses. The prenyl grouping is found to be a superior acceptor olefin compared to an allyl group in RCM processes with ruthenium alkylidenes derived from terminal alkenes. The prenyl group is also found to be a highly competent acceptor for a ruthenium alkylidene derived from a 1,1-disubstituted olefin in a RCM process.

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confidence: 99%

Kinetic Benchmarking Reveals the Competence of Prenyl Groups in Ring-Closing Metathesis

et al. 2017

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“…Taxol, one of the most famous anticancer drugs, is among the blockbuster drugs together with its derivatives and to be an attractive synthetic target (Mendoza et al, 2012). Prunet's group (Letort et al, 2016;Ma et al, 2016) investigated the synthesis of taxane and isotaxane derivatives, during which the tricyclic carbocycles were constructed via domino RCM of ene-yne-ene substrates. In the next year, Oterofraga and Granja (2017) reported one-step assembly of a taxanelike skeleton from an ene-yne-yne-ene substrate.…”

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 their study en route to an advanced intermediate of taxol, 55 the same authors succeeded in assembling the metathesis precursor 65, endowed with a protected hydroxy group at C7. The dienyne RCM turned out to be very challenging, since the presence of a substituent at C7 favored the formation of undesired RCM bicyclic products of type 62 rather than the tricyclic core of taxol.…”

Section: Scheme 17 Preparation Of Taxol-type Carbocyclic Systems Via mentioning

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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Study of Cascade Ring-Closing Metathesis Reactions en Route to an Advanced Intermediate of Taxol

Cited by 22 publications

References 36 publications

Kinetic Benchmarking Reveals the Competence of Prenyl Groups in Ring-Closing Metathesis

Kinetic Benchmarking Reveals the Competence of Prenyl Groups in Ring-Closing Metathesis

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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