Copper-Catalyzed Formal [4 + 1] Annulation toward Diverse Trifunctionalized Indolizines from Pyridinium 1,4-Zwitterionic Thiolates and Diazos

Liu, Wen; Wang, Hexiang; Zhang, Yuan; Zhao, Limin; Guo, Peijun; Cao, Hua; Liu, Xiang

doi:10.1021/acs.joc.3c00447

J. Org. Chem.

2023

DOI: 10.1021/acs.joc.3c00447

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Copper-Catalyzed Formal [4 + 1] Annulation toward Diverse Trifunctionalized Indolizines from Pyridinium 1,4-Zwitterionic Thiolates and Diazos

Wen Liu

Hexiang Wang

Yuan Zhang

et al.

Abstract: Pyridinium 1,4-zwitterionic thiolates were regarded as powerful and versatile building blocks to prepare nitrogen-and sulfur-containing heterocycles. Herein, we reported a coppercatalyzed formal [4 + 1] annulation of pyridinium 1,4-zwitterionic thiolates and diazo compounds without any additives to access a library of trifunctionalized indolizines in good yields. Besides, isoquinolinium 1,4-zwitterionic thiolates and imidazolium 1,4zwitterionic thiolates were also applied to this formal [4 + 1] annulation reac… Show more

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Cited by 9 publications

References 53 publications

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[(5+1)−1] Cyclization of Nitroepoxides to Pyridinium 1,4‐Zwitterionic Thiolates for the Synthesis of Indolizine Derivatives

Almaani,

Takallou,

Lotfi Nosood

et al. 2024

Adv Synth Catal

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The synthesis of indolizine derivatives was achieved through the reaction of pyridinium 1,4‐zwitterionic thiolates with a diverse array of 2‐methyl‐2‐nitro‐3‐aryloxiranes. Subsequent investigations unveiled a synthetic route to indolizines via a stepwise [(5 + 1) ‐ 1] pathway, with unstable pyridothiazines serving as transient intermediates. DFT calculations elucidated that this transformation entails sequential annulation, deacylation, desulfurization, and oxidation steps.

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[(5+1)−1] Cyclization of Nitroepoxides to Pyridinium 1,4‐Zwitterionic Thiolates for the Synthesis of Indolizine Derivatives

Almaani,

Takallou,

Lotfi Nosood

et al. 2024

Adv Synth Catal

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Recent Advances in the Development of Indolizine Scaffolds: Synthetic Methodology and Mechanistic Insights

Huang,

Li,

et al. 2024

Chin. J. Chem.

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Comprehensive SummaryIndolizine is a nitrogen‐containing heterocycle with strong aromaticity, possessing a delocalized 10π‐electron system. Based on the indolizine scaffolds, numerous molecules with biological activity and organic functional materials have been synthesized. Since 2016, over 110 papers have been published on the synthesis of indolizine scaffolds, but the reviews on synthesizing indolizine scaffolds have been incomplete and not up‐to‐date. Herein, from the perspective of the structure of indolizine with the combination of pyrrole and pyridine ring, we focus on the construction of indolizine scaffolds through the diversity of starting substrates, including pyridine derivatives (N1‐substituted pyridinium salt derivatives, C2‐substituted pyridine derivatives, N1‐ and C2‐free substituted pyridine derivatives), pyrrole derivatives and unoriginal ring substrates. Furthermore, the corresponding reaction mechanisms of synthetic methodologies are also elaborated. Therefore, this review not only paves the way for indolizine synthesis but also provides insight into exploring new reaction modes for constructing nitrogen‐containing heterocycles. Key ScientistsIndolizine was discovered by Angeli in 1890 and first prepared by Scholtz in 1912 from α‐picoline and acetic anhydride. A general approach was developed by Chichibabin in 1927, that is of practical value for the preparation of 2‐alkyl‐ or 2‐arylindolizines. The Chichibabin reaction was the ring closure of quaternary pyridinium halides. At the begining of the 21st century, Basavaiah introduced a new dimension in the Baylis‐Hillman chemistry leading to a novel facile convenient methodology for synthesis of indolizine scaffolds in one‐pot operation. In 2010, Barluenga reported Cu(I)‐catalyzed regioselective [3+2] cyclization of unsubstituted pyridines toward alkenyldiazoacetates leading to functionalized indolizine derivatives, that was the first successful example of metal‐catalyzed cyclization of a π‐deficient heterocyclic system with alkenyldiazo compounds. In 2019 and 2022, Xi and Liu exploited the methods of non‐pyridine derivatives as starting materials to synthesize indolizines, respectively. In 2022, Guo developed an environmentally benign electrooxidative approach for constructing formyl‐ and acyl‐substituted indolizines.

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Recent Advances on the Construction of Functionalized Indolizine and Imidazo[1,2‐a]pyridine Derivatives

Liu,

Fu,

et al. 2024

The Chemical Record

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Indolizines and imidazo[1,2‐a]pyridines are commonly found in natural products, synthetic drugs, and bioactive molecules. These two types of derivatives possess good antibacterial, antiparasitic, anticancer activities, and so on. The functionalization of indolizines and imidazo[1,2‐a]pyridines has always been a hot topic in organic chemistry research and has made significant progress. In recent years, our group has been dedicated to developing diverse synthetic methods for the preparation of such important compounds. 1) We have developed diverse C−H functionalization reactions for efficient modification of the parent indolizines and imidazo[1,2‐a]pyridines. 2) A variety of cycloaddition reactions were established for the construction of indolizine and imidazo[1,2‐a]pyridine derivatives from simple raw materials. 3) We have developed intriguing deconstruction‐functionalization reactions of indolizines, enabling the reorganization of heterocyclic frameworks. This paper outlines our group's latest advancements in constructing structurally diverse indolizine and imidazo[1,2‐a]pyridine derivatives. We hope that this work will offer valuable insights and inspiration for the ongoing research in the field of N‐heterocyclic compounds.

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Copper-Catalyzed Formal [4 + 1] Annulation toward Diverse Trifunctionalized Indolizines from Pyridinium 1,4-Zwitterionic Thiolates and Diazos

Cited by 9 publications

References 53 publications

[(5+1)−1] Cyclization of Nitroepoxides to Pyridinium 1,4‐Zwitterionic Thiolates for the Synthesis of Indolizine Derivatives

[(5+1)−1] Cyclization of Nitroepoxides to Pyridinium 1,4‐Zwitterionic Thiolates for the Synthesis of Indolizine Derivatives

Recent Advances in the Development of Indolizine Scaffolds: Synthetic Methodology and Mechanistic Insights

Recent Advances on the Construction of Functionalized Indolizine and Imidazo[1,2‐a]pyridine Derivatives

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