Isocanthine Synthesis via Rh(III)-Catalyzed Intramolecular C–H Functionalization

Chen, Anthony Y.; Lü, Qianqian; Fu, Yao; Sarpong, Richmond; Stoltz, Brian M.; Zhang, Haiming

doi:10.1021/acs.joc.7b02731

Cited by 15 publications

(8 citation statements)

References 43 publications

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“…In 2017, the group of Zhang and Fu reported a related approach to access substituted isocanthines, a class of tetracyclic γ‐carbolines possessing important clinical use to treat cardiovascular diseases and CNS disorders, among others (Scheme ) . The reaction relied on the formation of indole tert ‐butylimine intermediates in the presence of t BuNH 2 (Conditions B).…”

Section: Intramolecular Coupling With Alkynesmentioning

confidence: 99%

Recent Advances in [Cp*M^III] (M = Co, Rh, Ir)‐Catalyzed Intramolecular Annulation Through C–H Activation

2018

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This review aims to summarize the recent advances in the field of Cp*MIII (Co, Rh, Ir)‐catalyzed C–H activation followed by subsequent intramolecular reaction. This approach has allowed the synthesis of valuable heterocycles with high structural diversity and complexity, including polycyclic and macrocyclic compounds. In this review, a particular attention has been made to the nature of the coupling partner (alkene, alkyne, etc) and its connection either to the aryl (or vinyl) group or to the directing group. Hence, different types of transformation can occur, involving one or two cyclizations depending on the nature of the directing group. Finally, we discuss some mechanistical aspects (role of the external or internal oxidation, etc) to account for the formation of the cyclic structures.

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Section: Intramolecular Coupling With Alkynesmentioning

confidence: 99%

Recent Advances in [Cp*M^III] (M = Co, Rh, Ir)‐Catalyzed Intramolecular Annulation Through C–H Activation

2018

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“…demonstrated an effective amalgamation of substituted isocanthines utilizing an intramolecular Rh(III)‐ catalyzed C−H functionalization of alkyne‐tethered indoles within the sight of stoichiometric copper(II) acetate and catalytic tris(acetonitrile)pentamethylcyclopentadienyl rhodium‐(III) hexafluoroantimonate (Scheme 79). This isocanthine synthesis endures an assortment of electronically distinct 5‐ or 6‐substituted indoles with N‐tethered alkyne coupling associates and can likewise be reached out to pyrrole derivatives for the construction of annulated 5‐azaindoles [88] …”

Section: C−h Functionalization Of Pyrrolesmentioning

confidence: 99%

Recent Advances in Functionalization of Pyrroles and their Translational Potential

Hunjan

Panday

Gupta

et al. 2021

The Chemical Record

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Among the known aromatic nitrogen heterocycles, pyrrole represents a privileged aromatic heterocycle ranging its occurrence in the key component of “pigments of life” to biologically active natural products to active pharmaceuticals. Pyrrole being an electron‐rich heteroaromatic compound, its predominant functionalization is legendary to aromatic electrophilic substitution reactions. Although a few excellent reviews on the functionalization of pyrroles including the reports by Baltazzi in 1963, Casiraghi and Rassu in 1995, and Banwell in 2006 are available, they are fragmentary and over fifteen years old, and do not cover the modern aspects of catalysis. A review covering a comprehensive package of direct functionalization on pyrroles via catalytic and non‐catalytic methods including their translational potential is described. Subsequent to statutory yet concise introduction, the classical functionalization on pyrroles using Lewis acids largely following an ionic mechanism is discussed. The subsequent discussion follows the various metal‐catalyzed C−H functionalization on pyrroles, which are otherwise difficult to implement by Lewis acids. A major emphasize is given on the radical based pyrrole functionalization under metal‐free oxidative conditions, which is otherwise poorly highlighted in the literature. Towards the end, the current development of pyrrole functionalization under photocatalyzed and electrochemical conditions is appended. Only a selected examples of substrates and important mechanisms are discussed for different methods highlighting their scopes and limitations. The aromatic nucleophillic substitution on pyrroles (being an electron‐rich heterocycle) happened to be the subject of recent investigations, which has also been covered accentuating their underlying conceptual development. Despite great achievements over the past several years in these areas, many challenges and problems are yet to be solved, which are all discussed in summary and outlook.

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“…In 2018, Zhang and co-workers (Chen A. Y. et al, 2018) reported an efficient synthesis of isocanthines using a similar intramolecular strategy ( Figure 5B). The reaction proceeds in a one-pot two-stage fashion.…”

Section: Construction Of Polycyclic Heterocycles Fused Pyridines and mentioning

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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Isocanthine Synthesis via Rh(III)-Catalyzed Intramolecular C–H Functionalization

Cited by 15 publications

References 43 publications

Recent Advances in [Cp*M^III] (M = Co, Rh, Ir)‐Catalyzed Intramolecular Annulation Through C–H Activation

Recent Advances in [Cp*M^III] (M = Co, Rh, Ir)‐Catalyzed Intramolecular Annulation Through C–H Activation

Recent Advances in Functionalization of Pyrroles and their Translational Potential

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

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Isocanthine Synthesis via Rh(III)-Catalyzed Intramolecular C–H Functionalization

Cited by 15 publications

References 43 publications

Recent Advances in [Cp*MIII] (M = Co, Rh, Ir)‐Catalyzed Intramolecular Annulation Through C–H Activation

Recent Advances in [Cp*MIII] (M = Co, Rh, Ir)‐Catalyzed Intramolecular Annulation Through C–H Activation

Recent Advances in Functionalization of Pyrroles and their Translational Potential

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

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Product

Resources

About

Recent Advances in [Cp*M^III] (M = Co, Rh, Ir)‐Catalyzed Intramolecular Annulation Through C–H Activation

Recent Advances in [Cp*M^III] (M = Co, Rh, Ir)‐Catalyzed Intramolecular Annulation Through C–H Activation