Recent Strategies in the Nucleophilic Dearomatization of Pyridines, Quinolines, and Isoquinolines

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(3), P. 1122 - 1246

Published: Jan. 2, 2024

Dearomatization reactions have become fundamental chemical transformations in organic synthesis since they allow for the generation of three-dimensional complexity from two-dimensional precursors, bridging arene feedstocks with alicyclic structures. When those processes are applied to pyridines, quinolines, and isoquinolines, partially or fully saturated nitrogen heterocycles formed, which among most significant structural components pharmaceuticals natural products. The inherent challenge lies low reactivity heteroaromatic substrates, makes dearomatization process thermodynamically unfavorable. Usually, connecting event irreversible formation a strong C–C, C–H, C–heteroatom bond compensates energy required disrupt aromaticity. This aromaticity breakup normally results 1,2- 1,4-functionalization heterocycle. Moreover, combination these subsequent tandem stepwise protocols allows multiple heterocycle functionalizations, giving access complex molecular skeletons. aim this review, covers period 2016 2022, is update state art nucleophilic dearomatizations showing extraordinary ability dearomative methodology indicating their limitations future trends.

Language: Английский

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Divergent Synthesis of Sulfur‐Containing Bridged Cyclobutanes by Lewis Acid Catalyzed Formal Cycloadditions of Pyridinium 1,4‐Zwitterionic Thiolates and Bicyclobutanes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: May 31, 2024

Bridged cyclobutanes and sulfur heterocycles are currently under intense investigation as building blocks for pharmaceutical drug design. Two formal cycloaddition modes involving bicyclobutanes (BCBs) pyridinium 1,4-zwitterionic thiolate derivatives were described to rapidly expand the chemical space of sulfur-containing bridged cyclobutanes. By using Ni(ClO

Language: Английский

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Rhodium-Catalyzed Asymmetric Allylic Dearomatization of β-Naphthols with gem-Difluorinated Cyclopropanes

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4287 - 4293

Published: Feb. 25, 2025

Language: Английский

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Recent advances in the dearomative functionalisation of heteroarenes

Chemical Science, Journal Year: 2022, Volume and Issue: 13(48), P. 14213 - 14225

Published: Jan. 1, 2022

This Perspective outlines the myriad of products that can be obtained by dearomatisation and functionalization heteroarene substrates. Complex 3D molecules often prepared in one step from simple arene starting materials.

Language: Английский

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Gd(III)-Catalyzed Regio-, Diastereo-, and Enantioselective [4 + 2] Photocycloaddition of Naphthalene Derivatives

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(25), P. 16982 - 16989

Published: June 13, 2024

Catalytic asymmetric dearomatization (CADA) reactions have evolved into an efficient strategy for accessing chiral polycyclic and spirocyclic scaffolds from readily available planar aromatics. Despite the significant developments, CADA reaction of naphthalenes remains underdeveloped. Herein, we report a Gd(III)-catalyzed naphthalene with PyBox ligand via visible-light-enabled [4 + 2] cycloaddition. This features application Gd/PyBox complex, which regulates reactivity selectivity simultaneously, in excited-state catalysis. A wide range functional groups is compatible this protocol, giving highly enantioenriched bridged polycycles excellent yields (up to 96%) >20:1 chemoselectivity, dr, >99% ee). The synthetic utility demonstrated by 2 mmol scale reaction, removal directing group, diversifications products. Preliminary mechanistic experiments are performed elucidate mechanism.

Language: Английский

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Merging dearomatization with redox-neutral C(sp³)–H functionalization via hydride transfer/cyclization: recent advances and perspectives

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(18), P. 5041 - 5052

Published: Jan. 1, 2022

This review highlights the encouraging advances in hydride transfer-involved dearomatization reaction during past decade, content of which is categorized according to acceptors, namely vinylogous imines and quinone methides.

Language: Английский

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Recent Advances in the Dearomative Skeletal Editing of Mono-azaarenes

Synthesis, Journal Year: 2023, Volume and Issue: 56(01), P. 55 - 70

Published: Jan. 17, 2023

Abstract Despite its challenges, the skeletal editing of mono-azaarenes (pyridines, quinolines, and isoquinolines) has shown unparalleled synthetic utility in construction complex molecules that are difficult to access by conventional methods. In this short review, we summarize three most recently developed strategies for deconstruction azaarene cores, with a focus on their generality, limitations, mechanistic aspects. Also, application strategy total synthesis some important natural products is discussed. 1 Introduction 2 Skeletal Editing Mono-Azaarenes through Zincke-like Reactions 3 Mono-azaarenes Aza-Buchner 4 via Photoinduced Radical or Energy-Transfer Processes 5 Conclusion

Language: Английский

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Palladium-Catalyzed Ligand-Directed Divergent Decarboxylative Cycloadditions of Vinyloxazolidine-2,4-diones with 1,3,5-Triazinanes

Organic Letters, Journal Year: 2024, Volume and Issue: 26(8), P. 1589 - 1594

Published: Feb. 22, 2024

This study demonstrates a highly efficient regiodivergent ligand-controlled palladium-catalyzed cycloaddition reaction of vinyloxazolidine-2,4-diones with 1,3,5-triazinanes. In the presence diphosphine ligand, proceeds via (5+2) pathway to afford 1,3-diazepin-4-ones in excellent yields, while using monophosphine smoothly (3+2) give imidazolidin-4-ones good yields.

Language: Английский

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Skeletal remodeling of chalcone-based pyridinium salts to access isoindoline polycycles and their bridged derivatives

Chemical Science, Journal Year: 2021, Volume and Issue: 12(46), P. 15389 - 15398

Published: Jan. 1, 2021

A novel skeletal remodeling strategy to transform chalcone-based pyridinium salts into structurally intriguing polycyclic isoindolines was achieved through a dearomative ring-opening/ring-closing sequence.

Language: Английский

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Dearomative Periphery Modification of Quinolinium Salts to Assemble Ring-Encumbered Pyrrolidine–Tetrahydroquinoline Polycycles

Organic Letters, Journal Year: 2022, Volume and Issue: 24(10), P. 2008 - 2013

Published: March 10, 2022

We report an unexpected dearomative periphery modification strategy for transforming quinolinium salts into structurally crowded pyrrolidine–tetrahydroquinoline polycyclic systems with complete regio- and diastereoselectivity. Importantly, the reaction pathway was regulated by simply tuning substituents, achieving substituent-directed divergent synthesis. The notable features of this transformation include readily available starting materials, green conditions, a simple workup procedure, high bond- ring-forming efficiency, diverse

Language: Английский

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