Synthesis of 1-(Halo)alkyl-3-heteroaryl Bicyclo[1.1.1]pentanes Enabled by a Photocatalytic Minisci-type Multicomponent Reaction

ACS Catalysis, Год журнала: 2024, Номер 14(8), С. 6247 - 6258

Опубликована: Апрель 10, 2024

Aryl-substituted bicyclo[1.1.1]pentane (BCP-aryl) derivatives represent the most important bioisosteres of biaryl scaffolds and widely exist in numerous complex pharmaceutical molecules. The current synthetic method limitations using only tertiary radical precursors, prefunctionalized heteroarenes, toxic transition metals, expensive photocatalysts make it urgent to develop a more simple practical protocol. To confront enrich Minisci-type chemistry, herein, we disclose photocatalytic multicomponent reaction for synthesis various (halo)alkyl BCP-aryls [1.1.1]propellane, alkyl halides, unfunctionalized heteroarenes as starting materials. Diverse kinds radicals (primary, secondary, carbons) derived from chlorides, bromides, fluoroalkyl iodides are very compatible this transformation. practicability is additionally boosted by product derivatizations late-stage functionalization pharmaceutically relevant mechanistic studies demonstrate that relay mechanism initiated consecutive photoinduced electron transfer (ConPET) process operation. We anticipate methodology would act useful tool biaryl-type drug derivatives, ultimately resulting great utility discovery program.

Язык: Английский

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Strain-release transformations of bicyclo[1.1.0]butanes and [1.1.1]propellanes

Tetrahedron Chem, Год журнала: 2024, Номер 9, С. 100070 - 100070

Опубликована: Фев. 28, 2024

Bicyclo[1.1.0]butanes (BCBs) and [1.1.1]propellanes (tricyclo[1.1.1.01,3]pentanes, TCPs) are structurally unique compounds with different chemical properties. Strain-release driven reactions have emerged as an atom- step-economic strategy for the organic synthesis. Using this strategy, a variety of functional ring molecules been efficiently synthesized, including various cyclobutane molecules, bicyclo[2.1.1]hexanes, bicyclo[1.1.1]pentanes, others. More specifically, these strain release-driven include aspects nucleophilic addition, radical electrophilic or transition metal catalysis. This review will discuss recent developments in strain-release transformations bicyclo[1.1.0]butanes [1.1.1]propellanes.

Язык: Английский

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Paired Electrolysis-Enabled Arylation of Quinoxalin-2(1H)-ones

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(9), С. 6117 - 6125

Опубликована: Апрель 24, 2024

The first paired electrolysis-enabled arylation of quinoxalin-2(1H)-ones was achieved using cyanoarenes as the reagents. A variety 3-arylquinoxalin-2(1H)-ones with various important functional groups were obtained in moderate to good yields under metal- and chemical oxidant-free conditions. With a pair reductive oxidative processes occurring among substrates reaction intermediates, power consumption can be dramatically reduced.

Язык: Английский

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Merging Photoinduced Electron Transfer with Hydrogen Atom Transfer: Formal β-C(sp³)–H Pyridination of Carbonyls

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 9, 2025

In this study, a novel approach that combines photoinduced electron transfer (ET) with hydrogen atom (HAT) has been introduced for the selective β-C(sp3)–H pyridination of carbonyl compounds. This method is notable its absence transition metals and ability to function under benign reaction conditions, resulting in range pyridinated derivatives consistently moderate good yields. The significance technique further underscored by potential late-stage functionalization pharmaceutically significant molecules. Mechanistic investigations confirmed proceeds via radical-mediated pathway.

Язык: Английский

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Multicomponent Synthesis of Alkyl BCP-Heteroaryls via Electron Donor–Acceptor Complex Photoactivation under Mild Conditions

The Journal of Organic Chemistry, Год журнала: 2025, Номер 90(4), С. 1683 - 1696

Опубликована: Янв. 17, 2025

In the vanguard of sustainable chemistry, pursuit efficient pathways for synthesis alkyl bicyclo[1.1.1]pentane-heteroaryls has captured attention scientific vanguard. We herein report a groundbreaking and eco-conscious multicomponent coupling reaction that paves way alkylation heteroarylation [1.1.1]propellane, process uniquely enabled by photochemical prowess an electron donor–acceptor (EDA) complex. This method is distinguished its minimalist yet powerful approach: devoid transition metals, additives, photosensitizers. Its universality further exemplified seamless compatibility broad spectrum halides heteroarenes under standardized conditions, heralding new era synthetic versatility. The method's practicality underscored capacity late-stage modification pharmaceuticals, offering transformative tool enhancement existing drug molecules. Moreover, facile derivatization synthesized products underscores adaptability potential diverse applications. Our mechanistic studies have elucidated underlying radical-relay pathway, pinpointing pivotal role EDA complex in initiating transformation. discovery not only enriches our fundamental understanding but also opens avenues strategic optimization.

Язык: Английский

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Visible-Light-Induced Divergent C–H Esterification/Alkylation of Quinoxalin-2(1H)-ones with Aldehydes under Mild Conditions

Organic Letters, Год журнала: 2025, Номер 27(10), С. 2526 - 2531

Опубликована: Март 5, 2025

Herein, we introduce an efficient and straightforward strategy for the selective C-H esterification alkylation of quinoxalin-2(1H)-ones with aldehydes. A key feature our study is ability to perform both using different types The reaction system highly compatible a range aldehydes, yielding C3-esterified C3-alkylated products in moderate-to-good yields. applicability this approach further enhanced by its scalability through continuous-flow synthesis, late-stage modification significant molecules, product derivatization. Our mechanistic investigations reveal radical relay mechanism, triggered hydrogen atom transfer process.

Язык: Английский

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Energy-transfer photocatalysis for Minisci C–H (amino)alkylation of heteroarenes using oxime esters as dual-role reagents

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(18), С. 5122 - 5129

Опубликована: Янв. 1, 2024

This study demonstrates a strategy involving photoinduced energy transfer for decarboxylative Minisci C–H (amino)alkylation of heteroarenes employing diverse oxime esters (from carboxylic acids) as (amino)alkylating reagents.

Язык: Английский

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A General Approach for the Synthesis of Cyanoisopropyl Bicyclo[1.1.1]pentane (BCP) Motifs by Energy Transfer Process

Organic Letters, Год журнала: 2024, Номер 26(33), С. 7060 - 7065

Опубликована: Авг. 13, 2024

Bicyclo[1.1.1]pentane (BCP) heteroaryls make up an important class of BCP derivatives in drug discovery. Herein, we report the visible-light-mediated synthesis cyanoisopropyl BCP-heteroaryls motifs from

Язык: Английский

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Visible light-mediated ring opening and cyclization of aryl cyclopropanes: efficient synthesis of pyrrolo[1,2-a]quinoxalin-4(5H)-ones with antineoplastic activity

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(6), С. 1758 - 1764

Опубликована: Янв. 1, 2024

This study describes an efficient and green approach for the synthesis of potentially bioactive pyrrolo[1,2- a ]quinoxalin-4(5 H )-ones with appreciable functional group tolerance wide substrate scope.

Язык: Английский

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Transition-metal-, oxidant- and additive-free multi-component synthesis of alkyl heteroaryl BCPs enabled by visible-light-induced phosphine-catalyzed halogen-atom transfer

Organic Chemistry Frontiers, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

This study describes a pioneering visible-light-induced phosphine-catalyzed halogen-atom transfer (XAT) strategy that heralds new era in the difunctionalization of [1.1.1]propellane.

Язык: Английский

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