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

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 90(4), P. 1683 - 1696

Published: Jan. 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.

Language: 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, Journal Year: 2025, Volume and Issue: 27(10), P. 2526 - 2531

Published: March 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.

Language: Английский

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Visible-Light-Induced Energy-Transfer-Mediated Hydrofunctionalization and Difunctionalization of Unsaturated Compounds via Sigma-Bond Homolysis of Energy-Transfer Acceptors

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 1854 - 1941

Published: Jan. 17, 2025

Over the past decade, visible-light-mediated energy-transfer (EnT) catalysis, particularly triplet–triplet (TTEnT) has emerged as a mild and environmentally friendly approach for diverse organic synthetic transformations. In contrast to photoredox which typically requires sacrificial electron donors or acceptors complete catalytic cycle, EnT photocatalysis generally proceeds with high atom economy while minimizing generation of wasteful byproducts. Furthermore, successful catalysis is contingent upon precise control redox potentials both photocatalysts substrates, strategies are primarily influenced by triplet energy compatibility between these entities. Considering growing importance photocatalysis, well hydrofunctionalization difunctionalization reactions in synthesis, this review systematically summarizes significant advancements EnT-enabled unsaturated compounds via sigma-bond homolysis over decade. Special emphasis placed on elucidating substrate scopes mechanistic scenarios. Additionally, discusses versatile applications methodologies addresses current challenges opportunities within evolving research field. This structured into six main categories based different types sigma-bonds undergoing homolysis. These include transformations mediated 1) N–O bond oxime esters other N,O-radical precursors; 2) N–S N-sulfonyl imines N,S-radical 3) chalcogen–chalcogen disulfides oxy/thio/selenosulfonates; 4) C–S tri/difluoromethylated sulfinates, acetylenic triflones, arylsulfonium salts; 5) C–X (X = halogen) halides; 6) acceptors. Through providing theoretical backgrounds along comprehensive overview currently employed acceptors, photosensitizers, contemporary EnT-induced compounds, aims serve an invaluable resource future innovations rapidly

Language: 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, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 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.

Language: Английский

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N-Phenylphenothiazine-based Hyper-cross-linked Polymers for Recyclable, Heterogeneous Photocatalysis of Organic Transformations: A Strategy to Access 6-Difluoromethyl-phenanthridines

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 23, 2025

Herein, a N-phenylphenothiazine-based hyper-cross-linked polymer (PTH-HCP) was finely designed and constructed, which serves as metal-free heterogeneous photocatalyst for organic transformations. Characterization experiments have shown that this demonstrates outstanding stability, extensive surface area, exceptional photoelectric response properties. Moreover, PTH-HCP showed good catalytic efficiency recyclability in the photochemically driven difluoromethylation/cyclization reactions. This work provides strategy design construction of photocatalysts offers support their broad prospects synthetic applications.

Language: Английский

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Synthesis of Nafimidone Derivatives by Visible-Light-Induced α-C—H Functionalization of Carbonyl

Chinese Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 45(2), P. 677 - 677

Published: Jan. 1, 2025

Language: Английский

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Chemodivergent dearomatization of benzene-linked O-oxime esters via EnT-induced radical cross-coupling

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Radical-mediated dearomatization strategies offer a blueprint for building value-added and synthetically valuable three-dimensional skeletons from readily available aromatic starting materials.

Language: Английский

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The Importance of Strain on the Relative Energies of Bridgehead Radicals

Journal of Physical Organic Chemistry, Journal Year: 2025, Volume and Issue: 38(4)

Published: Feb. 21, 2025

ABSTRACT Bridgehead radicals are increasingly commonly‐encountered intermediates in organic chemistry. These carbon‐centered radicals, however, may experience unique strain energies due to pyramidalization at the bridgehead carbon as enforced by bicyclic frameworks. In this study, a series of related were analyzed using G3MP2B3 computational protocol. The adamantyl and cubyl also included study. with reference similarly‐substituted tert ‐butyl radical via hyperhomodesmotic equation. While relative found weakly correlate change carbons upon formation, much stronger correlation was observed difference between saturated compounds corresponding radicals.

Language: Английский

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Photoredox/Copper Cooperatively Catalyzed Arylalkynylation of [1.1.1]Propellane

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 20, 2025

We present a sp2–sp3/sp3–sp bond formation reaction through three-component coupling strategy involving terminal alkynes, [1.1.1]propellane, and aryl thianthrenium salts that are prepared from arenes. The employs dual photo/copper catalysis system provides streamlined approach for assembling 1-alkynyl-3-aryl bicyclo[1.1.1]pentane derivatives with broad spectrum of functional group compatibility. Mechanistic studies suggest the generation radicals copper alkynide intermediates was involved.

Language: Английский

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Photocatalytic Difunctionalization of [1.1.1]Propellane

The Chemical Record, Journal Year: 2025, Volume and Issue: unknown

Published: March 27, 2025

The hunt for new molecular structures to improve the efficacy of biologically active molecules is at forefront pharmaceutical chemistry. So synthetic chemists have always been busy in last few decades synthesizing and testing frameworks which would work as more efficient bioisosteres present bioactive functional groups. In this area, bicyclo[1.1.1]pentane (BCP) framework has identified a promising candidate. It being utilized bioisostere aryl, tert-butyl, alkynes, etc. Now major precursor various BCP derivatives [1.1.1]propellane functionalization drawn widespread attention organic chemist community. Over past two decades, use visible light synthesis rapidly gained popularity, it represents one most approaches aligned with principles green sustainable chemistry, several interesting papers covering photocatalytic difunctionalization also published decade. This particular field really attracted That why we decided compile review article articles related under conditions. Here review, categorized discussed three categories, namely i) without using any catalyst, ii) organocatalysts, iii) metal catalysts deeper understanding key aspects these transformations.

Language: Английский

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