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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Heterogeneous g-C₃N₄/NaI Dual Catalytic Difunctionalization of Alkenes with Heteroarenes and Methyl Carbazate under Visible Light

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

Published: April 26, 2025

Herein, a photoinduced heterogeneous catalytic system merging g-C3N4 and NaI has been established for the difunctionalization of alkenes in conjunction with heteroarenes methyl carbazate. This approach is notable its broad substrate tolerance, encompassing wide range leading to formation corresponding esters moderate good yields. Additionally, scalability synthetic process versatility product transformations have illustrated, highlighting potential practical application organic synthesis.

Language: Английский

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A Mechanistic Perspective on Photocatalytic EnT-Enabled C3-N-Heteroarylation of Aryl Quinoxaline via C(sp²)–C(sp²) Coupling

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

Published: April 11, 2025

An EnT-mediated C3-N-heteroarylation of 2-aryl quinoxalines via decarboxylative radical-radical cross-coupling (C(sp2)-C(sp2)) with oxime esters is presented. Upon photoactivation, the triplet energy photocatalyst transferred to both reacting partners (oxime ester and 2-phenylquinoxaline). The excited undergoes fragmentation a C-centered N-heteroaryl radical an N-centered imine radical. former attacks C3 site quinoxaline diradical, while latter acts as hydrogen atom abstractor (HAA). Computational studies revealed that C-C bond formation heteroaryl energetically more favorable than C-N formation.

Language: Английский

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Visible-Light-Mediated Perfluoroalkylation/Thioetherification of [1.1.1]Propellane under Photocatalyst-Free Conditions

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

Published: May 29, 2025

Perfluoroalkyl-functionalized bicyclo[1.1.1]pentane (BCP) derivatives have garnered significant attention in pharmaceuticals due to their special physicochemical property; however, establishing convenient synthetic protocols for these fluorinated molecular frameworks continues present substantial methodological challenges. Herein, we report a photocatalyst and additive-free perfluoroalkylation/thioetherification of [1.1.1] propellane with disulfide ether perfluoroalkyl iodines. Such photochemistry methodology utilizing an electron donor-acceptor (EDA) complex offers green novel way obtain various BCP containing thioether groups good functional group tolerance.

Language: Английский

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