Synthetic reactions driven by electron-donor–acceptor (EDA) complexes

Beilstein Journal of Organic Chemistry, Год журнала: 2021, Номер 17, С. 771 - 799

Опубликована: Апрель 6, 2021

The reversible, weak ground-state aggregate formed by dipole–dipole interactions between an electron donor and acceptor is referred to as electron-donor–acceptor (EDA) complex. Generally, upon light irradiation, the EDA complex turns into excited state, causing transfer give radicals initiate subsequent reactions. Besides external energy source, reactions involving participation of complexes are mild, obviating transition metal catalysts or photosensitizers in majority cases line with theme green chemistry. This review discusses synthetic concerned well mechanisms that have been shown over past five years.

Язык: Английский

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Generation of non-stabilized alkyl radicals from thianthrenium salts for C–B and C–C bond formation

Nature Communications, Год журнала: 2021, Номер 12(1)

Опубликована: Июль 26, 2021

Abstract Sulfonium salts bearing a positively charged sulfur atom with three organic substituents have intrigued chemists for more than century their unusual structures and high chemical reactivity. These compounds are known to undergo facile single-electron reduction emerge as valuable alternative source of aryl radicals synthesis. However, the generation non-stabilized alkyl from sulfonium has been challenge several decades. Here we report treatment S -(alkyl) thianthrenium generate key intermediates granting controlled selective outcome ensuing reactions under mild photoredox conditions. The value these reagents demonstrated through efficient construction alkylboronates other transformations, including heteroarylation, alkylation, alkenylation, alkynylation. developed method is practical, provides opportunity convert C–OH bond C–B C–C bonds.

Язык: Английский

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Synthesis of Polysubstituted 2-Oxabicyclo[2.1.1]hexanes via Visible-Light-Induced Energy Transfer

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(44), С. 20207 - 20213

Опубликована: Окт. 27, 2022

Synthesis of bicyclic scaffolds has attracted growing interest because they are high importance in modern pharmaceutical development. Here we report a strategy to access polysubstituted 2-oxabicyclo[2.1.1]hexanes single operation from readily accessible benzoylformate esters and bicyclo[1.1.0]butanes via visible-light-induced triplet energy transfer catalysis. The process is proposed involve formal [2π + 2σ] photocycloaddition/backbone C-H abstraction/aryl group migration sequence. A diverse range (hetero)aryl groups successfully underwent the backbone (C2) position provide previously inaccessible molecules, ester product can serve as handle for downstream manipulation, thus offering opportunities rapidly build up molecular complexity new sp3-rich chemical space.

Язык: Английский

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Photoactive electron donor–acceptor complex platform for Ni-mediated C(sp³)–C(sp²) bond formation

Chemical Science, Год журнала: 2021, Номер 12(15), С. 5450 - 5457

Опубликована: Янв. 1, 2021

This works demonstrates the implementation of an electron donor–acceptor (EDA) complex platform toward Ni-catalyzed C(sp³)–C(sp²) bond formation, circumventing need for exogenous photocatalysts, additives, and stoichiometric metal reductants.

Язык: Английский

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Photochemical radical cyclization reactions with imines, hydrazones, oximes and related compounds

Chemical Society Reviews, Год журнала: 2021, Номер 50(13), С. 7418 - 7435

Опубликована: Янв. 1, 2021

Photochemical reactions of imines, hydrazones, oximes and related compounds provides an efficient access to radical intermediates in the synthesis heterocycles.

Язык: Английский

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