Chinese Chemical Letters, Год журнала: 2025, Номер unknown, С. 111224 - 111224
Опубликована: Апрель 1, 2025
Язык: Английский
ACS Catalysis, Год журнала: 2023, Номер 13(24), С. 15991 - 16011
Опубликована: Ноя. 28, 2023
Carbon dioxide radical anion (CO2•–) is a highly reactive nucleophilic species that has recently emerged in organic chemistry as strong single electron donor (reductant) and reactant for the synthesis of carboxylic acids. In general, CO2•– can be generated by either direct reduction CO2 or HAT formate salts. Achievements reactions involving have been witnessed recent years. This Review summarizes advances highlighting some challenges identifying potential areas improvement, which may offer inspiration future studies.
Язык: Английский
Процитировано
58
Science, Год журнала: 2024, Номер 386(6717), С. 99 - 105
Опубликована: Окт. 3, 2024
The identity of a heteroatom within an aromatic ring influences the chemical properties that heterocyclic compound. Systematically evaluating effect single atom, however, poses synthetic challenges, primarily as result thermodynamic mismatches in atomic exchange processes. We present photocatalytic strategy swaps oxygen atom furan with nitrogen group, directly converting into pyrrole analog intermolecular reaction. High compatibility was observed various derivatives and nucleophiles commonly used drug discovery, late-stage functionalization furnished otherwise difficult-to-access pyrroles from naturally occurring furans high molecular complexity. Mechanistic analysis suggested polarity inversion through electron transfer initiates redox-neutral processes at room temperature.
Язык: Английский
Процитировано
19
Chemical Society Reviews, Год журнала: 2023, Номер 53(1), С. 263 - 316
Опубликована: Дек. 7, 2023
The employment of light and/or electricity - alternatively to conventional thermal energy unlocks new reactivity paradigms as tools for chemical substrate activations. This leads the development synthetic reactions and a vast expansion spaces. review summarizes recent developments in photo- electrochemical activation strategies functionalization strong bonds particularly carbon-heteroatom (C-X)
Язык: Английский
Процитировано
43
Science Bulletin, Год журнала: 2023, Номер 68(24), С. 3124 - 3128
Опубликована: Ноя. 8, 2023
Язык: Английский
Процитировано
37
Molecules, Год журнала: 2023, Номер 28(16), С. 6127 - 6127
Опубликована: Авг. 18, 2023
The functionalisation of C–H bonds has been an enormous achievement in synthetic methodology, enabling new retrosynthetic disconnections and affording simple equivalents for synthons. Hydrogen atom transfer (HAT) is a key method forming alkyl radicals from substrates. Classic reactions, including the Barton nitrite ester reaction Hofmann–Löffler–Freytag reaction, among others, provided early examples HAT. However, recent developments photoredox catalysis electrochemistry have made HAT powerful tool capable introducing wide range functional groups into bonds. Moreover, greater mechanistic insights stimulated development increasingly site-selective protocols. Site-selectivity can be achieved through tuning electron density at certain using additives, judicious choice reagent, solvent system. Herein, we describe latest methods functionalizing C–H/Si–H/Ge–H indirect between 2018–2023, as well critical discussion reagents, aspects, substrate scopes, background contexts
Язык: Английский
Процитировано
30
Journal of the American Chemical Society, Год журнала: 2023, Номер 145(31), С. 16966 - 16972
Опубликована: Июль 27, 2023
We present a new, unified approach for the transformation of benzylic and allylic alcohols, aldehydes, ketones into boronic esters under electroreductive conditions. Key to our strategy is use readily available pinacolborane, which serves both as an activator electrophile by first generating redox-active trialkylborate species then delivering desired deoxygenatively borylated product. This applicable variety substrates can be employed late-stage functionalization complex molecules.
Язык: Английский
Процитировано
29
Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(4)
Опубликована: Окт. 9, 2023
The advancement of sustainable photoredox catalysis in synthetic organic chemistry has evolved immensely because the development versatile and cost-effective reagents. In recent years, a substantial effort been dedicated to exploring utility formic acid salts various photochemical reactions. this context, formates have demonstrated diverse capabilities, functioning as reductants, sources carbonyl groups, reagents for hydrogen atom transfer. Notably, CO
Язык: Английский
Процитировано
29
ACS Catalysis, Год журнала: 2024, Номер 14(17), С. 13451 - 13496
Опубликована: Авг. 26, 2024
Alcohols are abundant with versatile structural variety and have ample use as pivotal functional groups in numerous organic processes. Because of their frequent occurrence enumerable natural products, bioactive molecules, medicinal components, alcohol functionalities provide a promising scope research to advance the operational diversity for improving clinical success. Recent years witnessed design modern C–C C–heteroatom bond-forming approaches easily accessible commercially available unactivated aliphatic alcohols native adaptive sp3 handles, hence offering groundbreaking transformative pathways functionalization complex molecular architectures. The judicial application appropriate activating generate alkyl radical from through C–O bond fragmentation employ it potential alkylating agent unfolds unique synthetic strategies, thereby replacing obvious requirement halides. This review elaborately discusses recent trends regarding using C(sp3)-centered various chemical transformations by exploiting different activation modes disrupter under photoredox catalysis. presentation is organized nature scaffolds, kind formation, progress achieved this domain since original discovery providing illustrative examples mechanistic details, focus on difficulties future prospects.
Язык: Английский
Процитировано
10
Beilstein Journal of Organic Chemistry, Год журнала: 2024, Номер 20, С. 346 - 378
Опубликована: Фев. 21, 2024
Due to their ease of preparation, stability, and diverse reactivity, N -hydroxyphthalimide (NHPI) esters have found many applications as radical precursors. Mechanistically, NHPI undergo a reductive decarboxylative fragmentation provide substrate capable engaging in transformations. Their reduction via single-electron transfer (SET) can occur under thermal, photochemical, or electrochemical conditions be influenced by number factors, including the nature electron donor, use Brønsted Lewis acids, possibility forming charge-transfer complexes. Such versatility creates opportunities influence reaction conditions, providing parameters with which control reactivity. In this perspective, we an overview different mechanisms for reactions involving esters, emphasis on recent additions, cyclizations cross-coupling reactions. Within these classes, discuss utility eye towards continued development complexity-generating
Язык: Английский
Процитировано
9
Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(25)
Опубликована: Апрель 15, 2024
Herein, we describe a general hydrodefunctionalization protocol of alcohols and amines through common isonitrile intermediate. To cleave the relatively inert C-NC bond, leveraged dual hydrogen atom transfer (HAT) photoredox catalysis to generate nucleophilic boryl radical, which readily forms an imidoyl radical intermediate from isonitrile. Rapid β-scission then accomplishes defunctionalization. This method has been applied both amine alcohol-containing pharmaceuticals, natural products, biomolecules. We extended this approach reduction carbonyls olefins their saturated counterparts, as well hydrodecyanation alkyl nitriles. Both experimental computational studies demonstrate facile reconcile differences in reactivity between nitriles isonitriles within our protocol.
Язык: Английский
Процитировано
9