Nature Communications, Год журнала: 2025, Номер 16(1)
Опубликована: Май 28, 2025
Язык: Английский
Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(18), С. 5278 - 5305
Опубликована: Янв. 1, 2024
This review summarizes the latest methodological advances in photocatalytic C(sp 3 )–H functionalization, with a particular emphasis on formation of C–P, C–B, C–S bonds, etc ., and some prominent efforts asymmetric C–H functionalization.
Язык: Английский
Процитировано
17
Journal of the American Chemical Society, Год журнала: 2024, Номер 146(27), С. 18218 - 18223
Опубликована: Июнь 26, 2024
Branched allylic esters and carboxylates are fundamental motifs prevalent in natural products drug molecules. The direct C-H oxygenation of internal alkenes represents one the most straightforward approaches, bypassing requirement for an leaving group as classical Tsuji-Trost reaction. However, current methods suffer from limited scope─often accompanied by selectivity issues─thus hampering further development. Herein we report a photocatalytic platform general solution to these problems, enabling coupling diverse with carboxylic acids, alcohols, other
Язык: Английский
Процитировано
15
Accounts of Chemical Research, Год журнала: 2025, Номер unknown
Опубликована: Фев. 26, 2025
ConspectusThe past decade has witnessed significant advancements of visible-light-induced photocatalysis, establishing it as a powerful and versatile tool in organic synthesis. The major focus this field centered on the development methodologies that either rely solely photocatalysts or combine photocatalysis with other catalytic methods, such transition metal catalysis, to address broader more diverse array transformations. Within rapidly evolving area, subfield we refer garnered attention due its growing impact mechanistic uniqueness. A distinguishing feature is dual functionality single complex, which not only acts photocatalyst initiate photochemical processes but also functions traditional catalyst, facilitating key bond-breaking bond-forming events. As such, an exogenous required photocatalysis. However, implications harnessing both excited- ground-state reactivities complex can extend beyond simplification. One most compelling aspects area photoexcited complexes exhibit unique inaccessible through conventional thermal photocatalytic approaches. These distinct be leveraged accomplish novel transformations by engaging entirely different substrate pool unlocking new known substrates.In 2016, our group pioneered use phosphine-ligated palladium catalysts upon visible-light irradiation engage substrates radical reactions. In initial discovery, showed photoexcitation redirect well-established oxidative addition Pd(0) into aryl iodides toward unprecedented process, generating hybrid Pd(I) species. We subsequently extended strategy formation alkyl radicals from halides. reactive intermediates have been harnessed wide variety transformations, including desaturation, Heck reactions, alkene difunctionalization cascades, among others.Seeking further expand avenue, achieved first example asymmetric context allylic C–H amination, where catalyst now plays triple duty additionally controlling stereochemical outcome reaction. parallel reaction established diazo compounds, strained molecules, electron-deficient alkenes serve precursors halides redox-active esters. Notably, engagement made possible photoinduced hydricity enhancement Pd–H species, representing mode reactivity.This Account presents discovery organized type explored. Given rapid progress field, anticipate will provide readers guiding principles inspiration for designing developing efficient
Язык: Английский
Процитировано
1
ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4384 - 4393
Опубликована: Фев. 26, 2025
Язык: Английский
Процитировано
1
Chemical Communications, Год журнала: 2024, Номер unknown
Опубликована: Янв. 1, 2024
Recent years have witnessed the emergence of direct intermolecular C(sp
Язык: Английский
Процитировано
9
Journal of the American Chemical Society, Год журнала: 2024, Номер 146(31), С. 21231 - 21238
Опубликована: Июль 29, 2024
Asymmetric Pd-catalyzed three-component carboamination reactions of dienes to construct chiral cyclohexenylamines, which are great importance in many fields chemistry, have remained largely unexplored. Here, we demonstrate a highly enantio- and regioselective Pd/Ming-Phos-catalyzed 1,3-cyclohexadiene with readily available aryl iodides anilines for facile access diverse valuable cyclohexenylamines. The process shows excellent functional group tolerance, easy scalability, mild conditions. Moreover, mechanistic studies suggest that this reaction has first-order dependence on the concentration palladium catalyst aniline.
Язык: Английский
Процитировано
8
Journal of the American Chemical Society, Год журнала: 2025, Номер unknown
Опубликована: Апрель 4, 2025
Efficient assembly of valuable chiral molecules from readily available and low-cost chemical feedstocks remains one the most challenging tasks in synthetic chemistry today. Radical-mediated three-component carboamination alkenes offers an attractive strategy for addressing this challenge. However, existing reports focus on racemic examples are largely limited to activated alkenes, preactivated alkylation reagents, or sufficiently active nucleophiles. Herein, we report a highly enantioselective carboamidation styrenes with unactivated alkanes weakly nucleophilic amides. Enantioselective control is achieved by using cationic copper catalysts. This method enables synthesis variety optically amides excellent enantioselectivity. Mechanistic studies reveal that reaction proceeds via hydrogen atom transfer alkane followed radical addition olefin.
Язык: Английский
Процитировано
1
Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(16), С. 4522 - 4528
Опубликована: Янв. 1, 2024
A novel strategy for the construction of polysubstituted pyrroles has been developed through visible-light-induced single-electron reduction C Ar –I bonds and following 1,5-hydrogen atom transfer (HAT) process.
Язык: Английский
Процитировано
6
Angewandte Chemie International Edition, Год журнала: 2024, Номер 64(1)
Опубликована: Сен. 17, 2024
Allylic sulfones are valuable motifs due to their medicinal and biological significance versatile chemical reactivities. While direct allylic C-H sulfonylation represents a straightforward desirable approach, these methods primarily restricted terminal alkenes, leaving the engagement of internal counterparts formidable challenge. Herein we report photocatalytic approach that accommodates both cyclic acyclic alkenes with diverse substitution patterns electronic properties. Importantly, obtained can be readily diversified into wide range products, thus enabling formal alkene transposition all-carbon quaternary center formation through sequential functionalization.
Язык: Английский
Процитировано
5
Organic Letters, Год журнала: 2024, Номер 26(26), С. 5528 - 5533
Опубликована: Июнь 20, 2024
This paper outlines an innovative three-component coupling strategy for the 1,4-difunctionalization of 1,3-butadiene, utilizing sodium decatungstate (NaDT) as a hydrogen atom transfer (HAT) photocatalyst. The photoinduced process efficiently generates homoallylic amino acid esters with 100% economy, employing readily available components under mild reaction conditions. light-induced protocol eliminates need additional transition metal catalysts, additives, or equivalent reducing agents. study explored various C(sp3)–H bearing partners, butadienes, and α-iminoesters, demonstrating versatility synthetic utility this method.
Язык: Английский
Процитировано
4