Organic Letters, Год журнала: 2024, Номер unknown
Опубликована: Окт. 2, 2024
Herein, a Mn catalytic protocol has been developed for the cycloalkene ring expansion synthesis of azaheterocycles, allowing broad-substrate-scope access to pyridine and isoquinoline derivatives. The initial monoaddition an azidyl radical alkene further as-generated C-radical addition O
Язык: Английский
Chemical Reviews, Год журнала: 2024, Номер 124(17), С. 10192 - 10280
Опубликована: Авг. 8, 2024
Radical C–H functionalization represents a useful means of streamlining synthetic routes by avoiding substrate preactivation and allowing access to target molecules in fewer steps. The first-row transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, Cu) are Earth-abundant can be employed regulate radical functionalization. use such is desirable because the diverse interaction modes between metal complexes species including addition center, ligand complexes, substitution single-electron transfer radicals hydrogen atom noncovalent complexes. Such interactions could improve reactivity, diversity, selectivity transformations allow for more challenging reactions. This review examines achievements this promising area over past decade, with focus on state-of-the-art while also discussing existing limitations enormous potential high-value regulated these metals. aim provide reader detailed account strategies mechanisms associated
Язык: Английский
Процитировано
12
Journal of the American Chemical Society, Год журнала: 2025, Номер unknown
Опубликована: Янв. 9, 2025
The direct synthesis of C(sp3)-rich architectures is a driving force for innovation in synthetic organic chemistry. Such scaffolds impart beneficial properties onto drug molecules that correlate with greater clinical success. Consequently, there strong impetus to develop new methods by which access sp3-rich from commercial feedstocks, such as alkenes. Herein, we report three-component aminoalkylation reaction utilizes the principles triple radical sorting regioselectively add N-centered and C-centered radicals across This process relies upon photoredox catalysis transform alkyl bromides reductively activated precursors into high-energy species redox-neutral fashion. A broad scope coupling partners demonstrated, multiple applications, including facile syntheses pharmacophoric substituted N-heterocycles.
Язык: Английский
Процитировано
1
Journal of the American Chemical Society, Год журнала: 2025, Номер 147(2), С. 1667 - 1676
Опубликована: Янв. 7, 2025
We report a Ni-catalyzed vicinal alkylarylation of unactivated alkenes in γ,δ- and δ,ε-alkenylamines with aryl halides alkylzinc reagents. The reaction is enabled by amine coordination can use all primary, secondary, tertiary amines. constructs two new C(sp3)-C(sp3) C(sp3)-C(sp2) bonds produces δ- ε-arylamines C(sp3)-branching at the γ- δ-positions. A variety heteroaryl iodides both primary secondary reagents be used as coupling carbon sources. Mechanistic studies suggest that cooperative effect organic nitriles electron-deficient (EDAs) ligands.
Язык: Английский
Процитировано
0
Science China Chemistry, Год журнала: 2025, Номер unknown
Опубликована: Янв. 3, 2025
Язык: Английский
Процитировано
0
Chemical Science, Год журнала: 2025, Номер 16(10), С. 4442 - 4449
Опубликована: Янв. 1, 2025
Catalytic methods by switching the least parameters for regioselective and site-divergent transformations to construct different architectures from identical readily available starting materials are among most ideal catalytic protocols. However, associated challenge precisely control both regioselectivity site diversity renders this strategy appealing yet challenging. Herein, Ni-catalyzed cross-electrophile 1,2- 1,3-arylalkylations of N-acyl allylic amines have been developed. This reductive three-component protocol enables 1,2-arylalkylation 1,3-arylalkylation with aryl halides alkyl excellent chemo-, regio- site-selectivity, representing first example controlled migratory difunctionalization alkenes under conditions. A wide range terminal internal unactivated amines, precursors were tolerated, providing straightforward efficient access diverse C(sp3)-rich branched aliphatic materials.
Язык: Английский
Процитировано
0
Organic Letters, Год журнала: 2025, Номер unknown
Опубликована: Фев. 21, 2025
A metal-free, visible-light-induced NHC-catalyzed multiple-component reaction involving aldehydes and aryl thianthrenium salts for the carboacylation of alkenes is reported. In this reaction, NHC-activated afforded Breslow intermediates, which reduced generated radicals. The resulting radicals underwent radical addition reactions to yield arylacylation products, in presence iodoalkane, participated halogen atom transfer process generate alkyl facilitate olefin alkylacylation.
Язык: Английский
Процитировано
0
Organic Letters, Год журнала: 2025, Номер unknown
Опубликована: Март 3, 2025
Alkyl radicals represent some of the most intriguing prospects in organic synthesis, showing diverse patterns reactivity for versatile transformations. In light this, methyl radical, addition to being a methylating agent, is also good proposition hydrogen atom transfer (HAT). Similarly, acetonitrile has dual facets its reactivity, acting as an amination reagent Ritter reaction while progenitor cyanomethyl through HAT. We hereby take advantage merging reactivities these radicals, allowing facile access amines various types from olefins when conjugated with photoredox amination.
Язык: Английский
Процитировано
0
Journal of the American Chemical Society, Год журнала: 2024, Номер 146(51), С. 35035 - 35042
Опубликована: Дек. 12, 2024
Herein, we introduce a new platform for alkene carboxy-alkylation. This reaction is designed around CO
Язык: Английский
Процитировано
3
Organic Letters, Год журнала: 2024, Номер 26(26), С. 5560 - 5565
Опубликована: Июнь 25, 2024
An intermolecular nickel-catalyzed reductive 1,2-alkylarylation of acrylates with cyclopropylamine NHP esters and aryl iodides is reported. This operationally simple protocol provides direct access to 1-alkylcyclopropylamine scaffolds. The mild conditions are compatible four-membered α-amino strained rings as well five- six-membered ring systems. products undergo cyclization α-arylated spirocyclic γ-lactams─a motif present in several pharmaceuticals.
Язык: Английский
Процитировано
2
Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(51)
Опубликована: Сен. 5, 2024
Benzo[1,3,2]dithiazole-1,1,3-trioxides are bench-stable and easy-to-use reagents. In photoredox catalysis, they generate methyl perdeuteromethyl radicals which can add to a variety of radical acceptors, including olefins, acrylamides, quinoxalinones, isocyanides, enol silanes, N-Ts acrylamide. As byproduct, salt is formed be regenerated the original methylating agent. Flow chemistry provides an option for reaction scale-up further underscoring synthetic usefulness these methylation Mechanistic investigations suggest single-electron transfer (SET) pathway induced by catalysis.
Язык: Английский
Процитировано
2