Cobalt‐Catalyzed Electroreductive Alkylation of Unactivated Alkyl Chlorides with Conjugated Olefins

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(1)

Опубликована: Ноя. 14, 2023

Reactions of unactivated alkyl chlorides under mild and sustainable conditions are rare compared to those bromides or iodides. As a result, synthetic methods capable modifying the vast chemical space chloroalkane reagents, wastes, materials limited. We report cobalt-catalyzed reductive addition conjugated alkenes. Co-catalyzed activation is performed electroreductive conditions, resulting reactions constitute formal alkyl-alkyl bond formation. In developing an operationally simple methodology, detailed mechanistic studies provide insights into elementary steps proposed catalytic cycle. particular, we propose switch in mechanism C-Cl from nucleophilic substitution halogen atom abstraction, which critical for efficiently generating radicals. These were leveraged designing ligands that enable couplings primary, secondary, tertiary chlorides.

Язык: Английский

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Photochemical Reduction of Quinolines with γ-Terpinene

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Янв. 3, 2024

The saturation of aromatic scaffolds is valuable for the synthesis complex rings. Herein, we demonstrate a process photochemical dearomative reduction quinolines. involves capture quinoline excited state with γ-terpinene. Importantly, reaction chemoselective as other easily reduced functionalities such halogens or alkenes do not undergo reduction. mechanism has also been investigated. Finally, generality approach towards substrates demonstrated.

Язык: Английский

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Iron‐Catalyzed Allylic C(sp³)−H Silylation: Spin‐Crossover‐Efficiency‐Determined Chemoselectivity

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(21)

Опубликована: Март 12, 2024

Abstract The nuanced role of spin effects remains a critical gap in designing proficient open‐shell catalysts. This study elucidates an iron‐catalyzed allylic C( sp 3 )−H silylation/alkyne hydrosilylation reaction, which the state iron catalyst dictates reaction kinetics and pathway. Specifically, crossover led to alkyne hydrosilylation, whereas conservation resulted novel silylation reaction. chemoselectivity, governed by spin‐crossover efficiency, reveals unexpected dimension first realm transition‐metal‐catalyzed situ bonds, had been previously inhibited heightened reactivity alkenes reactions. Furthermore, this can either accelerate or hinder at different stages within single catalytic phenomenon scarcely documented. Moreover, we identify substrate‐assisted C−H activation mechanism, departure from known ligand‐assisted processes, offering fresh perspective on strategies.

Язык: Английский

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Enantioselective Hydrofunctionalization of Cyclobutenones: Total Synthesis of gem‐Dimethylcyclobutane Natural Products

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(20)

Опубликована: Март 18, 2024

Cyclobutanes with a gem-dimethyl group are common motifs in natural products. However, strategies for constructing enantioenriched cyclobutanes still underdeveloped. Herein, we report an enantioselective approach to synthesize broad of chiral 2,3-disubstituted cyclobutanones through sequential 1,4-conjugate addition/trapping/cross-coupling readily available cyclobutenones. The intermediate 2-bromocyclobutanone provides valuable synthetic handle further coupling transformations. In addition, this strategy was successfully utilized cyclobutane-containing products, including (+)-β-caryophyllene, (-)-raikovenal, (-)-1β,9αH-5-linoleoyloxy-4,5-secocaryophyllen-4-one, and (-)-rumphellanones A-C.

Язык: Английский

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Deuteration of arenes in pharmaceuticals via photoinduced solvated electrons

Chem, Год журнала: 2024, Номер 10(11), С. 3374 - 3384

Опубликована: Июль 18, 2024

Язык: Английский

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