Overview of Recent Scale-Ups in Organic Electrosynthesis (2000–2023)

Organic Process Research & Development, Год журнала: 2024, Номер 28(2), С. 338 - 366

Опубликована: Янв. 18, 2024

This review summarizes examples of organic electrosynthesis from the peer-reviewed literature 2000 to 2023 that have been conducted on scales 20 g or above. A significant portion these were a ≤100 scale, while detailed reports kilogram-scale remain scarce in pharmaceutical industry. In addition chemical transformation, this also highlights type reactor used and projected productivity metric as ways compare different reports. The selected scale-ups described herein illustrate remaining challenges currently preventing routine use large-scale

Язык: Английский

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Mechanisms of Photoredox Catalysis Featuring Nickel–Bipyridine Complexes

ACS Catalysis, Год журнала: 2024, Номер 14(11), С. 9055 - 9076

Опубликована: Май 29, 2024

Metallaphotoredox catalysis can unlock useful pathways for transforming organic reactants into desirable products, largely due to the conversion of photon energy chemical potential drive redox and bond transformation processes. Despite importance these processes cross-coupling reactions other transformations, their mechanistic details are only superficially understood. In this review, we have provided a detailed summary various photoredox mechanisms that been proposed date Ni-bipyridine (bpy) complexes, focusing separately on photosensitized direct excitation reaction By highlighting multiple key findings, depict how mechanisms, which ultimately define substrate scope, themselves defined by ground- excited-state geometric electronic structures Ni-based intermediates. We further identify knowledge gaps motivate future studies development synergistic research approaches spanning physical, organic, inorganic chemistry communities.

Язык: Английский

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Stereoselective amino alcohol synthesis via chemoselective electrocatalytic radical cross-couplings

Nature Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 3, 2025

Язык: Английский

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Nickel-mediated aerobic C(sp2)–nucleophile coupling reactions for late-stage diversification of aryl electrophiles

Nature Synthesis, Год журнала: 2025, Номер unknown

Опубликована: Янв. 16, 2025

Язык: Английский

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Simplified Modular Access to Enantiopure 1,2-Aminoalcohols via Ni-Electrocatalytic Decarboxylative Arylation

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(9), С. 6209 - 6216

Опубликована: Фев. 22, 2024

Chiral aminoalcohols are omnipresent in bioactive compounds. Conventional strategies to access this motif involve multiple-step reactions install the requisite functionalities stereoselectively using conventional polar bond analysis. This study reveals that a simple chiral oxazolidine-based carboxylic acid can be readily transformed substituted with high stereochemical control by Ni-electrocatalytic decarboxylative arylation. general, robust, and scalable coupling used synthesize variety of medicinally important compounds, avoiding protecting functional group manipulations, thereby dramatically simplifying their preparation.

Язык: Английский

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Red Light–Blue Light Chromoselective C(sp²)–X Bond Activation by Organic Helicenium-Based Photocatalysis

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(12), С. 7922 - 7930

Опубликована: Март 18, 2024

Chromoselective bond activation has been achieved in organic helicenium (nPr-DMQA+)-based photoredox catalysis. Consequently, control over chromoselective C(sp2)–X multihalogenated aromatics demonstrated. nPr-DMQA+ can only initiate the halogen atom transfer (XAT) pathway under red light irradiation to activate low-energy-accessible C(sp2)–I bonds. In contrast, blue initiates consecutive photoinduced electron (conPET) more challenging C(sp2)–Br Comparative reaction outcomes have demonstrated α-arylation of cyclic ketones with and lights. Furthermore, red-light-mediated selective bonds activated iodobromoarenes keep bromo functional handle untouched. Finally, strength catalysis highlighted two-fold functionalization using both photo-to-transition metal photo-to-photocatalyzed transformations.

Язык: Английский

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Enantiocovergent Cross-Coupling Reaction with 1,4-Dihydropyridine Derivatives via Photoinduced Nickel Catalysis

ACS Catalysis, Год журнала: 2024, Номер 14(5), С. 3278 - 3286

Опубликована: Фев. 15, 2024

Herein, we reported the enantioconvergent Csp3–Csp2 cross-coupling reaction with 1,4-dihydropyridine (DHP) derivatives via photoredox/nickel dual catalysis to access chiral products good yield and enantioselectivity. The operationally simple was carried out under mild conditions functional group tolerance. Due use of a stoichiometric equivalent aryl/alkenyl halides as coupling partners, sequential iterative synthesis could be achieved smoothly in one pot for position isomers stereoisomers. In proposed mechanism, kinetic experiments mechanistic studies indicated that radical generation, depended on excited photocatalyst DHP, rate-determining step.

Язык: Английский

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Direct Amino-α-C–H Heteroarylation of Amides under Electrochemical Conditions

Organic Letters, Год журнала: 2024, Номер 26(2), С. 493 - 497

Опубликована: Янв. 8, 2024

An electrochemical hydrogen atom transfer (HAT) strategy for the direct amino-α-C–H heteroarylation of amides is described. The cheap TMSN3 acts as a reagent. A series heteroarenes including quinoxalin-2(1H)-ones, 4-methylquinoline, isoquinoline, 2-methylquinoxaline, benzothiazole, etc., and various readily available amides/lactams were suitable. reaction has characteristics wide range substrates, good regioselectivity, chemical oxidant-free conditions, etc.

Язык: Английский

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Electrochemical and Photocatalytic Synthesis of Organic Compounds Utilizing a Greener Approach. A review

Molecular Catalysis, Год журнала: 2024, Номер 559, С. 114087 - 114087

Опубликована: Апрель 1, 2024

Язык: Английский

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Alcohols as Alkyl Synthons Enabled by Photoredox-Catalyzed Deoxygenative Activation

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

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