Recent Advances in Electron Donor‐Acceptor (EDA)‐Complex Reactions involving Quaternary Pyridinium Derivatives

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(10), P. 1538 - 1564

Published: March 6, 2023

Abstract Quaternary pyridinium compounds are valuable intermediates in organic synthesis, which have gained immense popularity the synthetic community. The application of transition metal or photoredox catalysis transforming quaternary into various C−C and C−X bonds is well established. A majority these methods require high temperatures, expansive catalysts, delicate conditions for successful execution. On other hand, use metal‐free photocatalysis‐free strategies constructing using derivatives has been sought‐after. In this context, electron‐donor‐acceptor (EDA)‐complex reactions emerged as a state‐of‐the‐art methodology, do not any photocatalyst their EDA‐complex photochemistry takes advantage electron‐acceptor ability derivatives, can quickly generate radical precursor via deaminative process. These newly generated useful several transformations. We hereby, review, discuss an area major progress mediated involving with mechanism, substrate scope, limitations. magnified image

Language: Английский

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1,4‐Aminoarylation of Butadienes via Photoinduced Palladium Catalysis

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(14)

Published: Feb. 9, 2024

Abstract A visible‐light‐induced, three‐component palladium‐catalyzed 1,4‐aminoarylation of butadienes with readily available aryl halides and aliphatic amines has been developed, affording allylamines excellent E ‐selectivity. The reaction exhibits exceptional control over chemo‐, regio‐, stereoselectivity, a broad substrate scope, high functional group compatibility, as demonstrated by the late‐stage functionalization bioactive molecules. Mechanistic investigations are consistent photoinduced radical Pd(0)‐Pd(I)‐Pd(II)‐Pd(0) Heck‐Tsuji–Trost allylation cascade.

Language: Английский

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Ligand-Enabled “Two-in-One” Metallaphotocatalytic Cross Couplings

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 1635 - 1654

Published: Jan. 15, 2025

Metallaphotoredox cross coupling (MCC) is ranking among the most advanced synthetic methodology as it can access chemical space that difficult to attain under conventional conditions. Earlier developed MCC mandates an independent transition metal catalyst and respective photocatalyst, thus constituting a dual catalytic manifold. Complementarily, paradigm-shifting metallaphotoredox strategy capitalizes on single photoreactive complex emerging, which brings not only operational simplification but also unexpected mechanistic insights. This perspective compiled recent advances in monocatalytic couplings categorized them based ligands confer distinct photoreactivities various mechanisms. To this end, ligand-enabled oxidative addition, transmetalation, reductive elimination other radical-involving pathways were summarized with notable examples. In way, we wish provide handy guideline for readers who are interested emerging field inspire more future endeavors MCCs beyond.

Language: Английский

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A modular approach to catalytic stereoselective synthesis of chiral 1,2-diols and 1,3-diols

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 3, 2025

Optically pure 1,2-diols and 1,3-diols are the most privileged structural motifs, widely present in natural products, pharmaceuticals chiral auxiliaries or ligands. However, their synthesis relies on use of toxic expensive metal catalysts suffer from low regioselectivity. Catalytic asymmetric optically 1,n-diols bulk chemicals a highly stereoselective atom-economical manner remains formidable challenge. Here, we disclose versatile modular method for enantioenriched high-production-volume ethane-1,2-diol (MEG) 1,3-propanediol (PDO), respectively. The key to success is temporarily mask diol group as an acetonide, which imparts selectivity step C(sp3)-H functionalization. Additionally, containing two stereogenic centers also prepared through diastereoselective late-stage functionalization biological active compounds expedient ligands pharmaceutically relevant molecules further highlight synthetic potential this protocol. authors report ethylene glycol 1,3-propanediol,

Language: Английский

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Biocatalysis with Laccases: An Updated Overview

Catalysts, Journal Year: 2020, Volume and Issue: 11(1), P. 26 - 26

Published: Dec. 28, 2020

Laccases are multicopper oxidases, which have been widely investigated in recent decades thanks to their ability oxidize organic substrates the corresponding radicals while producing water at expense of molecular oxygen. Besides successful (bio)technological applications, for example, textile, petrochemical, and detoxifications/bioremediations industrial processes, synthetic potentialities mild green preparation or selective modification fine chemicals outstanding value biocatalyzed synthesis. Accordingly, this review is focused on reporting rationalizing some most interesting exploitations laccases. Applications so-called laccase-mediator system (LMS) alcohol oxidation discussed with a focus carbohydrate chemistry natural products as well bio- chemo-integrated processes. The laccase-catalyzed Csp2-H bonds activation via monoelectronic also by examples enzymatic C-C C-O radical homo- hetero-couplings, aromatic nucleophilic substitutions hydroquinones quinoids. Finally, laccase-initiated domino/cascade synthesis valuable (hetero)cycles, elegant strategies documented literature across more than three decades, presented.

Language: Английский

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