Photocatalytic Late-Stage C–H Functionalization

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(8), P. 4237 - 4352

Published: Jan. 24, 2023

The emergence of modern photocatalysis, characterized by mildness and selectivity, has significantly spurred innovative late-stage C–H functionalization approaches that make use low energy photons as a controllable source. Compared to traditional strategies, photocatalysis paves the way toward complementary and/or previously unattainable regio- chemoselectivities. Merging compelling benefits with workflow offers potentially unmatched arsenal tackle drug development campaigns beyond. This Review highlights photocatalytic strategies small-molecule drugs, agrochemicals, natural products, classified according targeted bond newly formed one. Emphasis is devoted identifying, describing, comparing main mechanistic scenarios. draws critical comparison between established ionic chemistry photocatalyzed radical-based manifolds. aims establish current state-of-the-art illustrate key unsolved challenges be addressed in future. authors aim introduce general readership functionalization, specialist practitioners evaluation methodologies, potential for improvement, future uncharted directions.

Language: Английский

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A decade of pyridine containing heterocycles in the approved USFDA drugs: A medicinal chemistry-based analysis

RSC Medicinal Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Heterocyclic scaffolds, particularly, pyridine-containing azaheterocycles, constitute a major part of the drugs approved in past decade. In present review, we explored pyridine ring US FDA-approved small molecules (2014-2023). The analysis bearing revealed that total 54 were approved. Among them, significant number comprised anticancer category (18 drugs, 33%), followed by affecting CNS system (11 20%), which include to treat migraines, Parkinsonism disorders, chemotherapeutic-induced nausea, insomnia, and ADHD or as CNS-acting analgesics sedatives. Next, six (11%) also rare conditions, five affect hematopoietic system. drug approval was granted for antibiotics, antivirals, antifungals, including treatment tropical sub-tropical diseases. Primary targets kinases, metabolizing enzyme CYP3A4. Further formulation types 50% tablets, 17% capsules 15% injections. Elemental showed most contained sulfur, while fluorine noted 32 compounds. Therefore, review is concerted effort cover rings last decade provide thorough discussion commentary on their pharmacokinetics pharmacodynamics aspects. Furthermore, in-depth structural elemental analyses explored, thus providing comprehensive guidance medicinal chemists scientists working allied science domains.

Language: Английский

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Harnessing Visible/UV Light for the Activation and/or Functionalization of C−H Bonds: Metal‐ and Photocatalyst‐Free Approach

The Chemical Record, Journal Year: 2025, Volume and Issue: unknown

Published: March 12, 2025

Abstract Photosynthesis in plants has inspired photochemical reactions organic chemistry. Synthetic chemists always seek cost‐effective, operationally simple, averting the use of toxic and difficult‐to‐remove metallic catalysts, atom economical, high product purity reactions. In last few decades, light as a catalyst increased exponentially literature exploded with examples, particularly by using expensive metal complexes, photosensitizers like dyes, hypervalent iodine, or inorganic semiconductors. this report, we have selected interesting examples performed without any photosensitizers. These inherent potential reactants to utilize energy initiate chemical Our main emphasis is highlight structural features that can absorb form an electron donor‐acceptor (EDA) complex during reaction reaction. Considering degree variability reactions, utmost care been taken present most accurate conditions. A short introductory section on will act anchor revolve around discussed explain underlying principle mechanism.

Language: Английский

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Recent advancements in metal-free C–C bond formation via C–H bond functionalization

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review delves into the peroxides or visible light induced metal-free C–H bond cleavage to accomplish C(sp/sp 2 /sp 3 )–H alkylation, alkenylation, arylation, carbonylation, carbamoylation, alkynylation and cyanation.

Language: Английский

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Advances in Photoinduced Minisci-like Reactions

Synthesis, Journal Year: 2024, Volume and Issue: unknown

Published: July 29, 2024

Abstract The Minisci reaction, which has been around for more than five decades, is still the preferred tool straightforward alkylation of basic heteroarenes. recent developments in photocatalysis have opened novel pathways radical generation under milder and sustainable conditions. Implementing this approach into reaction renewed interest transformation, attractive per se Medicinal Chemistry. Aspects such as sacrificial oxidants, catalysts, specific conditions should be carefully examined to evaluate practicability protocol. This short review focuses on advances (2020 February 2024) photoinduced Minisci-type reactions, emphasizing sustainability. 1 Introduction 2 Using Noble-Metal-Based Photocatalysts 3 Noble-Metal-Free Methods Sacrificial Oxidants 4 Without 5 Conclusions Perspectives

Language: Английский

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Visible light-induced direct and highly selective C–H functionalization of quinoxalin-2(1H)-one without orientating group

Catalysis Science & Technology, Journal Year: 2022, Volume and Issue: 13(2), P. 305 - 309

Published: Dec. 6, 2022

Using eosin Y and KI as photocatalysts to facilitate the conversion of quinoxaline-2(1 H )-one phenylhydrazine hydrochloride compounds into corresponding 3-arylated )-one, a simple efficient synthesis method has been developed.

Language: Английский

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Modular synthesis of C₂-symmetric nitrogen-containing polyaromatics via visible light-enabled reductive aza-6π electrocyclization

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(10), P. 2884 - 2890

Published: Jan. 1, 2024

Here, an unprecedented one-step modular construction of C 2 -symmetric N-PACs through reduction/aza-6π electrocyclization was reported and the resultant N-PAC could be converted into a powerful organic photocatalyst.

Language: Английский

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From Conventional to Sustainable Catalytic Approaches for Heterocycles Synthesis

ChemSusChem, Journal Year: 2023, Volume and Issue: 17(8)

Published: Dec. 23, 2023

Abstract Synthesis of heterocyclic compounds is fundamental for all the research area in chemistry, from drug synthesis to material science. In this framework, catalysed synthetic methods are great interest effective reach such important building blocks. review, we will report on some selected examples last five years, major improvement field, focusing most conventional catalytic systems, as transition metals, organocatalysts, more sustainable ones photocatalysts, iodine‐catalysed reaction, electrochemical reactions and green innovative methods.

Language: Английский

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Pioneering Metal‐Free Late‐Stage C‐H Functionalization Using Acridinium Salt Photocatalysis

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(67)

Published: Aug. 13, 2024

Abstract Using organic dyes as photocatalysts is an innovative approach to photocatalytic transformations. These offer advantages such widespread availability, adaptable absorption properties, and diverse chemical structures. Recent progress has led the development of that can utilize visible light modify chemically inert C−H bonds. catalysts are sustainable, selective, versatile, enabling mild reactions, late‐stage functionalization, various transformations in line with green chemistry principles. As photoredox chemistry, they contribute efficient environmentally friendly synthetic pathways. Acridinium‐based have proved valuable transformative reactions under conditions. This review emphasizes their features, frameworks, applications modifying complex molecules. It provides overview recent advancements use acridinium‐based for bond functionalization without need transition metals, showcasing potential expedite new molecules igniting excitement about prospects this research field.

Language: Английский

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Chichibabin‐Type Phosphonylation of 2‐(Hetero)aryl Pyridines: Selective Synthesis of 4‐Phosphinoyl Pyridines via an Activated N‐Benzylpyridinium Salt

Advanced Synthesis & Catalysis, Journal Year: 2022, Volume and Issue: 364(14), P. 2387 - 2394

Published: June 16, 2022

Abstract A direct C−H phosphonylation of pyridine by N ‐benzylating activation is reported, which afforded 4‐pyridylphosphine oxides with high regioselectivity, without the employment metal catalyst or expensive activator. By increasing electrophilicity pyridinium electron‐withdrawing substituents on ‐benzyl group, process could be realized at room temperature. Control experiments and NMR investigation confirmed interaction between DBU diphenylphosphine oxide generated true phosphorus nucleophile. Moreover, DFT calculations offered enough insight into an intermolecular cooperative dehydrogenation‐debenzylation mechanism, helped to elucidate origin C4‐regioselectivity in this metal‐free Chichibabin‐type phosphonylation. magnified image

Language: Английский

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