Fifty Shades of Phenanthroline: Synthesis Strategies to Functionalize 1,10-Phenanthroline in All Positions

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(11), P. 6700 - 6902

Published: May 15, 2024

1,10-Phenanthroline (phen) is one of the most popular ligands ever used in coordination chemistry due to its strong affinity for a wide range metals with various oxidation states. Its polyaromatic structure provides robustness and rigidity, leading intriguing features numerous fields (luminescent scaffolds, catalysis, supramolecular chemistry, sensors, theranostics, etc.). Importantly, phen offers eight distinct positions functional groups be attached, showcasing remarkable versatility such simple ligand. As result, has become landmark molecule chemists, serving as must-use ligand versatile platform designing polyfunctional arrays. The extensive use substituted phenanthroline different metal ions resulted diverse array complexes tailored applications. For instance, these have been utilized sensitizers dye-sensitized solar cells, luminescent probes modified antibodies biomaterials, creation elegant architectures like rotaxanes catenanes, exemplified by Sauvage's Nobel Prize-winning work 2016. In summary, found applications almost every facet chemistry. An aspect specific reactivity each pair carbon atoms ([2,9], [3,8], [4,7], [5,6]), enabling functionalization Furthermore, it possible differentiate position pairs, resulting non-symmetrical systems tremendous versatility. this Review, authors aim compile categorize existing synthetic strategies stepwise polyfunctionalization positions. This comprehensive toolbox will aid chemists virtually any survey encompass seminal from 1950s present day. scope Review limited 1,10-phenanthroline, excluding more intracyclic heteroatoms or fused aromatic cycles. Overall, primary goal highlight both old recent that find applicability mentioned By doing so, hope establish first reference synthesis, covering all on backbone, inspire concerned devise new not yet explored.

Language: Английский

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Aliphatic C–H Functionalization Using Pyridine N-Oxides as H-Atom Abstraction Agents

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(16), P. 10499 - 10505

Published: Aug. 10, 2022

The alkylation and heteroarylation of unactivated tertiary, secondary, primary C(sp3)-H bonds was achieved by employing an acridinium photoredox catalyst along with readily available pyridine Noxides as hydrogen atom transfer (HAT) precursors under visible light. Oxygen-centered radicals, generated single-electron oxidation the Noxides, are proposed key intermediates whose reactivity can be easily modified structural adjustments. A broad range aliphatic C-H substrates electron-donating or -withdrawing groups well various olefinic radical acceptors heteroarenes were tolerated.

Language: Английский

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Recent Advances in C–H Functionalisation through Indirect Hydrogen Atom Transfer

Molecules, Journal Year: 2023, Volume and Issue: 28(16), P. 6127 - 6127

Published: Aug. 18, 2023

The functionalisation of C–H bonds has been an enormous achievement in synthetic methodology, enabling new retrosynthetic disconnections and affording simple equivalents for synthons. Hydrogen atom transfer (HAT) is a key method forming alkyl radicals from substrates. Classic reactions, including the Barton nitrite ester reaction Hofmann–Löffler–Freytag reaction, among others, provided early examples HAT. However, recent developments photoredox catalysis electrochemistry have made HAT powerful tool capable introducing wide range functional groups into bonds. Moreover, greater mechanistic insights stimulated development increasingly site-selective protocols. Site-selectivity can be achieved through tuning electron density at certain using additives, judicious choice reagent, solvent system. Herein, we describe latest methods functionalizing C–H/Si–H/Ge–H indirect between 2018–2023, as well critical discussion reagents, aspects, substrate scopes, background contexts

Language: Английский

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Alkanes in Minisci-Type Reaction under Photocatalytic Conditions with Hydrogen Evolution

Organic Letters, Journal Year: 2023, Volume and Issue: 25(48), P. 8541 - 8546

Published: Oct. 11, 2023

We report herein a protocol for the selective activation of C(sp3)–H bonds based on interplay two readily available organic catalysts and their successful implementation in cross-coupling azaarenes with alkanes. This Minisci-like reaction is promoted by visible light at room temperature free from chemical oxidants, metals, chlorinated solvents. A wide range substrates are compatible, including some bioactive molecules. Mechanistic studies support dual catalytic cycle H2 evolution.

Language: Английский

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Photocatalyzed Minisci-type reactions for late-stage functionalization of pharmaceutically relevant compounds

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(7), P. 3595 - 3626

Published: Jan. 1, 2024

The application of photocatalyzed Minisci-type reactions in LSF accelerates the discovery drug candidates a green way.

Language: Английский

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Visible-light induced direct C(sp³)–H functionalization: recent advances and future prospects

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(18), P. 5278 - 5305

Published: Jan. 1, 2024

This review summarizes the latest methodological advances in photocatalytic C(sp 3 )–H functionalization, with a particular emphasis on formation of C–P, C–B, C–S bonds, etc ., and some prominent efforts asymmetric C–H functionalization.

Language: Английский

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Photoinduced Three-Component Carboarylation of Unactivated Alkenes with Protic C(sp³)–H Feedstocks

Organic Letters, Journal Year: 2022, Volume and Issue: 24(41), P. 7677 - 7684

Published: Oct. 10, 2022

A general and mild strategy involving three-component carboarylation of unactivated alkenes with protic C(sp3)–H feedstocks via photoredox catalysis was reported. This catalytic system is compatible a broad range alkenes, cyano-substituted arenes, diverse feedstocks. The synthetic value this protocol demonstrated by the late-stage functionalization complex molecules synthesis antiallergies including pheniramine, chlorpheniramine, brompheniramine.

Language: Английский

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Catalytic acceptorless dehydrogenative coupling mediated by photoinduced hydrogen-atom transfer

Nature Synthesis, Journal Year: 2023, Volume and Issue: 2(3), P. 209 - 216

Published: Jan. 2, 2023

Language: Английский

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A Modular Tubular Flow System with Replaceable Photocatalyst Membranes for Scalable Coupling and Hydrogenation

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(22)

Published: March 29, 2023

Heterogeneous photocatalysis is effective for the selective synthesis of value-added chemicals at lab-scale, yet falls short requirements mass production (low cost and user friendliness). Here we report design fabrication a modular tubular flow system embedded with replaceable photocatalyst membranes scalable photocatalytic C-C, C-N homocoupling hydrogenation reactions, which can be operated in either circular continuous mode high performance. The almost fully occupy volume reactor, thus enabling optimal absorption incident light. Additionally, porous structured facilitate transfer reactants to efficiently use active sites, resulting 0th -order reaction kinetics space-time yield compared batch practical application levels prolonged times.

Language: Английский

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2-Isopropylthioxanthone-Catalyzed Divergent Functionalization of Bicyclo[1.1.0]butanes under Visible-Light Irradiation

Organic Letters, Journal Year: 2023, Volume and Issue: 25(33), P. 6184 - 6188

Published: Aug. 9, 2023

1,3-Functionalized cyclobutane structural motifs are ubiquitous in natural products and pharmaceuticals. Photoinduced alkylation of bicyclo[1.1.0]butanes (BCBs) offers a step-economical strategy for accessing 1,3-functionalized motifs. Herein, we disclose general mild photocatalytic protocol bromoallylation BCBs metal, additive-free manner by using the same photocatalyst, 2-isopropylthioxanthone, different catalytic roles. Furthermore, synthetic utility these was illustrated synthesis various valuable complex derivatives.

Language: Английский

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