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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Palladium-Catalyzed Aerobic Oxidative Spirocyclization of Alkyl Amides with Maleimides via β-C(sp³)–H Activation

Organic Letters, Journal Year: 2023, Volume and Issue: 25(34), P. 6305 - 6310

Published: Aug. 22, 2023

An efficient method for the synthesis of bicyclic spirodiamine molecules via β-C(sp3)–H bond activation aliphatic amides, followed by cyclization with maleimides, has been developed. The reaction proceeds through an amide-directed alkyl amides and subsequent maleimides. methodology is highly compatible a wide variety Amides derived from biologically active fatty acids were also found to be protocol. A palladacycle was synthesized intermediate in this reaction. plausible mechanism proposed account spirocyclization.

Language: Английский

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Synthesis of γ-Lactams via Palladium-Catalyzed C(sp³)–H Bond Activation of Alkyl Sulfonamides with Substituted Alkenes

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 20, 2025

A methodology for the γ-butyrolactam scaffolds via ligand-enabled C(sp3)–H bond functionalization of sulfonamides with olefins has been demonstrated. The protocol found to be compatible several activated and unactivated olefins, desired lactams were formed in excellent yields. plausible mechanism described account lactamization reaction as well supported by mechanistic investigation including a 1H NMR study isolation palladacycle intermediate.

Language: Английский

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Photoredox Catalyzed Tandem Denitrogenative [4 + 2] Annulation of 1,2,3-Benzotriazin-4(3H)-ones with Terminal Olefins

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(21), P. 16043 - 16048

Published: Oct. 15, 2024

The dihydroisoquinolones skeleton is ubiquitous in natural products and biological molecules. Reported strategies for constructing usually require noble metal catalysts or stoichiometric oxidants, which limit their wide applications. Herein, we developed a photoredox catalyzed tandem denitrogenative [4 + 2] annulation reaction of 1,2,3-benzotriazin-4(3H)-ones with terminal olefins. A variety can be accessed moderate to excellent yield. This protocol features high atom-economy, mild conditions, external oxidant-free, enabling the synthesis various substituted dihydroisoquinolones.

Language: Английский

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