Late-Stage Saturation of Drug Molecules

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(17), P. 11866 - 11875

Published: April 15, 2024

The available methods of chemical synthesis have arguably contributed to the prevalence aromatic rings, such as benzene, toluene, xylene, or pyridine, in modern pharmaceuticals. Many sp

Language: Английский

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Recent Advances in Dearomative Partial Reduction of Benzenoid Arenes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(21)

Published: March 14, 2024

Abstract Dearomative partial reduction is an extraordinary approach for transforming benzenoid arenes and has been well‐known many decades, as exemplified by the dehydrogenation of Birch hydroarylation Crich addition. Despite its remarkable importance in synthesis, this field experienced slow progress over last half‐century. However, a revival observed with recent introduction electrochemical photochemical methods. In Minireview, we summarize advancements dearomative arenes, including dihydrogenation, hydroalkylation, arylation, alkenylation, amination, borylation others. Further, intriguing utilization synthesis natural products also emphasized. It anticipated that Minireview will stimulate further arene transformations.

Language: Английский

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High Performance Polyoxometalate-Stabilizing Pt Nanocatalysts for Quinoline Hydrogenation with Water-Mediated Dynamic Hydrogen

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 5344 - 5355

Published: March 26, 2024

In this work, a Keggin-type platinum substituted polyoxometalate (POM) is constructed by the reaction of monolacunary phosphotungstate precursor [PW11O39]7– with chloroplatinic acid. The as-obtained tetrabutylammonium salt (TBA-PWPt) demonstrates that dimeric Pt2+ ions are incorporated into POM frameworks and linked two anions. Notably, once Pt-substituted anion reduced H2, anion-stabilizing Pt nanocatalysts generated, which greatly facilitates forming oxygen vacancies adjacent to Pt0 species. show superior catalytic activity stability for selective hydrogenation quinoline 1,2,3,4-tetrahydroquinoline in water. Detailed investigations elucidate stronger adsorption on surface H2 activated at POMs-Pt interface site. Moreover, density functional theory (DFT) calculations H2O adsorbed interfacial then undergoes homolytic dissociation produce hydroxyl group (OH–) hydride (H–) H– species transferred N-containing pyridine ring hydrogenation, OH– help promote heterolytic H+ Sequentially, produced proton groups generate H2O, cycle completed.

Language: Английский

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Dearomative dimerization of quinolines and their skeletal rearrangement to indoles triggered by single-electron transfer

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

Published: Oct. 1, 2024

Language: Английский

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Photochemical Reduction of Quinolines with γ-Terpinene

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 3, 2024

The saturation of aromatic scaffolds is valuable for the synthesis complex rings. Herein, we demonstrate a process photochemical dearomative reduction quinolines. involves capture quinoline excited state with γ-terpinene. Importantly, reaction chemoselective as other easily reduced functionalities such halogens or alkenes do not undergo reduction. mechanism has also been investigated. Finally, generality approach towards substrates demonstrated.

Language: Английский

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Chemodivergent dearomatization of benzene-linked O-oxime esters via EnT-induced radical cross-coupling

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Radical-mediated dearomatization strategies offer a blueprint for building value-added and synthetically valuable three-dimensional skeletons from readily available aromatic starting materials.

Language: Английский

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Ligand-Controlled Regioselective Dearomative Vicinal and Conjugate Hydroboration of Quinolines

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 27, 2025

A dearomative strategy to regioselectively modify arenes using a "diene" synthon within aromatic rings provides access highly functionalized heterocycles from abundant feedstocks and represents an alternative synthetic approach besides traditional cross-coupling C-H functionalization methodologies. In this study, we present efficient method for selectively introducing boron onto quinolines through hydroboration easily accessible stable phosphine-ligated borane complexes. The vicinal 5,6- conjugate 5,8-hydroborated products could be obtained by modifying the phosphine ligand. Drawing inspiration diverse organoboron transformations, these building blocks were diversified range of downstream functionalizations, providing modular pathways skeletal modifications variety challenging heterocycles.

Language: Английский

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A D–A–D-type di-lophine derivative-based photoactive metal–organic framework: fluorescence sensing of UO₂²⁺ and photochromic behavior

Inorganic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(16), P. 5127 - 5136

Published: Jan. 1, 2024

A cadmium-based photoactive MOF was designed to achieve fluorescence sensing various hazardous analytes, especially UO 2 2+ , and exhibit photochromic behavior in response light exposure.

Language: Английский

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Excited-state protonation and reduction enables the umpolung Birch reduction of naphthalenes

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

Published: Nov. 1, 2024

Language: Английский

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Dearomative dimerization of quinolines and their skeletal rearrangement to indoles triggered by single-electron transfer

Published: May 29, 2024

Dearomatization of two-dimensional (2D) planar aromatic feedstocks enables the introduction three-dimensional (3D) vectors to new molecular scaffolds, vastly expanding chemical space for drug discovery. Here, we demonstrate that photoinduced single-electron reduction quinolines under polysulfide anion photocatalysis triggers dearomative dimerization and an unprecedented skeletal rearrangement. In presence excess formate as stoichiometric reductant, a complex polyheterocyclic hybrid 2,5-methanobenzo[b]azepine tetrahydroisoquinoline is formed in net-reductive manner, whereas trialkylamine instead formate, sequential rearrangement occurs afford 4-(3-indolylmethyl)quinolines redox-neutral manner. The remarkable way which additive dictates reaction course showcases unique tunability mediated redox photocatalysis. These observations enabled design 4-arylquinolines 3-(arylmethyl)indoles. Detailed mechanistic investigations reveal this umpolung transformation from electron-deficient electron-rich indoles via 1,2-aryl migration/ring-contraction sequence, opposed more commonly invoked neophyl-like

Language: Английский

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