B(C6F5)3-catalyzed selective C–H chalcogenation of arenes and heteroarenes

Chem, Journal Year: 2024, Volume and Issue: 10(9), P. 2901 - 2915

Published: June 27, 2024

The synthesis of organochalcogenides remains a valuable area research due to their widespread biological applications, particularly in pharmaceuticals. Herein, our study details the B(C6F5)3-catalyzed Csp2–H functionalization diverse arenes, heteroarenes, and pharmacophores with thiosuccinimides or selenosuccinimides, providing selective access chalcogenated products. This protocol enables late-stage chalcogenation drug molecules such as anti-inflammatory naproxen, estrogen steroid hormone estradiol derivatives, industrially relevant trifluoromethylthiolation reaction. Furthermore, this C–S coupling methodology provides facile metal-free route synthesize vortioxetine, an antidepressant drug, plethora significant organic motifs. Detailed NMR, EPR analyses, density functional theory (DFT) computational studies indicate that elongation thiosuccinimide N–S bond is assisted by boron-centered adduct, which then leads stable ion pair arene. analysis shows transient radical pair, potentially off-cycle species, not directly involved catalytic process.

Language: Английский

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Electro-photochemical Functionalization of C(sp³)–H bonds: Synthesis toward Sustainability

JACS Au, Journal Year: 2024, Volume and Issue: 4(9), P. 3340 - 3357

Published: Sept. 9, 2024

Over the past several decades, there has been a surge of interest in harnessing functionalization C(sp

Language: Английский

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Recent Advances in Asymmetric Catalysis Using p‐Block Elements

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(9)

Published: Dec. 1, 2023

The development of new methods for enantioselective reactions that generate stereogenic centres within molecules are a cornerstone organic synthesis. Typically, metal catalysts bearing chiral ligands as well organocatalysts have been employed the synthesis compounds. In this review, we highlight recent advances in main group catalysis using p-block elements (boron, aluminium, phosphorus, bismuth) complementary and sustainable approach to molecules. Several these benefit terms high abundance, low toxicity, selectivity, excellent reactivity. This minireview summarises utilisation element asymmetric value-added

Language: Английский

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Borane-Catalyzed Enantioselective α-Alkylation of Unactivated 2-Alkylbenzoxazoles with Electron-Deficient Olefins

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(35), P. 24663 - 24669

Published: Aug. 20, 2024

Chiral borane–catalyzed reactions have recently emerged as a powerful tool for the enantioselective production of chiral scaffolds. In this study, we demonstrated first time that bisborane catalyst can be used α-functionalization 2-alkylazaarenes; specifically, accomplished unprecedented highly α-alkylation unactivated 2-alkylbenzoxazoles with electron-deficient olefins. The strong Lewis acidity and steric bulk were essential to observed reactivity selectivity.

Language: Английский

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Cu(II) complexes with unsymmetrical N3O-type Schiff base ligands: Synthesis, crystal structures, in vitro antiproliferative studies against the human breast (MCF-7), colon (HCT-116) and lung (A549) cancer cell lines, and molecular docking studies

Inorganic Chemistry Communications, Journal Year: 2025, Volume and Issue: unknown, P. 114367 - 114367

Published: March 1, 2025

Language: Английский

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Recent advances in crystallization-induced deracemization of racemic mixtures

Separation and Purification Technology, Journal Year: 2025, Volume and Issue: unknown, P. 133842 - 133842

Published: June 1, 2025

Language: Английский

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Borane‐Catalyzed Asymmetric Reduction of 2‐Alkylpyridines^†

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(23), P. 3088 - 3092

Published: Aug. 8, 2024

Comprehensive Summary Herein, a method for the enantioselective reduction of unprotected 2‐alkylpyridines is reported first time. By using pinacolborane and an amide as reducing agents, large number 2‐alkylpiperidines were synthesized with high yields excellent enantioselectivities via cascade process involving 1,4‐hydroboration subsequent transfer hydrogenation. The resulting products can be easily converted to natural alkaloids.

Language: Английский

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Synthesis of bismuthanyl-substituted monomeric triel hydrides

Chemical Science, Journal Year: 2024, Volume and Issue: 15(36), P. 14837 - 14843

Published: Jan. 1, 2024

The syntheses of first, extremely sensitive donor-stabilized monomeric bismuthanylboranes D·BH 2 Bi(SiMe 3 ) (D = NHC, DMAP) and the bismuthanylgallane IDipp·GaH are presented representing unique element combinations bismuth triels.

Language: Английский

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Zintl Clusters as a Platform for Lewis Acid Catalysis

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(43), P. 20117 - 20125

Published: May 30, 2024

Clusters of the main group elements phosphorus and arsenic, commonly categorized as Zintl clusters, have been known for over a century. And, only now is application these systems catalysts organic synthesis being investigated. In this work, boranes are tethered via an aliphatic linker to Zintl-based clusters their Lewis acidity examined experimentally, by Gutmann–Beckett test competency in hydroborative reduction six substrates, well computationally, fluoride ion affinity hydride methods. The effects tuning length, substituents at boron, changing cluster from seven-atom system arsenic on reactivity studied.

Language: Английский

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Hydrophosphinylation of Alkynes via Neutral Magnesium Complexes: Evidence for Ligand Dependency in Structure-Activity Relationships

Published: Dec. 13, 2024

The pursuit of practical, straightforward, and sustainable methods for forming carbon-phosphorus bonds is crucial in both academia industry. Traditional synthetic often rely on hazardous, halogenated precursors through salt-metathesis routes. In this study, we have synthesized characterized magnesium complexes [L(Mg-nBu)2] (L = bis(diiminate); nBu n-butyl) 1 2. Complex effectively catalyzes the hydrophosphinylation alkynes resulting stepwise hydrophosphinylated products namely monophosphinylated vinyledene- 1,2-diphosphinylated alkanes. While doubly addition with are predominant, catalytic reaction produces anti-Markovnikov inactivated alkenes, whereas activated alkenes giving rise to conjugated products. This transformation showcases an excellent atom economy, broad functional group tolerance gram scale synthesis organophosphorus compounds. Through controlled experiments, kinetic studies, density theoretical calculations, elucidated mechanism, identifying active species revealing a process alkynes. Although complex showed its potential alkynes, 2 3 produced lower yield products, indicating role ligand (spacer) transformation. work first demonstrate that neutral can independently catalyse offers opportunities other compounds catalyzed by main-group metal complexes.

Language: Английский

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