Formal meta-C–H-Fluorination of Pyridines and Isoquinolines through Dearomatized Oxazinopyridine Intermediates

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(45), P. 30758 - 30763

Published: Nov. 1, 2024

Organofluorine compounds, including fluorinated pyridines and isoquinolines, play a crucial role in pharmaceuticals, agrochemicals, materials science. However, step-economic selective C-H-functionalization to access these azaarenes is still underexplored, with

Language: Английский

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Trinuclear Borane (B₃H₇)-Mediated Selective C4–H Alkylation and Phosphonation of Quinolines and Tetrahydroquinolines

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

Published: Jan. 1, 2025

Herein, we report a method for the regioselective alkylation and phosphonation of quinoline C4–H via B3H7-mediated nucleophilic addition Turbo Grignard reagents phosphine oxide anions to quinolines bearing different substituents, affording 4-alkyl 4-phosphoryl tetrahydroquinolines after one-pot oxidation or reduction. The results indicate that coordination B3H7 group can activate substrates toward potential 1,4-dearomative subtly control regioselectivity by preventing 1,2-dearomative addition.

Language: Английский

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Synthesis, structures, and optical properties of N-heterocycle and amino acid ester-coordinated B₃H₇

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

Published: Jan. 1, 2025

Starting from NMe 4 [B 3 H 8 ], various N-Het·B 7 and AAE·B complexes have been synthesized under mild conditions with moderate to high yields, the optical properties of representative products preliminarily studied.

Language: Английский

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Advances in Pyridine C – H Functionalizations: Beyond C2 Selectivity

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 31(2)

Published: Nov. 28, 2024

The pyridine core is a crucial component in numerous FDA-approved drugs and Environmental Protection Agency (EPA) regulated agrochemicals. It also plays significant role ligands for transition metals, alkaloids, catalysts, various organic materials with diverse properties, making it one of the most important structural frameworks. However, despite its significance, direct selective functionalization still relatively underdeveloped due to electron-deficient nature strong coordinating ability nitrogen. Among variety synthetic transformation, C-H bond straightforward atom economical approach it's advantageous late-stage containing drugs. In recent years, innovative strategies regioselective pyridines azines have emerged, offering benefits such as high regioselectivity, mild conditions, enabling transformations that were challenging traditional methods. This review emphasizes latest advancements meta para-C-H through approaches, including phosphonium salts, photocatalytic methods, temporary de-aromatization, Minisci-type reactions, metal-catalyzed activation techniques. We discuss advantages limitations these current methods aim inspire further progress this field.

Language: Английский

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On the road to isolable geminal carbodications

Chem, Journal Year: 2024, Volume and Issue: 10(11), P. 3294 - 3308

Published: Oct. 10, 2024

Language: Английский

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Nucleophilic Dearomatization of Activated Pyridines Using Vinyl Sulfoxonium Ylides: Application to the Synthesis of Bis-Heterocycles

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

Published: Dec. 5, 2024

A highly efficient method has been developed for synthesizing 4-dienyl dihydropyridines through the nucleophilic dearomatization of activated pyridines using vinyl sulfoxonium ylides. This reaction follows sequence involving ylide addition to pyridine, [2,3]-sigmatropic rearrangement, and subsequent sulfenic acid elimination. The resulting are then used in synthesis substituted bis-heterocyles. Control experiments quantum chemical calculations were conducted elucidate selectivity mechanistic pathway.

Language: Английский

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