Mechanistic Insights into Copper-Mediated Benzylic C(sp³)−H Bond Trifluoromethylation

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

The trifluoromethylation of primary and secondary benzylic C(sp 3 )−H bonds by Cu II species proceeds via a radical recombination/reductive elimination pathway, while tertiary prefer the single-electron transfer (SET) pathway.

Language: Английский

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Kinetico‐Mechanistic Studies of Cu(II)‐Mediated Cyclization of Imines via C–H Bond Activations§

European Journal of Inorganic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 16, 2024

Abstract Herein, we focus on the kinetico‐mechanistic studies of a carboxylate and Cu(II)‐assisted synthesis imidazo[1,5‐ ]pyridines encompassing C(sp 3 )−H amination cyclization imines coupled with 2 cyanation using time‐resolved UV‐Vis reaction monitoring ex‐situ analyses. Thus, kinetic have been carried out, providing proof elementary steps involved, allowing for batch analysis compounds present in solution via MS. The experimental data obtained are consistent formation cyclometalated complex ( k 1 ) involving bond cleavage followed by reductive elimination/proton abstraction event ), both showing high enthalpy‐demanding transition states. two processes show well‐defined Eyring behavior values Δ H ≠ S within expected range. Further insights intermediate fast )–cyanation also presented together control reactions.

Language: Английский

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Copper-Catalyzed Difluoromethylation of Alkenyl Thianthrenium Salts

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

Published: Dec. 5, 2024

We have developed a novel and straightforward protocol that facilitates the transformation of alkenylsulfonium salts leading to direct synthesis

Language: Английский

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