Palladium-Catalyzed Difluoroalkylation of Isocyanides: Access to Difluoroalkylated Phenanthridine Derivatives

An efficient and general method for the synthesis of difluoroalkylated phenanthridine derivatives through palladium-catalyzed reaction of difluoroalkyl bromides with isocyanides is described. The reaction can also be extended to perfluoroalkyl iodides. Mechanistic studies reveal that a difluoroalkyl radical via a single-electron-transfer pathway is involved in the reaction

Copper Catalyzed Cross-Coupling of Iodobenzoates with Bromozinc-difluorophosphonate

A copper-catalyzed cross-coupling of iodobenzoates with bromozinc-difluorophosphonate, generated from diethyl bromodifluoromethylphosphonate and zinc in dioxane, is reported. The notable features of this reaction are its high reaction efficiency, excellent functional group compatibility, and operational simplicity. This protocol provides a useful and facile access to aryldifluorophosphonates of interest in life science

Copper-Catalyzed Dehydrogenative Cross-Coupling of Benzothiazoles with Thiazoles and Polyfluoroarene

A copper-catalyzed dehydrogenative cross-coupling of benzothiazoles with thiazoles and polyfluoroarene under mild reaction conditions is described. This protocol provides a straightforward and operationally simple method for the synthesis of the 2,2′-linkage of thiazoles and 2-polyfluoroarylthiazoles of interest in life and material sciences

Access to Difluoromethylated Arenes by Pd-Catalyzed Reaction of Arylboronic Acids with Bromodifluoroacetate

An unprecedented example of Pd-catalyzed difluoromethylation of aryl boronic acids with bromodifluoroacetate is described. The reaction proceeds under mild reaction conditions with hydroquinone and Fe­(acac)₃ as additives. Preliminary mechanistic studies reveal that a difluorocarbene pathway is involved in the reaction, which is unusual compared to the most traditional approaches. This reaction has advantages of high efficiency and excellent functional group compatibility, even toward bromide and hydroxy group, thus providing a useful protocol for drug discovery and development

Highly Selective Pd-Catalyzed Direct C–F Bond Arylation of Polyfluoroarenes

A directing-group-free palladium-catalyzed direct arylation of simple polyfluoroarenes with arylboronic acids through selective C–F bond activation is described. The combination of Pd­(OAc)₂ with BrettPhos was identified as an efficient catalytic system to promote the reaction with high regioselectivity and broad substrate scope. Preliminary mechanistic studies reveal that the oxidative addition of Pd to the C–F bond is involved in the catalytic cycle

Pd-Catalyzed Direct Arylation of Polyfluoroarenes on Water under Mild Conditions Using PPh₃ Ligand

We report a Pd-catalyzed direct arylation of polyfluoroarenes with aryl iodides. The advantages of this reaction are its high reaction efficiency, excellent functional group compatibility, mild reaction conditions (70 °C), inexpensive PPh₃ ligand, and use of pure water as reaction medium. The usefulness of this reaction has also been demonstrated by rapid preparation of highly functionalized polyfluoroarenes via iterative Pd-catalyzed C–H bond functionalization

Palladium-Catalyzed Aerobic Dehydrogenative Cross-Coupling of Polyfluoroarenes with Thiophenes: Facile Access to Polyfluoroarene–Thiophene Structure

We report a Pd-catalyzed aerobic dehydrogenative cross-coupling of polyfluoroarenes with thiophenes via 2-fold C–H functionalization. The advantages of this reaction are its high reaction efficiency, excellent functional group compatibility, and use of molecular O₂ as terminal oxidant. This reaction provides a useful and facile protocol for the preparation of polyfluoroarene–thiophene structure of interest in functional materials. Mechanistic studies revealed that the reaction is initiated by the C–H bond cleavage of polyfluoroarenes

Nickel-Catalyzed Reductive Cross-Coupling of (Hetero)Aryl Iodides with Fluorinated Secondary Alkyl Bromides

A mild and efficient nickel-catalyzed reductive cross-coupling between fluorinated secondary alkyl bromides and (hetero)­aryl iodides is described. The use of FeBr₂ as an additive successfully overcomes the hydrodebromination and β-fluorine elimination of fluorinated substrates and allows the efficient synthesis of a wide range of trifluoromethyl and difluoroalkyl containing aliphatic compounds with a fluoroalkyl substituted tertiary carbon center. The notable features of this protocol are the synthetic and operational simplicity without preparation of moisture sensitive organometallic reagents and excellent functional group compatibility, even toward active proton containing substrates

Heteroaryldifluoromethylation of Organoborons Catalyzed by Palladium: Facile Access to Aryl(Heteroaryl)difluoromethanes

A first example of Pd-catalyzed heteroaryldifluoromethylation of organoborons with bromodifluoromethylated heteroarenes has been described. The use of phosphine ligand PAd₂(<i>n</i>-Bu)·HI is critical for the reaction efficiency. With use of this ligand, a wide range of aryl­(heteroaryl)­difluoromethanes were obtained with high efficiency. The notable features of this reaction are its broad substrate scope and excellent functional group compatibility, thus providing a facile protocol for application in drug discovery and development

Correction to “Copper-Catalyzed Direct Propargylation of Polyfluoroarenes with Secondary Propargyl Phosphates”

Correction to “Copper-Catalyzed Direct Propargylation of Polyfluoroarenes with Secondary Propargyl Phosphates