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Abstract: While acid fluorides can readily be made from widely available or biomass‐feedstock‐derived carboxylic acids, their use as functional groups in metal‐catalyzed cross‐coupling reactions is rare. This report presents the first demonstration of Pd‐catalyzed decarbonylative functionalization of acid fluorides to yield trifluoromethyl arenes (ArCF3). The strategy relies on a Pd/Xantphos catalytic system and the supply of fluoride for transmetalation through intramolecular redistribution to the the Pd center. This strategy eliminated the need for exogenous and detrimental fluoride additives and allows Xantphos to be used in catalytic trifluoromethylations for the first time. Our experimental and computational mechanistic data support a sequence in which transmetalation by R3SiCF3 occurs prior to decarbonylation. [ABSTRACT FROM AUTHOR]

A novel method for the conversion of vinyl triflates into α-trifluoromethylated ketones in the absence of external trifluoromethyl sources is described. This process accomplishes an efficient migration of the trifluoromethyl group of the triflate to the α-position in the ketone through a radical process. The reaction proceeds by the addition of a trifluoromethyl radical to the vinyl triflate and subsequent fragmentation of the trifluoromethane sulfonyl radical. Based on this reaction, a one-pot two-step procedure for the trifluoromethylation of ketones was developed. The method presented herein also allows the transfer of perfluoroalkyl groups from vinyl perfluoroalkanesulfonates, which are readily accessible from alkynes and perfluoroalkanesulfonic acids. [ABSTRACT FROM AUTHOR]

RBF3K is a chemist's BFF: A metal‐free synthetic route to unprecedented organoboron compounds bearing an α‐trifluoromethyl substituent, employing a variety of trifluoroborate (RBF3K) starting materials, is reported. These substrates represent the first isolated α‐trifluoromethylated alkylboron building blocks, and these reagents lead to a variety of useful bench‐stable, synthetic intermediates. Pin=pinacol. [ABSTRACT FROM AUTHOR]

The incorporation of fluorine-containing moieties into organic compounds is of great importance in pharmaceutical, agricultural, and materials science. Transition-metal-mediated perfluoroalkylation reactions have been studied in the past few decades and, owing to need for low-cost and environmentally friendly processes in the industrial and academic communities, the catalytic reaction has attracted much attention and has become a hot research field. Herein, an overview of recent advances on transition-metalcatalyzed trifluoromethylation and difluoromethylation reactions is given. Trifluoromethylthiolation and trifluoromethoxylation reactions are also reviewed. 1 Introduction 1.1 Transition-Metal-Trifluoromethyl Complexes 1.2 Stoichiometric Trifluoromethylation 2 Transition-Metal-Catalyzed Trifluoromethylation 2.1 Copper-Catalyzed Reactions 2.2 Palladium-Catalyzed Reactions 2.3 Other Transition-Metal-Catalyzed Reactions 3 Difluoromethylation 3.1 Direct Difluoromethylation 3.2 Indirect Difluoromethylation 4 Trifluoromethylthiolation 5 Trifluoromethoxylation 6 Conclusion [ABSTRACT FROM AUTHOR]

The article presents a study which examines a radical trifluoromethylation of olefins through applying the Langlois reagent. It notes that unactivated olefins have been used as the starting materials. It states that using an olefin as the synthetic precursor instead of a preformed substrate makes the method advantageous. It mentions that mild reaction conditions, wide functional-group tolerance, and the use of an inexpensive trifluoromethylating agent are the main features of the reaction.

Copper capabilities: Diazonium salts are converted into the corresponding trifluoromethyl derivatives in the presence of a trifluoromethyl–copper complex generated in situ from CuSCN and the inexpensive, easy‐to‐use trifluoromethylating reagent Me3Si‐CF3 (see scheme). This Sandmeyer‐type reaction allows the straightforward synthesis of trifluoromethylated arenes and heteroarenes from the corresponding amines. [ABSTRACT FROM AUTHOR]

Abstract: Aryl(methoxy)(trifluoromethyl)boranes, generated in situ, readily react with ethyl diazoacetate and N-(4-methoxyphenyl)imines to give derivatives of β-amino acids. In this process, the electron-deficient borane reacts with the diazo compound followed by trapping of the intermediate boron enolate by the imine. The final products are predominantly produced as syn isomers. [Copyright &y& Elsevier]