Acyl fluorides have emerged as versatile reagents in various synthetic endeavors, offering a range of advantages over their counterparts, acyl chlorides. This study delves into the properties and reactivity of acyl fluorides, particularly their reaction with amines and alcohols, to elucidate their distinct characteristics. We also introduce a facile and practical synthesis of acyl fluorides from a stable solution of CF3O− salt. Additionally, we establish an efficient one‐pot process for the direct preparation of amides or esters from corresponding acids and amines or alcohols, showcasing the remarkable efficiency of acyl fluorides in these transformations.

Thiocarbamoyl fluoride is an understudied fluorinated group, mainly due to the paucity of data on its properties. Herein, an in-depth study of the stability of thiocarbamoyl fluorides, especially under near-physiological conditions, is described. Since efficient and easy to implement syntheses of these compounds are still under-described, a new method, based on the use of a trifluoromethanesulfenamide, a well-described reagent, has also been developed. This trifluoromethanesulfenamide turned out to be able to generate in situ difluorothiophosgene, which was able to react rapidly with amines to provide various thiocarbamoyl fluorides. image

CO2 reacts with simple amines in presence of water to generate dynamic combinatorial libraries of majority (i.e., am-monium carbamates) and minority (i.e., ammonium carbonates) non-isoenergetic covalent adducts. Over the past decade, our laboratory has reported a new class of cavitands, namely dyn[n]arenes, from which a polyanionic macro-cycle is an highly efficient receptor for linear poly-ammoniums to form [2]pseudorotaxanes in water at neutral pH. Herein, we demonstrate that this formation of [2]pseudorotaxanes shifts the equilibrium of CO2 capture by polyam-ines in water towards the quasi-exclusive formation of carbonate adducts, providing the first example of a switch between two competitive and reversible covalent processes triggered by host-guest interactions. In addition, this su-pramolecular approach to CO2 capture exhibits enhanced capture efficiency by increasing the state of protonation of complexed vs. uncomplexed polyamines. Altogether, we report here that a templating approach can divert the out-come of two reversible covalent chemistries involving nucleophilic additions and acid-base reactions, challenging therefore the common knowledge that non-covalent interactions are weaker bonds than covalent ones.

CO2 reacts with simple amines in the presence of water to generate dynamic combinatorial libraries of majority (i.e., ammonium carbamates) and minority (i.e., ammonium carbonates) nonisoenergetic covalent adducts. Over the past two decades, our laboratory has reported on a new class of cavitands, namely, dyn[n]arenes, from which a polyanionic macrocycle is a highly efficient receptor for linear polyammoniums that forms [2]pseudorotaxanes in water at neutral pH. Herein, we demonstrate that the formation of [2]pseudorotaxanes shifts the equilibrium of CO2 capture by polyamines in water toward the quasi-exclusive formation of carbonate adducts, providing the first example of a switch between two competitive and reversible covalent processes triggered by host-guest interactions. In addition, this supramolecular approach to CO2 capture exhibits enhanced capture efficiency by increasing the state of protonation of complexed vs uncomplexed polyamines. Altogether, we report here that a templating approach can divert the outcome of two reversible covalent chemistries involving nucleophilic additions and acid-base reactions, challenging therefore the common knowledge that noncovalent and covalent bonds operate in separate energy frames.

Flaming treatments have been used at the industry level since the 1950s to improve the chemical reactivity of polyolefins. This treatment allows the grafting of polar functional groups onto the substrate to improve its chemical affinity with paints and adhesives, which is important in fields such as the automotive industry. Therefore, the primary purpose of this study is to identify which groups grafted by flaming treatments are involved in the adhesion between polypropylene long glass fibers (PPGFL) and polyurethane (PU) adhesives, with or without surrounding water. The effect of an alternative low-pressure nitrogen plasma treatment on the PPGFL/PU interface was then studied. The main conclusions arising from the study of flaming are the following. X-ray photoelectron spectroscopy analyses revealed that the flaming treatment grafted four different chemical groups: hydroxyl, ether, ketone, and acid. Model reactions studied using nuclear magnetic resonance spectroscopy showed that only hydroxyl groups played a role in PPGFL/PU adhesion, as long as the environment was not saturated with water. On the other hand, the low-pressure nitrogen plasma study showed that adhesion could also be obtained through amine groups. Model reactions showed that these groups were very reactive with the isocyanates contained in the adhesive; the reaction was complete and immediate. In addition, this particular reaction produced urea groups that were only slightly parasitized by water, which made the process more robust than flaming. This study primarily aims to link the chemical mechanisms occurring at the interface with a macroscopic adhesion measurement of a bonded system. Further, kinetic monitoring allows the comparison of the reaction speed of each grafted group with the adhesive. Consequently, this makes it possible to determine the functional groups that are most important for adhesion and the most efficient and robust treatment method.

Carbamoyl fluoride is a fluorinated group that, to this date, remains underexplored, probably due to the lack of data concerning its properties. In this paper, a study of carbamoyl fluoride is presented. Stability studies, in particular under physiological conditions, and lipophilicity measurement were performed. A new easy, safe, inexpensive, and metal-free synthesis method is also described. Finally, a potential use in radiochemistry through a F-18/F-19 isotopic exchange is demonstrated.

Carbamoyl fluorides are among the emerging fluorinated motifs. but are still quite underexplored. So, an efficient, fast, inexpensive, metal-free and easy-to-perform method to access such compounds easily, even with sophisticated molecules, is described. The physicochemical properties of these compounds were measured to give an insight into the potential of carbamoyl fluorides—in particular, their stability under close-to-physiological conditions. Finally, a first application in radiochemistry to obtain fluorine-18 radiolabeled compounds easily is proposed. More information can be found in the Research Article by F. Toulgoat, T. Billard, and co-workers (DOI: 10.1002/chem.202201589).

The synthesis of trifluoromethylselenolated aromatic molecules via an auxiliary-assisted, palladium catalyzed, C-H bonds functionalization with trifluoromethyl tolueneselenosulfonate as reagent is described. The mono- or bis-products can be preferentially formed. Some mechanistic investigations were realized to better understand the reaction. This methodology was also extended to fluoroalkylselenyl groups.

Monocationic complexes of yttrium with various bis-alkyl and bis-allyl ligands Y(CH2SiMe2Ph)(2)(THF)(4)][B(C6F5)(4)], [Y-(CH2C6H4NMe2)(2)(THF)(2)][B(C(6)Fs)(4)], and [Y[1,3-(SiMe3)(2)C3H3](2) (THF)(2)][B-(C6F5)(4)] have been prepared by protonolysis of the corresponding homoleptic tris-alkyl or -allyl complexes using the anilinium borate salt [PhNMe2H][B-(C6F3)(4)]. The resulting ion-pair complexes have been isolated and characterized by different techniques such as elemental analysis, H-1, C-13, and Y-89 NMR, and EXAFS for the allyl cationic complex [Y[1,3-(SiMe3)(2)C3H3](2) (THF)(2)][B(C(6)Fs)(4)]. More specifically, a H-1-coupled Y-89 INEPT sequence has been developed in order to quantify the metal/alkyl ligand stoichiometry of both synthesized neutral tris-alkyl and cationic bis-alkyl yttrium complexes. The activity of the cationic complexes toward ethylene and isoprene homopolymerization has been assessed. In presence of TiBA, polyethylene was produced with activities ranging from 6 to 26 kg(PE) mol(Y)(-1) h(-1) bar(-1). The molar mass of the yielded polymers shows a bimodal distribution. Under similar conditions, polyisoprene was produced up to full conversion of the monomer. The microstructure of the yielded polyisoprene displayed mainly cis-1,4-units (ca. 60-70%) and 3,4-units (ca. 20-30%). Only a few percent of trans-1,4 units was revealed.

Trifluoromethyl tolueneselenosulfonate is a versatile reagent which can be reduced by iron powder to generate in situ trifluoromethylselenolate anion. This species can then react with alkyl bromide to perform SN2 reaction.

Despite recent advances, trifluoromethoxylation remains a challenging reaction. Here we describe an efficient trifluoromethoxylative substitution, using an inexpensive and easy-to-handle reagent. By mixing DMAP with a slight excess of 1,4-dinitro-trifluoromethoxybenzene (DNTFB), a stable solution of trifluoromethoxide anion is obtained and can be used to perform a SN 2 reaction without any silver additives. A precise study of the properties and behavior of this unusual stable solution of CF3 O- species is also performed.