Rim-differentiated pillar[5]arene-modified surfaces for rapid PFOA/PFOS detection.

A new rim-differentiated pillar[5]arene (RD-P5) has been synthesized and immobilized onto an Al2O3 surface for the rapid detection of perfluoroalkyl acids. This P5-Al2O3 surface provides a novel approach for measuring perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) using contact angle measurements, with limits of detection down to 10 ng L-1.

2-Methylimidazole-1-(N-tert-octyl)sulfonimidoyl Fluoride: A Bench-Stable Alternative to SOF4 as Precursor to N,O-Substituted S(VI) Compounds.

S(VI) compounds with multiple N or O substituents are often difficult to make and several crucial routes, such as multimodal SuFEx (Sulfur (VI) Fluoride Exchange) chemistry, rely on the highly useful but hazardous SOF4 gas. Safety issues and inaccessibility of SOF4 strongly hamper the developments of these organic compounds. Here we describe the synthesis and applications of 2-methylimidazole-1-(N-tert-octyl)sulfonimidoyl fluoride (ImSF), a novel bench-stable analogue of SOF4. ImSF is synthesized on a gram scale via a double fluorination of t-OctNSO. We show ImSF can undergo substitution reactions with phenols and amines, which lead to sulfurimidates and sulfuramidimidates, respectively, the intrinsically chiral analogous of medicinally relevant sulfates and sulfamates in which an S=O moiety is replaced by S=NR unit. Finally we demonstrate that such substitutions can occur enantiospecifically, providing the first entry to chiral sulfurimidates and sulfuramidimidates.

2D and 3D Self-Assembly of Fluorine-Free Pillar-[5]-Arenes and Perfluorinated Diacids at All-Aqueous Interfaces.

The interaction of perfluorinated molecules, also known as "forever chemicals" due to their pervasiveness, with their environment remains an important yet poorly understood topic. In this work, the self-assembly of perfluorinated molecules with multivalent hosts, pillar-[5]-arenes, is investigated. It is found that perfluoroalkyl diacids and pillar-[5]-arenes rapidly and strongly complex with each other at aqueous interfaces, forming solid interfacially templated films. Their complexation is shown to be driven primarily by fluorophilic aggregation and assisted by electrostatic interactions, as supported by the crystal structure of the complexes, and leads to the formation of quasi-2D phase-separated films. This self-assembly process can be further manipulated using aqueous two-phase system microdroplets, enabling the controlled formation of 3D micro-scaffolds.

Rim-Based Binding of Perfluorinated Acids to Pillararenes Purifies Water.

Per- and polyfluoroalkyl substances (PFAS) pose a rapidly increasing global problem as their widespread use and high stability lead worldwide to water contamination, with significant detrimental health effects.[1] Supramolecular chemistry has been invoked to develop materials geared towards the specific capture of PFAS from water,[2] to reduce the concentration below advisory safety limits (e.g., 70 ng/L for the sum of perfluorooctane sulfonic acid, PFOS and perfluorooctanoic acid, PFOA). Scale-up and use in natural waters with high PFAS concentrations has hitherto posed a problem. Here we report a new type of host-guest interaction between deca-ammonium-functionalized pillar[5]arenes (DAF-P5s) and perfluoroalkyl acids. DAF-P5 complexes show an unprecedented 1 : 10 stoichiometry, as confirmed by isothermal calorimetry and X-ray crystallographic studies, and high binding constants (up to 106 M-1) to various polyfluoroalkyl acids. In addition, non-fluorinated acids do not hamper this process significantly. Immobilization of DAF-P5s allows a simple single-time filtration of PFAS-contaminated water to reduce the PFOS/PFOA concentration 106 times to 15-50 ng/L level. The effective and fast (<5 min) orthogonal binding to organic molecules without involvement of fluorinated supramolecular hosts, high breakthrough capacity (90 mg/g), and robust performance (>10 regeneration cycles without decrease in performance) set a new benchmark in PFAS-absorbing materials.

Synthesis and Reactivity of Ruthenium(BINAP)(PPh3).

Ru(BINAP)(PPh3)HCl cleanly reacts with LiCH2TMS to give Ru(BINAP)(PPh3) (1) that has been fully characterized, including by X-ray diffraction (BINAP and TMS stand for (2,2'-bis(diphenylphosphino)-1,1'-binaphthyl and trimethylsilyl respectively). In sharp contrast with other carbonyl-free phosphine complexes of Ru(0), 1 demonstrates a strikingly high thermal stability and no propensity for intramolecular C-H activation (cyclometalation). Yet 1 coordinates acetonitrile and readily exchanges its PPh3 ligand with alkenes and dienes, thus behaving like a "masked" 16-e Ru(0) species. Electron-poor alkenes coordinate more readily than electron-rich ones, which testifies for the nucleophilic character of the Ru(0)-BINAP fragment. While being thermally stable, 1 is highly reactive and is capable of activating C-H and N-H bonds, and even of cleaving an inert N-Et bond. The combination of high reactivity and stability originates from the P,arene-chelation by the BINAP ligand, i.e., the coordinated π-arene stabilizes Ru(0) to prevent cyclometalation, yet it can slide upon substrate coordination, thereby enabling a variety of inert bond activation reactions to occur under mild conditions.

A Platform for the Liebeskind-Srogl Coupling of Heteroaromatic Thioethers for Medicinal-Chemistry-Relevant Transformations.

General and robust conditions for the Liebeskind-Srogl coupling were developed and used in functionalization of medicinal-chemistry-relevant heterocyclic substrates. Applicability in HTE and library synthesis, combined with its orthogonality to other cross-coupling reactions, make it highly attractive for discovery chemistry workflows. Additionally, the results suggest that the nature of the Cu(I)-carboxylate plays a more prominent role in the reaction performance than the nature of Pd-catalysts, which is rather uncommon for Pd-catalysis and can be used in further optimization of Liebeskind-Srogl coupling.