Fluorous Catalysis: From the Origin to Recent Advances

Abstract

Among the various strategies developed in the last two decades to recycle catalysts, fluorous catalysis has emerged as one of the most powerful approaches as it combines the advantages of homogeneous catalysis for reactivity (molecular catalysts, most often reactions conducted in one-phase homogeneous conditions) and heterogeneous catalysis for catalyst recovery (liquid/liquid- or solid/liquid-phase separation protocols). Of particular interest is the general character of this approach and the variety and efficiency of separation protocols available to recover catalysts.

Anion-Initiated Trifluoromethylation by TMSCF3: Deconvolution of the Siliconate–Carbanion Dichotomy by Stopped-Flow NMR/IR

“…The inclusion of fluorine substituents in organic molecules is of pivotal importance to developments in, inter alia , pharmaceuticals, 1 agrochemicals, 2 electronics, 3 materials chemistry, 4 polymers, 5 synthesis, 6 and catalysis. 7 The transfer of a formally nucleophilic CF 3 -moiety to an electrophile is a preeminent method for the synthesis of trifluoromethylated compounds. 8 Conditions range from base-mediated reactions with fluoroform (CF 3 H) 9 through to finely tuned borazine-based CF 3 carriers recently reported by Szymczak.…”

Charge-tagged ligands: useful tools for immobilising complexes and detecting reaction species during catalysis

“…Indeed, an incorrect solvent pairing can lead to low conversions, poor product extraction, no phase separation and catalyst lixiviation. 2 Historically, one of the best strategies to avoid lixiviation is to insert organic moieties into the ligand structure with the same features for anchoring the media, 3 for example fluorinated ligands in organofluorinated solvents, 4,5 polyethyleneglycol (PEG)-substituted ligands in PEG media 6–8 and charged ligands in highly polar solvents. 9–11 …”