C−H•••F−C Interactions: A Guide for Designing Fluorous Monodentate Ligands for the Highly Linear-Selective Hydroformylation at Near-Ambient Pressure

Organofluorine compounds often exhibit unique catalytic capabilities with novel structural scaffold, reactivity and mechanisms. Herein, we report a Rh-catalyzed hydroformylation under mild conditions using monodentate phosphite ligands P(OCH2CF3)3 (TTFP) and P(OCH2CF2CH3)3 (TDFP). The ligand were designed with the principle that the inclusion of fluorine-rich group can significantly change the physical and chemical properties of the complex through H•••F hydrogen bonds, the existence of which has been confirmed by crystal-packing studies. These monodentate phosphite ligands self-assemble to form bidentate ligands through C–H•••F–C interactions, and catalysts based on these ligands deliver extremely high regioselectivities in hydroformylation. Aldehydes were formed with up to 92% chemoselectivity, with linear aldehydes formed in high regioselectivity (n:iso=28/1) under a syngas pressure of only 2 atm.

Efficient modular phosphorus-containing ligands for stereoselective catalysis

Over several years, our research team has contributed to ligand design for metal-catalyzed stereoselective transformations. This has been achieved with the synthesis and application to organic transformations of interest of an array of structurally diverse P-containing ligands. These range from highly modular enantiopure phosphine–phosphite ligands to supramolecularly regulated enantioselective phosphorus-based catalysts. Our research in supramolecular interactions has also led to the discovery of an unprecedented halogen-bonded rhodium-catalyst.