Facile Catalyst Separation Without Water: Fluorous Biphase Hydroformylation of Olefins

• Published in: Science (American Association for the Advancement of Science) Vol. 266; no. 5182; pp. 72 - 75
• Main Authors: HORVATH, IT, RABAI, J
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Society for the Advancement of Science 07.10.1994; Amer Assoc Advancement Science; American Association for the Advancement of Science
• Subjects: Alkenes; Catalysis; Catalysts; Catalytic reactions; Chemical processes; Chemical reactions; Chemistry; Exact sciences and technology; Fluorocarbons; General and physical chemistry; Hydrocarbons; Innovations; Multidisciplinary Sciences; Organic compound synthesis; Organic compounds; Phosphines; Reagents; Rhodium; Room temperature; Science & Technology; Science & Technology - Other Topics; Solubility; Solvents; Synthesis; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; PHASE; COMPLEXES; Rhodium Carbonyl Complexes; Phase transfer catalysis; Catalytic reaction; Organic perhalocompound; Organic ligand; Transition metal Carbonyl Complexes; Fluorocarbon; Experimental study; Platinoid Carbonyl Complexes; Biphasic system; Phase separation; Hydroformylation; Catalyst; Ethylenic compound
• ISSN: 0036-8075; 1095-9203
• DOI: 10.1126/science.266.5182.72

A novel concept for performing stoichiometric and catalytic chemical transformations has been developed that is based on the limited miscibility of partially or fully fluorinated compounds with nonfluorinated compounds. A fluorous biphase system (FBS) consists of a fluorous phase containing a dissolved reagent or catalyst and another phase, which could be any common organic or nonorganic solvent with limited or no solubility in the fluorous phase. The fluorous phase is defined as the fluorocarbon (mostly perfluorinated alkanes, ethers, and tertiary amines)-rich phase of a biphase system. An FBS compatible reagent or catalyst contains enough fluorous moieties that it will be soluble only or preferentially in the fluorous phase. The most effective fluorous moieties are linear or branched perfluoroalkyl chains with high carbon number; they may also contain heteroatoms. The chemical transformation may occur either in the fluorous phase or at the interface of the two phases. The application of FBS has been demonstrated for the extraction of rhodium from toluene and for the hydroformylation of olefins. The ability to separate a catalyst or a reagent from the products completely at mild conditions could lead to industrial application of homogeneous catalysts or reagents and to the development of more environmentally benign processes.