The use of fluorinated alcohols as solvents, cosolvents or additives in homogeneous catalysis is reviewed. The effect of these particular compounds on efficiency, regioselectivity and stereoselectivity of metal-catalyzed reactions, as well as on reactions mediated by organocatalysts, is described. Where available in several cases, the effect of fluorous alcohols on the catalytic mechanism is analyzed in detail and rationalized by their unique physical and chemical properties. In most instances, a comparison to the effect of commonly employed solvents is elaborated.
A penny saved is a penny earned: The use of propylene carbonate as the solvent in iridium‐catalyzed hydrogenations of nonfunctionalized olefins allows efficient catalyst recycling through the formation of two‐phase mixtures with nonpolar solvents such as n‐hexane. In the picture, the hydrogenated tetrahydronaphthalene derivative is extracted into the hydrocarbon phase.
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