Despite its long history as an active area of research,fluorine chemistry is currently undergoing a surge of activity,particularly in the development of new and selective methods for fluorinating organic molecules and for engaging the strong C-F bond in chemistry of its own. Molecules containing carbon-fluorine bonds play signifi cant positive and sometimes deleterious roles in the lives of human beings. Half of the top 10 drugs sold contain C-F bonds,as do about 20% of all pharmaceuticals and 30-40% of agrochemicals.As a result, the importance of the introduction of strategically placed C-F, C-CF, and C-CF,H bonds in pharmaceutical, medicinal, and bioorganic chemistry has led to the development of new methodology for their selective generation. Methods for late-stage introduction of fluorine in synthesis have also burgeoned, due to the need for rapid introduction of short-lifetimeF into Positron Emission Tomography markers. Fluorinated materials, such as Teflon and other tailored fluoropolymers, continue to have a positive impact on the quality of human life, and their physical properties and chemical inertness are often a boost to technological advances.Positive societal roles of fluorocarbons are sometimes offset by deleterious environmental effects. Accumulated atmospheric chlorofluorocarbons, now banned under the Montréal Protocol, contribute to ozone depletion and global warming. Hvdrofluorocarbons,important in applications such as refrigerants,aerosols, foaming agents,inhalation anesthetics, and semiconductor cleaning solvents, are more environmentally benign. However, many saturated perfluorocarbons and their derivatives, used as cleaning agents and solvents for chemical separations and catalysis, have significant global warming potential,and environmental lifetimes of thousands of years because there is no environmental mechanism for their degradation.Fluorine forms the strongest single bond to carbon,and the selective introduction or chemical manipulation of C-F bonds is a serious challenge to the imaginative chemist. Many of the methods for introduction of fluorine atoms and fluoroalkyl substituents into organic scaffolds involve organometallic reactions and catalysis.This volume presents reviews of recent advances from expert practi- tioners in the field.We begin with an extensive review from Campbell, Hoover,and Ritter on stoichiometric and catalytic methods for the introduction of fluorine into organic molecules,with reference to late stage fluorination methods.Second comes a comprehensive review by the LaBerge and Love on the selective introduction and manipulation of C-F bonds in aromatic systems using transition metal reagents. Reviews on C-F bond formation are followed by the discussion by Chen and Vicic on catalytic C-C bond formation methods for the introduction of -CF,H and=CF2 groups using transition metal complexes.A replacement of a C-F bond by a C-H bond in fluorinated molecules to access new building blocks is the focus of the review of Hu and Zhang on catalytic hydro defluorination methods.This is complemented by a discussion of catalytic transformations, mainly by C-F bond activation,of fluorinated olefins by Ohashi and Ogoshi.Finally an update on the remarkable application of the physical properties of long fluorous chains in organometallic compounds is provided by Hope, Simayi and Stuart. Berlin, Germany Thomas Braun Hanover,NH, USA Russell P.Hughes

Transition Metal-Mediated and Metal-Catalyzed Carbon-Fluorine Bond Formation 1 Michael G. Campbell, Andrew J.Hoover,and Tobias Ritter

Activation and Formation of Aromatic C-F Bonds 55 Nicole A. LaBerge and Jennifer A. Love

Transition-Metal-Catalyzed Difluoromethylation,Difluoromethylenation,and Polydifuoromethylenation Reactions 113 Bo Chen and David A. Vicic

Hydrodefluorination Reactions Catalyzed by Transition-Metal Complexes 143 Ji-Yun Hu and Jun-Long Zhang

Catalytic Transformations of Fluorinated Olefins 197 Masato Ohashi and Sensuke Ogoshi

Fluorous Organometallic Chemistry 217 Eric G. Hope, Rena Simayi, and Alison M. Stuart

Index 241

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