Organometallic Fluorine Chemistry

Table of Contents

1. Frontmatter

2. Transition Metal-Mediated and Metal-Catalyzed Carbon–Fluorine Bond Formation

   Michael G. Campbell, Andrew J. Hoover, Tobias Ritter

   Abstract

   The development of new C–F bond forming reactions from organotransition metal complexes has played a key role in advancing the field of fluorination chemistry and has allowed for improved access to fluorinated organic molecules of interest in medicine, materials, and agrochemicals. In this review, we describe the development of transition metal-mediated and metal-catalyzed fluorination methods over the past decade. Special attention is paid to the variety of organometallic mechanisms by which C–F bond formation can occur and the strengths and limitations of different approaches.

3. Activation and Formation of Aromatic C–F Bonds

   Nicole A. LaBerge, Jennifer A. Love

   Abstract

   The presence of aryl C–F bonds in pharmaceuticals and agrochemicals is increasing rapidly. Incorporation of a fluorine substituent into biologically relevant molecules yields many benefits such as decreased metabolism, solubility, hydrophobicity and decreased negative side effects. Since there are no known examples of naturally occurring aryl fluorides all must be accessed through chemical synthesis. The formation and activation of aryl C–F bonds is a challenging endeavor, nevertheless several strategies are possible. Recent developments towards the synthesis of fluoroaromatics, as well as routes to selectively remove fluorine from polyfluoroaromatics are surveyed.

4. Transition-Metal-Catalyzed Difluoromethylation, Difluoromethylenation, and Polydifluoromethylenation Reactions

   Bo Chen, David A. Vicic

   Abstract

   One way to introduce fluorine into a molecule is through fluoroalkylation reactions. Transition-metal catalysts play an increasing role in selectively incorporating fluoroalkyl groups into organic molecules, especially during the late stages of a synthesis. In this review, we highlight the development of methodologies to incorporate the [CF₂H], [CF₂R], and [(CF₂) _n ] functionalities into organic substrates by transition-metal complexes. Also discussed are the structural changes that can arise when repeating arrays of [CF₂] or [CH₂CF₂] units are introduced into a single molecule through polydifluoromethylenation reactions.

   Graphical Abstract

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5. Hydrodefluorination Reactions Catalyzed by Transition-Metal Complexes

   Ji-Yun Hu, Jun-Long Zhang

   Abstract

   Activation of the C–F bond by transition-metal catalysts not only advances fundamental understanding of the formation and reactivity of organometallic fluoride complexes but also provides a potential approach to partially fluorinated organic compounds from readily available perfluorinated bulk chemicals. Hydrodefluorination (HDF) is regarded as a simple but important reaction among various C–F functionalizations, which features a mechanistic diversity as model reactions for C–F bond activations. Following Lentz and Braun’s review (Angew Chem Int Ed 52, 3328–3348, 2013), we review transition-metal-mediated HDF reactions according to periodic table from group 3–12 metals.

6. Catalytic Transformations of Fluorinated Olefins

   Masato Ohashi, Sensuke Ogoshi

   Abstract

   Progress in the development of catalytic transformation reactions of fluorinated olefins is reviewed. Four different types of transition-metal-catalyzed transformations have been distinguished: (a) oligomerization, (b) hydrodefluorination, (c) C–X bond formation via C–F bond cleavage, and (d) C–C bond formation via C–F bond cleavage.

7. Fluorous Organometallic Chemistry

   Eric G. Hope, Rena Simayi, Alison M. Stuart

   Abstract

   The synthesis, characterisation and application of organometallic complexes functionalised with fluorous substituents are reviewed.

8. Backmatter