Functionalisation of Carbon–Fluorine Bonds with Main Group Reagents

Abstract Synthetic approaches to produce reactive chemical building blocks from fluorinated molecules by the functionalization of carbon–fluorine bonds with main group reagents are reviewed. The reaction types can be categorized as: (i) the formal 1,2-addition of C–F bonds across Si–Si, B–B, or Mg–Mg bonds; (ii) the oxidative addition of C–F bonds to Si(II), Ge(II), and Al(I) centres; and (iii) the dehydrogenative coupling of C–F bonds with Al–H or B–H bonds. Many of the advances have emerged between 2015–2016 and are largely focused upon aromatic substrates that contain sp 2 C–F bonds. 1 Introduction 2 C–F Borylation of Aromatic sp 2 C–F Bonds 2.1 Rhodium Catalysis 2.2 Nickel Catalysis 3 C–F Alumination of sp 2 C–F Aromatic and sp 3 C–F Aliphatic Bonds 4 C–F Silylation and Germylation of Aromatic sp 2 C–F Bonds 5 C–F Magnesiation of Aromatic sp 2 C–F Bonds 6 C–F Silylation and Borylation of Alkenes 7 Conclusions and Future Directions