Synthesis 2017; 49(04): 810-821
DOI: 10.1055/s-0036-1588663
short review
© Georg Thieme Verlag Stuttgart · New York

Functionalisation of Carbon–Fluorine Bonds with Main Group Reagents

Wenyi Chen, Clare Bakewell, Mark R. Crimmin*
Further Information

Publication History

Received: 17 October 2016

Accepted after revision: 31 October 2016

Publication Date:
08 December 2016 (eFirst)

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 sp2 C–F bonds.

1 Introduction

2 C–F Borylation of Aromatic sp2 C–F Bonds

2.1 Rhodium Catalysis

2.2 Nickel Catalysis

3 C–F Alumination of sp2 C–F Aromatic and sp3 C–F Aliphatic Bonds

4 C–F Silylation and Germylation of Aromatic sp2 C–F Bonds

5 C–F Magnesiation of Aromatic sp2 C–F Bonds

6 C–F Silylation and Borylation of Alkenes

7 Conclusions and Future Directions