Outer-Sphere Electrophilic Fluorination of Organometallic Complexes.
Organofluorine chemistry plays a key role in materials science, pharmaceuticals, agrochemicals, and medical imaging. However, the formation of new carbon-fluorine bonds with controlled regiochemistry and functional group tolerance is synthetically challenging. The use of metal complexes to promote fluorination reactions is of great current interest, but even state-of-the-art approaches are limited in their substrate scope, often require activated substrates, or do not allow access to desirable functionality, such as alkenyl C(sp(2))-F or chiral C(sp(3))-F centers. Here, we report the formation of new alkenyl and alkyl C-F bonds in the coordination sphere of ruthenium via an unprecedented outer-sphere electrophilic fluorination mechanism. The organometallic species involved are derived from nonactivated substrates (pyridine and terminal alkynes), and C-F bond formation occurs with full regio- and diastereoselectivity. The fluorinated ligands that are formed are retained at the metal, which allows subsequent metal-mediated reactivity.
Department of Chemistry, University of York , Heslington, York YO10 5DD, United Kingdom.
Lucy M
LM
Milner
Department of Chemistry, University of York , Heslington, York YO10 5DD, United Kingdom.
Natalie E
NE
Pridmore
Department of Chemistry, University of York , Heslington, York YO10 5DD, United Kingdom.
Adrian C
AC
Whitwood
Department of Chemistry, University of York , Heslington, York YO10 5DD, United Kingdom.
Jason M
JM
Lynam
Department of Chemistry, University of York , Heslington, York YO10 5DD, United Kingdom.
John M
JM
Slattery
D004583:Electrons; D054879:Halogenation; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D013237:Stereoisomerism
D009942:Organometallic Compounds