Conversion of Carbon–Fluorine Bonds α to Transition Metal Centers to Carbon–Hydrogen, Carbon–Carbon, and Carbon–Heteroatom Bonds

Pseudo‐tetrahedral primary fluoroalkyl complexes of iridium provide a template on which to study the stereoselectivity of carbon–fluorine bond activation α to iridium by external protic acids. Coupled with migration of internal nucleophiles, this reaction leads to diastereoselective formation of new carbon–oxygen, carbon–sulfur, carbon–hydrogen, and carbon–carbon bonds. Stereochemical studies of the conformational properties of starting fluoroalkyl complexes and relativestereocenter configurations for diastereomeric products, together with kinetic studies of reactions in different solvents, allow a self‐consistent mechanism for these reactions to be established. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)