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 alpha 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 proper-ties of starting fluoroalkyl complexes and relative stereocenter configurations for diastereomeric products, together with kinetic studies of reactions in different solvents, allow a self-consistent mechanism for these reactions to be established. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)