Advances in Organic Synthesis

Volume: 2

Modern Organofluorine Chemistry-Synthetic Aspects

Indexed in: Chemical Abstracts, EBSCO, Ulrich's Periodicals Directory

The volume focuses on recent advances in organofluorine chemistry directed towards selective fluorine introduction into various target molecules, employing both traditional and contemporary, ...
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Recent Advances in the Chemistry of Fluorine-Containing π-Allylmetal and Allenylmetal Complexes

Pp. 491-522 (32)

Tsutomu Konno and Takashi Ishihara

Abstract

π-Allylmetal complexes derived from α-fluoroalkylated allyl mesylates react smoothly with various nucleophiles such as stabilized carbanions, carboxylates, and amines at the carbon distal to a fluoroalkyl group in a highly regioselective manner to give the corresponding γ-products in high to excellent yields. Treatment of the above fluorine-containing π-allylmetal complexes with hydride nucleophile gives the adducts derived from the hydride attacking on the carbon attached to a fluoroalkyl group. The γ-adducts, obtained by the reaction of π-allylpalladium complex with α-methoxy acetate or N-protected glycine, undergo smooth Ireland-Claisen rearrangement to give the corresponding multifunctionalized molecules in high yields. On the other hand, the reaction of α- fluoroalkylated propargylic mesylates with zinc reagents or stabilized carbanions in the presence of palladium catalyst affords fluorine-containing allene or furan derivatives respectively, in high yields, via allenylpalladium complex.

Affiliation:

Department of Chemistry and Materials Technology, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan.