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Pd(OAc)2/P(cC6H11)3-Catalyzed Allylation of Aryl Halides with Homoallyl Alcohols via Retro-Allylation

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journal contribution
posted on 11.04.2007, 00:00 by Masayuki Iwasaki, Sayuri Hayashi, Koji Hirano, Hideki Yorimitsu, Koichiro Oshima
Allylations of aryl halides take place upon treatment of tertiary homoallyl alcohols with aryl halides in the presence of cesium carbonate and a palladium catalyst. The allylation reaction would consist of the following steps:  (1) oxidative addition of aryl halide to palladium, (2) ligand exchange between the halide and the homoallyl alcohol affording aryl(homoallyloxy)palladium, (3) retro-allylation of the palladium alkoxide to generate σ-allyl(aryl)palladium with concomitant liberation of the relevant ketone, and (4) productive reductive elimination. Since the retro-allylation step proceeds in a concerted fashion via a conformationally regulated six-membered cyclic transition state, the allylation reactions are highly regio- and stereospecific when homoallyl alcohols having a substituted allyl group are used. Whereas triarylphosphine is known to serve as a ligand for the palladium-catalyzed allyl transfer reactions, tricyclohexylphosphine proves to significantly expand the scopes of aryl halides to electron-rich aryl chlorides and of homoallyl alcohols to cyclic homoallyl alcohols. The new arylative ring-opening reactions of cyclic homoallyl alcohols allow for the synthesis of ketones having a branched or linear allylarene moiety at the remote terminus in regio- and stereospecific manners.