Pd(OAc)2/P(cC6H11) 3-catalyzed allylation of aryl halides with homoallyl alcohols via retro-allylation

被引：0
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作者：
Iwasaki, Masayuki [1 ]
Hayashi, Sayuri [1 ]
Hirano, Koji [1 ]
Yorimitsu, Hideki [1 ]
Oshima, Koichiro [1 ]
机构：
[1] Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto-daigaku Katsura, Nishikyo-ku, Kyoto 615-8510, Japan
来源：
Journal of the American Chemical Society | 2007年 / 129卷 / 14期
关键词：
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. © 2007 American Chemical Society;
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页码：4463 / 4469
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