%0 Journal Article %A Iwasaki, Masayuki %A Hayashi, Sayuri %A Hirano, Koji %A Yorimitsu, Hideki %A Oshima, Koichiro %D 2007 %T Pd(OAc)2/P(cC6H11)3-Catalyzed Allylation of Aryl Halides with Homoallyl Alcohols via Retro-Allylation %U https://acs.figshare.com/articles/journal_contribution/Pd_OAc_sub_2_sub_P_i_sup_c_sup_i_sup_sup_C_sub_6_sub_H_sub_11_sub_sub_3_sub_Catalyzed_Allylation_of_Aryl_Halides_with_Homoallyl_Alcohols_via_Retro_Allylation/3013549 %R 10.1021/ja067372d.s001 %2 https://acs.figshare.com/ndownloader/files/4714861 %K aryl halides %K cyclic homoallyl alcohols %K palladium %K homoallyl alcohols %X 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. %I ACS Publications