%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