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

Masayuki Iwasaki, Sayuri Hayashi, Koji Hirano, Hideki Yorimitsu, Koichiro Oshima

Research output: Contribution to journalArticle

67 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)4463-4469
Number of pages7
JournalJournal of the American Chemical Society
Volume129
Issue number14
DOIs
Publication statusPublished - Apr 11 2007
Externally publishedYes

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Allylation
Palladium
Alcohols
Ketones
Ligands
Cesium
palladium(II) acetate
Chlorides
Carbonates
Electrons
Catalysts

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Pd(OAc)2/P(cC6H11) 3-catalyzed allylation of aryl halides with homoallyl alcohols via retro-allylation. / Iwasaki, Masayuki; Hayashi, Sayuri; Hirano, Koji; Yorimitsu, Hideki; Oshima, Koichiro.

In: Journal of the American Chemical Society, Vol. 129, No. 14, 11.04.2007, p. 4463-4469.

Research output: Contribution to journalArticle

Iwasaki, Masayuki ; Hayashi, Sayuri ; Hirano, Koji ; Yorimitsu, Hideki ; Oshima, Koichiro. / Pd(OAc)2/P(cC6H11) 3-catalyzed allylation of aryl halides with homoallyl alcohols via retro-allylation. In: Journal of the American Chemical Society. 2007 ; Vol. 129, No. 14. pp. 4463-4469.
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