Mechanism of remote conjugate addition of lithium organocuprates to polyconjugated carbonyl compounds

Naohiko Yoshikai, Tatsuya Yamashita, Eiichi Nakamura

研究成果: Article査読

25 被引用数 (Scopus)

抄録

Regioselective reaction of a lithium organocuprate (R2CuLi) and a polyconjugated carbonyl compound affords a remote-conjugate-addition product. This reaction proceeds particularly cleanly when the conjugation is terminated by a C-C triple bond. The reaction pathways and the origin of the regioselectivity of this class of transformations are explored with the aid of density functional calculations. The outline of the reaction pathway is as follows. An initially formed β-cuprio-(III) enolate intermediate undergoes smooth copper migration along the conjugated system. This process takes place faster than reductive elimination of intermediary σ/π-allylcopper(III) species, since the latter reaction disrupts the conjugation in the substrate and hence is not preferred. The copper migration to the acetylenic terminal affords a σ/π-allenylcopper(III) intermediate, which undergoes facile and selective C-C bond forming reductive elimination at the terminal carbon atom. The present mechanistic framework shows good agreement with some pertinent experimental data, including 13C NMR chemical shifts and kinetic isotope effects.

本文言語English
ページ(範囲)322-330
ページ数9
ジャーナルChemistry - An Asian Journal
1
3
DOI
出版ステータスPublished - 2006
外部発表はい

ASJC Scopus subject areas

  • 生化学
  • 有機化学

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