Mechanism of the nucleophilic substitution of acyl electrophiles using lithium organocuprates

Naohiko Yoshikai, Ryoko Iida, Eiichi Nakamura

研究成果: Article査読

24 被引用数 (Scopus)

抄録

The mechanism of nucleophilic substitution reaction at an sp2 carbon center of a thioester or an acid chloride with a lithium organocuprate reagent has been investigated. Density functional calculations indicated that the thioester undergoes oxidative addition of the C-S bond to the copper(I) atom through a three-centered transition state to afford an organocopper(III) intermediate, which gives the product through reductive elimination of the alkyl and the acyl groups. On the other hand, the acid chloride loses a chloride anion very easily when it interacts with the cuprate, because the chloride anion is captured by a lithium(I) cation rather than a copper(I) atom. 13C kinetic isotope effect (KIE) experiments showed excellent agreement with computational predictions for the thioester reaction, but suggested that the nucleophilic displacement transition state of the acid chloride occurs much more advanced than the calculations predict.

本文言語English
ページ(範囲)1063-1072
ページ数10
ジャーナルAdvanced Synthesis and Catalysis
350
7-8
DOI
出版ステータスPublished - 2008 5月 5
外部発表はい

ASJC Scopus subject areas

  • 触媒
  • 有機化学

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