Reaction mechanism for the LiCl-mediated directed zinc insertion: A computational and experimental study

Ching Yuan Liu, Xuan Wang, Taniyuki Furuyama, Shuji Yasuike, Atsuya Muranaka, Keiji Morokuma, Masanobu Uchiyama

Research output: Contribution to journalArticlepeer-review

19 Citations (Scopus)

Abstract

An experimental/computational study on the LiCI-mediated zinc insertion, and the questions of the generation mechanism of Li ion ZnRCIHal, the role of LiCI, and the origin of the regioselectivity in the reaction has been demonstrated. The acceleration of Zn insertion by LiC1 was thermodynamically and kinetically confirmed. The exchange of electrons occurs exclusively among the three atoms, and the charges of the Li and the Cl atoms remain essentially constant during the reaction, indicating that LiCI does not participate in any oxidation/reduction process. The origin of the LiCI effect was investigated by natural bond orbital (NBO) analysis. Origin of the directed oct/to selectivity of the zinc insertion reaction. The theoretical analysis delineated above further advances the understanding of recent zinc insertion chemistry and should contribute to rational design for efficient preparation of functionalized aryl zinc reagents and its application to useful synthetic transformations.

Original languageEnglish
Pages (from-to)1780-1784
Number of pages5
JournalChemistry - A European Journal
Volume16
Issue number6
DOIs
Publication statusPublished - 2010 Feb 8

Keywords

  • Density functional calculations
  • Insertion
  • Lithium chloride
  • Reaction mechanisms
  • Regioselectivity
  • Zinc

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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