Origin of chemoselectivity of TMP zincate bases and differences between TMP zincate and alkyl lithium reagents: A DFT study on model systems

Masanobu Uchiyama, Yotaro Matsumoto, Shinya Usui, Yuichi Hashimoto, Keiji Morokuma

Research output: Contribution to journalArticlepeer-review

44 Citations (Scopus)

Abstract

(Chemical Equation Presented) Transition-state structures of the type illustrated were found to be crucial in determining whether directed ortho-metalation (DoM) or 1,2-addition occurs in the reaction of benzonitrile or methyl benzoate with Me2Zn(TMP)Li or (MeLi)2. The origin of the high chemoselectivity of the reaction was investigated. TMP = 2,2,6,6-tetramethylpiperidide.

Original languageEnglish
Pages (from-to)926-929
Number of pages4
JournalAngewandte Chemie - International Edition
Volume46
Issue number6
DOIs
Publication statusPublished - 2007
Externally publishedYes

Keywords

  • Chemoselectivity
  • Density functional calculations
  • Metalation
  • Transition states
  • Zincates

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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