Structure and reaction pathway of TMP-zincate: Amido base or alkyl base?

Masanobu Uchiyama, Yotaro Matsumoto, Daisuke Nobuto, Taniyuki Furuyama, Kentaro Yamaguchi, Keiji Morokuma

Research output: Contribution to journalArticlepeer-review

105 Citations (Scopus)

Abstract

The novel directed ortho metalation (DoM) reagents for functionalized aromatic rings, TMP-Zn-ates (R2Zn(TMP)Li (R = Me, 1; tBu, 2)), have been reported to be synthetically useful for the chemo- and regioselective construction of multi-functionalized aromatic compounds. Here, we present the first comprehensive structural and mechanistic investigation by means of X-ray, NMR, and DFT studies on the DoM reaction employing our original TMP-Zn-ate base. The structures of TMP-Zn-ates in solution and in the solid state were determined. The DFT study strongly suggested that the deprotonation involving the TMP ligand on the TMP-Zn-ate is kinetically more favorable than that involving the alkyl ligand, and this view was supported by monitoring of the 13C NMR spectrum of the reaction mixture.

Original languageEnglish
Pages (from-to)8748-8750
Number of pages3
JournalJournal of the American Chemical Society
Volume128
Issue number27
DOIs
Publication statusPublished - 2006 Jul 12

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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