An aluminum ate base: Its design, structure, function, and reaction mechanism

Hiroshi Naka, Masanobu Uchiyama, Yotaro Matsumoto, Andrew E.H. Wheatley, Mary McPartlin, James V. Morey, Yoshinori Kondo

Research output: Contribution to journalArticlepeer-review

157 Citations (Scopus)

Abstract

An aluminum ate base, i-Bu3Al(TMP)Li, has been designed and developed for regio- and chemoselective direct generation of functionalized aromatic aluminum compounds. Direct alumination followed by electrophilic trapping with I2, Cu/Pd-catalyzed C-C bond formation, or direct oxidation with molecular O2 proved to be a powerful tool for the preparation of 1,2- or 1,2,3-multisubstituted aromatic compounds. This deprotonative alumination using i-Bu3Al(TMP)Li was found to be effective in aliphatic chemistry as well, enabling regio- and chemoselective addition of functionalized allylic ethers and carbamates to aliphatic and aromatic aldehydes. A combined multinuclear NMR spectroscopy, X-ray crystallography, and theoretical study showed that the aluminum ate base is a Li/Al bimetallic complex bridged by the nitrogen atom of TMP and the α-carbon of an i-Bu ligand and that the Li exclusively serves as a recognition point for electronegative functional groups or coordinative solvents. The mechanism of directed ortho alumination reaction of functionalized aromatic compounds has been studied by NMR and in situ FT-IR spectroscopy, X-ray analysis, and DFT calculation. It has been found that the reaction proceeds with facile formation of an initial adduct of the base and aromatic, followed by deprotonative formation of the functionalized aromatic aluminum compound. Deprotonation by the TMP ligand rather than the isobutyl ligand was suggested and reasoned by means of spectroscopic and theoretical study. The remarkable regioselectivity of the ortho alumination reaction was explained by a coordinative approximation effect between the functional groups and the counter Li+ ion, enabling stable initial complex formation and creation of a less strained transition state structure.

Original languageEnglish
Pages (from-to)1921-1930
Number of pages10
JournalJournal of the American Chemical Society
Volume129
Issue number7
DOIs
Publication statusPublished - 2007 Feb 21

ASJC Scopus subject areas

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

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