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Highly Selective Alkyl Addition Reactions with Highly Active Zinc(II) Ate Complexes

  • School of Engineering/Graduate School of Engineering
  • Department of Molecular and Macromolecular Chemistry
  • Research Group of Molecular Chemistry
  • (Laboratory of Catalysis in Organic Synthesis)

Kazuaki Ishihara [Professor]

http://www.ishihara-lab.net/english/

  • School of Engineering/Graduate School of Engineering
  • Department of Molecular and Macromolecular Chemistry
  • Research Group of Molecular Chemistry
  • (Laboratory of Catalysis in Organic Synthesis)

Manabu Hatano [Associate Professor]

Outline of Seeds

Grignard reagent is a traditional organometallic reagent, and widely used for alkyl addition to carbonyl compounds in both laboratory and industry. Grignard reagent can be easily prepared from inexpensive materials. Moreover, Grignard reagent is highly stable and can be stocked in a long term. However, the control of reactions is usually difficult since Grignard reagent is too reactive and many side reactions occur. In this regard, our group developed the usefulness of zinc(II) ate complexes, which are prepared in situ from Grignard reagent and zinc(II) chloride. We developed Zn(II) ate complex-catalyzed Grignard addition reaction to ketones for the first time. We also developed a highly regioelective ZnCl2-Grignard reagent addition reactions of alpha-aldimino esters toward the efficient amino acid synthesis. Moreover, we developed a highly regioselective conjugate additions of Grignard reagent-derived organozinc(II)ates to poly-conjugated esters.

Novelty and originality of this research

We can control the highly selective Grignard-alkyl addition to a variety of substrates
by using catalytic or stoichiometric amount of inexpensive and non-toxic zinc(II) chloride.

Application and research area for Industry collaboration

Syntheis of tertiary alcohol-derived photoresist material, amino acid, and poly-conjugate compounds

Key Takeaway

Extremely good synthetic technology of selective alkyl addition without any side reactions

Keywords

Zn(II) ate complex, catalyst, ketone, tertiary alcohol, imino ester, amino acid, poly-conjugate ester, conjugate addition

Technologies

  • Synthetic method of tertiary alcohols
  • Synthetic method of chiral amino acids
  • Regioselective conjugate addition

Patents

  • JP4873502

Monographs, Papers and Articles

  • Manabu Hatano, Shinji Suzuki, Kazuaki Ishihara: J. Am. Chem. Soc. 2006, 128(31), 9998–9999.
  • Manabu Hatano, Kenji Yamashita, Mai Mizuno, Orie Ito, Kazuaki Ishihara: Angew. Chem. Int. Ed. 2015, 54(9), 2707-2711.
  • Manabu Hatano, Mai Mizuno, Kazuaki Ishihara: Org. Lett. 2016, 18, in press.