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Chiral Catalysts to Synthesize Optically Active Alchools

  • 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

Catalytic enantioselective dialkylzinc addition to aldehydes and ketones was developed. Chiral diaminophoshine oxides derived from L-valine were effective as chiral ligands or catalysts. Not only cmmercially available dialkylzincs but also in situ generated organozincs from Grignard reagents or arylboronic acids were available as alkylation reagents.

Novelty and originality of this research

Optically active secondary alcohols can be synthesized by the enantioselective reduction of ketones. However, optically active tertiary alcohols cannot be synthesized by the same method. The present dialkylzinc addition method is quite effective for synthesizing not only secondary alcohols but also tertiary alcohols with high enantioselectivity. Chiral ligands can be easily prepared from L-valine.

Application and research area for Industry collaboration

Pharmaceuticals and their intermediates in synthetic process

Key Takeaway

Our interest is rational design of high performance catalysts based on acid-base combination chemistry.

Keywords

Synthetic organic chemistry, biomimetic chemistry, green chemistry, process chemistry, organometallic chemistry, chemistry of catalysis, acid-base combination chemistry, chemical catalysts, artificial catalysts, asymmetric synthesis, stereoselective syntheisis, pharmaceuticals, natural products, bioactive compounds, functional organic materials

Technologies

  • Synthetic technology of organic compounds
  • Experiments into a glove box
  • Structural analysis of organic compounds

Equipment

  • NMR, IR, Polarimeter, HPLC, Recycling preparative HPLC, GC, GCMS, GPC, X-ray diffraction instrument, globe box, Ultrasound, Microwave, Freezer, Karl Fischer Moisture Titrator, High vaccum line, Pararel Synthsizer, Melting-point instrument, High-pressure instrument

Patents

  • “Phosphoroamide compound, method for producing the same, ligand, complex, catalyst, and method for producing optically active alcohol,” WO2008/111371

Monographs, Papers and Articles

  • “Highly active chiral phosphoramide-Zn(II) complexes as conjugate acid–base catalysts for enantioselective organozinc addition to ketones,” Manabu Hatano, Takashi Miyamoto, Kazuaki Ishihara, Org. Lett. 2007, 9(22), 4535–4538.
  • “Commercially available neat organozincs as highly reactive reagents for catalytic enantioselective addition to ketones and aldehydes under solvent free conditions,” Manabu Hatano, Tomokazu Mizuno, Kazuaki Ishihara, Tetrahedron 2011, 67(24), 4417–4424.
  • "“Catalytic enantioselective alkyl and aryl addition to aldehydes and ketones with organozinc reagents derived from alkyl Grignard reagents or arylboronic acids,” Manabu Hatano, Riku Gouzu, Tokokazu Mizuno, Hitoshi Abe, Toshihide Yamada, Kazuaki Ishihara, Catal. Sci. Technol. 2011, 1(7), 1149–1158."
  • “Catalytic enantioselective synthesis of sterically demanding alcohols using di(2°-alkyl)zinc prepared by the refined Charette’s method,” Manabu Hatano, Tomokazu Mizuno, Kazuaki Ishihara, Chem. Commun. 2010, 46(30), 5443–5445.