Research

○Research Theme

 
Recent medicines are prepared mainly by various organic reactions. Therefore, the investigations 
for the effective, selective and pollution-free reactions are strongly desired. On this concept 
we are studying novel reactions and the reaction mechanisms concerning photochemical, catalytic 
and asymmetric reactions. Our recent research themes are as follows: 

 1. Photochemical reactions (e.g. [3+2] cycloaddition) of small-ring-containing compounds (epoxide
  or aziridine) conjugated with nitrile or ester have been investigated systematically.
　Currently we are focusing on asymmetric photoinduced [3+2] cycloaddition of aziridine and 
　alkenes in chiral media.

 2. We are also investigating the reaction of benzylic carbocationic species generated from 
  the corresponding benzylic alcohols by rare earth metal catalysts with carbon, nitrogen and 
  oxygen nucleophiles. 

 3. We are also interested in the application of these reactions for practical synthetic use and 
  asymmetric synthesis. Asymmetric desymmetrization of prochiral serinol possessing a chiral 
  substituent on its nitrogen has been studied. High value-added products are synthesized 
  efficiently and conveniently.

○Recent Publications

 
  1) Noji M., Sunahara H., Tsuchiya K., Mukai T., Komasaka A., and Ishii K., "A Novel Synthetic Route
    to 2-Arylalkanoic Acids by a Ruthenium-Catalyzed Chemoselective Oxidation of Furan Rings", 
    Sythesis, 2008, 3835-3845.
  2) Ishii K., Kido M., Noji M., and Sugiyama S., "Photoreactions of Bicyclic Aziridines with 
    Aziridines with Alkenes and alkynes: a Novel Synthetic Methodology for 8-Azabicyclo[3.2.1]octane 
    Derivatives", Org. Biomol. Chem., 6, 3186-3195 (2008).
  3) S. Sugiyama, H. Fukuchi, and K. Ishii, "Diastereoselective Intramolecular acyl Transfer of 5-(α-
    Methylbenzyl)amino-1,3-dioxan-2-one to 4-Hydroxymethyl-2-oxazolidinones", Tetrahedron, 63,
    12047-12057 (2007).
  4) Noji M., Konno Y., and Ishii K., "Metal Triflate-Catalyzed Cationic Benzylation 
    and Allylation of 1,3-Dicarbonyl Compounds", J. Org. Chem., 72, 5161-5167 (2007).
  5) Sugiyama S., Aoki Y., and Ishii K., "Enantioselective Addition of Diethylzinc to Aldehydes
    Catalyzed by Monosubstituted [2.2]Paracyclophane-Based N,O-Ligands: Remarkable Cooperative 
    Effects of Planar and Central Chiralities", Tetrahedron Asymmetry, 17, 2847-2856 (2006).
  6) Ishii K., Sone T., Shigeyama T., Noji M., and Sugiyama S., "Photoreactions of β-
    Aziridinylacrylonitriles and Acrylates with Alkenes: the Substituent-Effects on the 
    Formation of [3+2] Cycloadducts", Tetrahedron, 62, 10865-10878 (2006).
  7) Sugiyama S., Arai S., and Ishii K., "Stereoselective Gram-Scale Synthesis of (S)-5,5-
    Dimethyl-4-phenyloxazolidin-2-one", Heterocycles, 65, 149-159 (2005).
  8) Sugiyama S., Arai S., Kiriyama M., and Ishii K., "A Convenient Synthesis of
    Immunosuppressive Agent FTY720 Using the Petasis Reaction", Chem. Pharm. Bull., 53,
    100-102 (2005).
  9) Ishii K., Sone T., Shimada Y., Shigeyama T., Noji M., and Sugiyama S., "Photoreactions
    of β-Aziridinylacrylonitriles and Acrylates with Alkenes: Formation of Head-to-Head 
    Adducts and Application to the Preparation of Pyrrolizidine Alkaloid",  Tetrahedron, 60, 
    10887-10898 (2004).
 10) Sugiyama S., Arai S., and Ishii K., "Short Synthesis of Both Enantiomers of Cytoxazone
    Using the Petasis Reaction", Tetrahedron Asymmetry, 15, 3149-3153 (2004).
 11) Noji M., Ohno T., Fuji K., Futaba N., Tajima H., and Ishii K., "Secondary Benzylation
    Using Benzyl Alcohols Catalyzed by Lanthanoid, Scandium, and Hafnium Triflate",
    J. Org. Chem., 68, 9340-9347 (2003).
 12) Sugiyama S., Inoue T., and Ishii K., "One-Pot Acylation and Fractional Crystallization: 
    Preparation of Optically Active Serinol Monobenzoates", Tetrahedron Asymmetry, 14, 
　　2153-2160 (2003).
 13) Sugiyama S., Watanabe S., Inoue T., Kurihara R., Itou T., and Ishii K., "A Novel Dynamic
    Kinetic Resolution Accompanied by Intramolecular Transesterification: Asymmetric Synthesis
    of a 4-Hydroxymethyl-2-oxazolidinone from Serinol Derivatives", Tetrahedron, 59, 
　　3417-3425 (2003).