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Hypoiodite Catalysis

  • 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)

Muhammet Uyanik [Assistant Professor]

Outline of Seeds

We developed oxidative coupling reactions catalyzed by hypoiodite salts, which are generated in situ from the catalytic amount of quaternary ammonium iodide with hydrogen peroxide or alkyl hydroperoxides (TBHP or CHP) as an environmentally benign oxidant. Hypoiodite-catalyzed intra- or intermolecular oxidative coupling of carbonyl compounds at -position with carboxylic acids afforded -acyloxycarbonyl compounds, which are significant building blocks in synthetic organic chemistry. Enantioselective hypoiodite catalysis could be realized by introducing a chiral counter cation. A chiral quaternary ammonium hypoiodite-catalyzed enantioselective oxidative cycloetherification of ketophenols gave the correspoding 2-acyl-2,3-dihydrobenzofuran or 2-acyl chroman derivatives with excellent enantioselectivities. Moreover, enantioselective cycloetehrification

Novelty and originality of this research

In contrast to conventional oxidation catalysts, hypoiodite salts can be generated in situ from the relatively safe and inexpensive precatalysts and oxidants. Notably, a high-performance catalytic oxidation system (turnover number of the catalyst = 2000) has been achieved by using an inorganic base like potassium carbonate. The most important features of the hypoiodite catalytic oxidation system are: (1) metal-free oxidation, (2) milder reaction conditions, (3) high chemoselectivity, (4) wide range of substrates, and (5) water or alcohol is an only by-product derived from the oxidant used.

Application and research area for Industry collaboration

Enviromentally benign oxidative coupling reactions for the synthesis of biologically active compounds and functional organic materials

Key Takeaway

Metal-free hypoiodite salt-catalyzed oxidative coupling reactions

Keywords

hypoiodite salt, oxidative coupling, -acyloxycarbonyl, dihydrobenzofuran, chroman

Technologies

  • Oxidative coupling, Enantioselective oxidative coupling

Patents

  • JP5770160(B2)
  • JP5544596(B2)
  • JP5929767(B2)

Monographs, Papers and Articles

  • M. Uyanik, H. Okamoto, T. Yasui, K. Ishihara, Science 2010, 328(5984), 1376–1379.
  • M. Uyanik, H. Hayashi, K. Ishihara, Science 2014, 345(6194), 291–294.
  • M. Uyanik, D. Suzuki, T. Yasui, K. Ishihara, Angew. Chem. Int. Ed. 2011, 50(23), 5331–5334
  • M. Uyanik, N. Sasakura, E. Kaneko, K. Ohori, T. Yasui, K. Ishihara, Chem. Lett. 2015, 44(2), 179–181.