Development of novel molecular catalysts having tetraphenylphenyl unit

• Project/Area Number: 17550026
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: KYUSHU UNIVERCITY (2006); Hokkaido University (2005)
• Principal Investigator: TOKUNAGA Makoto Kyushu univercity, Science, Chemistry, Professor, 理学研究院, 教授 (40301767)
• Project Period (FY): 2005 – 2006
• Project Status: Completed (Fiscal Year 2006)
• Budget Amount: ¥3,600,000 (Direct Cost: ¥3,600,000); Fiscal Year 2006: ¥1,000,000 (Direct Cost: ¥1,000,000); Fiscal Year 2005: ¥2,600,000 (Direct Cost: ¥2,600,000)
• Keywords: homogeneous catalysts / asymmetric synthesis / hydrolysis / alcoholysis / axially chiral compounds / P-chirogenic compounds / kinetic optical resolution / nanotechnology / 合成化学 / 触媒・化学プロセス / 分子触媒 / 分子認識 / 選択的合成

Research Abstract

We have elucidated that the function of ligands bearing tetraphenylphenyl group, which have rigid and spatially spread structure. The oxygen-, nitrogen-, and phosphorous-ligands having tetraphenylphenyl group were synthesized and were examined catalytic reactions using several kinds of metals. We aimed to find new reactions, high catalytic activity, and high selectivity compared to conventional catalysts. Indeed, in the last year we have explored the enhancement effect of stereoselectivity by the large asymmetric environment produced by tetraphenylphenyl group. The size of the tetraphenylphenyl group is approximately 1.3 nano meters. This is relatively larger than the ligands, which is used in usual homogeneous metal complex catalysts, however, smaller than supermolecular catalysts such as dendrimers. An advantage over the supermolecular catalysts is synthetic accessibility. In reality, we have examined asymmetric alcoholysis of vinyl ethers of 2,2'-dihydroxy-1.1'-biaryls and found tha t the diamine ligands bearing tetraphenylphenyl group exhibited higher performance : 1.3 times higher stereoselectivity and 2.0 times higher catalytic activity. This reaction is very useful because asymmetric synthesis of 2,2'-dihydroxy-1.1'-binaphtols is relatively easy but 2,2'-dihydroxy-1.1'-binphenols are not so easy. The reason is mainly due to the stability of radicals generating during the reaction. Therefore oxidative coupling of 2-naphtol is easy but phenol is difficult. We extended the research to the asymmetric synthesis of 2,2'-dihydroxy-1.1'-biaryls having phosphoryl and sulfonyl groups and succeeded kinetic resolution of these compounds in high selectivity. In addition, the compounds which have asymmetric center at phosphorous atom were examined to the reaction and found that kinetic resolution of these class of compounds can be carried out with high selectivities up to 39. Since asymmetric synthesis of these compounds are extremely difficult, the value of our reactions should be very high.

Research Products

• [Journal Article] Metal complexes-catalyzed hydrolysis and alcoholysis of organic substrates and their application to kinetic resolution (2007)
  • Author(s): Tokunaga, M., Aoyama, H., Kiyosu, J., Shirogane, Y., Iwasawa, T, Obora, Y., Tsuji,Y.
  • Journal Title: J. Organomet. Chem. 692 Pages: 472-480
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Rhodium(I) complexes with N-heterocyclic carbenes bearing a 2,3,4,5-tetraphenyl-phenyl and its higher dendritic frameworks (2007)
  • Author(s): Sato, H., Fujihara, T., Obora, Y., Tokunaga, M., Kiyosu, J., Tsuji Y.
  • Journal Title: ChemComm. Pages: 269-271
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Metal complexes-catalyzed hydrolysis and alcoholysis of organic substrates and their application to kinetic resolution. (2007)
  • Author(s): Tokunaga, M., Aoyama, H., Kiyosu, J., Shirogane, Y., Iwasawa, T., Obora, Y., Tsuji, Y
  • Journal Title: J.Organomet.Chem. 692 Pages: 472-480
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Metal complexes-catalyzed hydrolysis and alcoholysis forganic substrates and their application to kinetic resolution (2007)
  • Author(s): Tokunaga, M., Aoyama, H., Kiyosu, J., Shirogane, Y., Iwasawa, T., Obora, Y., Tsuji, Y.
  • Journal Title: J. Organomet. Chem. 692
• [Journal Article] Phosphines having a 2,3,4,5-tetraphenylphenyl moiety : effective ligands in palladium-catalyzed transformations of aryl chlorides (2006)
  • Author(s): Iwasawa, T., Komano, T., Tajima, A., Tokunaga.M., Obora, Y., Fujihara, T., Tsuji Y.
  • Journal Title: Organometallics 25 Pages: 4665-4669
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Kinetic Resolution Displaying Zeroth Order Dependence on Substrate Consumption : Copper-catalyzed Asymmetric Alcoholysis of Azlactones (2006)
  • Author(s): Tokunaga.M., Kiyosu, J., Obora, Y., Tsuji, Y.
  • Journal Title: J. Am. Chem. Soc. 128 Pages: 4481-4486
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] 珍しい液-液抽出による光学分割 (2006)
  • Author(s): 徳永 信, 山本英治
  • Journal Title: 化学 61(10) Pages: 61-62
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Phosphines having a 2,3,4,5-tetraphenylphenyl moiety : effective ligands in palladium-catalyzed transformations of aryl chlorides (2006)
  • Author(s): Iwasawa, T., Komano, T., Tajima, A., Tokunaga, M., Obora, Y., Fujihara, T., Tsuji Y.
  • Journal Title: Organometallics 25 Pages: 4665-4669
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Kinetic Resolution Displaying Zeroth Order Dependence on Substrate Consumption : Copper-catalyzed Asymmetric Alcoholysis of Azlactones (2006)
  • Author(s): Tokunaga, M., Kiyosu, J., Obora, Y., Tsuji, Y.
  • Journal Title: J.Am.Chem.Soc. 128 Pages: 4481-4486
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] An uncommon liquid-liquid extraction for optical resolution (2006)
  • Author(s): Tokunaga, M, Yamamoto, E.
  • Journal Title: Kagaku 61(10) Pages: 61-62
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Kinetic Resolution Displaying Zeroth Order Dependence on Substrate Consumption : Copper-catalyzed Asymmetric Alcoholysis of Azlactones (2006)
  • Author(s): Tokunaga, M., Kiyosu, J., Obora, Y., Tsuji, Y.
  • Journal Title: J. Am. Chem. Soc. 128 Pages: 4481-4486
• [Journal Article] Kinetic Resolution of Axially Chiral 2,2'-Dihydroxy-1,1'-biaryls by Palladium Catalyzed Alcoholysis (2005)
  • Author(s): Aoyama, H 他
  • Journal Title: J.Am.Chem.Soc. 127・30 Pages: 10474-10475
• [Journal Article] MALDI TOF Mass Study on Oligomerization of Pd(OAc)2(L)2(L=Pyridine Derivatives) : Relevance to Pd Black Formation in Pd-catalyzed Air Oxidation of Alcohols (2005)
  • Author(s): Komano, T.他
  • Journal Title: Org.Lett. 7・21 Pages: 4677-4679
• [Book] Recent Research Development in Organic Chemistry (2005)
  • Author(s): Tokunaga, M.他
  • Total Pages: 13
  • Publisher: Transworld Research Network, Kerala, India.
• [Book] デンドリティック高分子 (2005)
  • Author(s): 辻 康之, 他
  • Total Pages: 10
  • Publisher: エヌ・ティー・エス