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2002 Fiscal Year Final Research Report Summary

The chemistry of Boron cation (boronium, borenium, borinium)-promoted transformation reaction

Research Project

Project/Area Number 12440206
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field 物質変換
Research InstitutionKyushu University (2002)
Kochi University (2000-2001)

Principal Investigator

KIYOOKA Syun-ichi  Kyushu University, Institute for Fundamental Research of Organic Chemistry, Prof., 有機化学基礎研究センター, 教授 (00036584)

Project Period (FY) 2000 – 2002
Keywordsboron cation / boronium ion / Lewi acidity / catalyst / ^<11>B NMR
Research Abstract

This research was undertaken to study solvent effects on chiral oxazaborolidinone-promoted asymmetric aldol reaction, followed by detection of cationic boron species when the B-H bond of the oxazaborolidinone was changed to the B-X. Using the B-Br compound related to (R,R)-stien, existence of the boron species and its utilization to organic syntheses were investigated in detail. It turned out to be quite difficult to control two vacant orbitals of the hypothetical chiral boron cation in asymmetric reactions. In addition, the complete boron cations lead easily to neutral trivalent boronic compounds by attack of nucleophiles because of the extensively high electrophilicity and it is also difficult to catalytically recycle the boron cation. Thus, the reaction system should be necessarily restricted to some concerted reactions.
Physical organic researches on boron cations were interestingly developed. Diphenylboron perchlorate, which was considered as a conventional standard compound of boron cations, was found to be a trivalent boronic compound having a covalent B-O bond by ^<11>B-NMR and calculation studies. Boron cation species in solution were suggested to be solvated tetravalent species, not divalent species. The true boron cationic species were detected for the first time by using laser flash-photolysis.

  • Research Products

    (18 results)

All Other

All Publications (18 results)

  • [Publications] S.-i.Kiyooka: "Diphenylboron perchlorate as an efficient catalyst for self-and cross-condensation reactions of aldehydes having a-active hydrogens"Tetrahedron Lett.. 44. 927-930 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.A.Shahid: "A straightforward, Highly stereoselective construction of eight stereogenic centers in (+)-discodermolide C_1-C_<13> segment, based on strategy of iterative aldol reactions"Tetrahedron Lett.. 43. 6377-6381 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.A.Shahid: "A short synthesis of the C_<15>-C_<21> segment of (+)-discodermolide, based on an asymmetric approach from achiral 2-methyl-1,3-propanediol to versatile enantiopure strereotriads"Tetrahedron Lett.. 43. 6373-6376 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.-i.Kiyooka: "A straightforward strategy toward the construction of polypropionate frameuorks, based on a sequence of diastereoselective Lewis acid-mediated aldol reaction and diasteroselective radical debromination reation"Tetrahedron Lett.. 43. 5377-5380 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.-i.Kiyooka: "Versatile, high 2,4-syn dialkyl diastereoselection in the radical debromination of α-brome-d-methyl-8-valerolactones with tri-n-butylfin hyaride and a catalytic amouut of triethylborame"Tetrahedron Lett.. 42. 7299-7301 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.-i.Kiyooka: "Is diphenylboronium perchlorate in nitoromethane …"Tetrahedron Lett.. 42. 4151-4153 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.G.Ahmed, et al.: "A convenient one pot synthesis of substituted and unsubstituted 2, 4-diaryl-5-oxo-5,6,7,8-tetrahydro-2-chronienes"Indian Journal of Chemistry, Section B. 41B(2). 368-371 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.-i.Kiyooka, et al.: "Superior substrate control on diastereoselection in boric Lews acid-promoted aldol reactions. Asymmetric synthesis of a 3,4-syn homologous series of ethyl 3,5-dihydroxy-2,4-dimethyl-5-phenylpentanoates"Tetrahedron : Asymmetry. 12. 2343-2349 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.-i.Kiyooka, et al.: "A divergent syntheisis of essentially enantioixire syn-and anti-propionate aldol adducts based on the chiral 1,3,2-oxazaborolidin-5-one-promoted asymmetric aldol reaction followed by diastereoselective radical reduction"Bull. Chem. Soc. Jpn.. 74. 1485-1495 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S. -i. Kiyooka, H. Fujimoto, M. Mishima, S. Kobayashi, K. M. Uddin, and M. Fujio: "Diphenylboron perchlorate as an efficient catalyst for self- and cross-condensation reactions of aldehydes having α-active hydrogens"Tetrahedron Lett.. 44. 927-930 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. G. Ahmed, S. A. Ahmed, U. K. R. Romman, T. Sultana, M. A. Hena, and S. -i. Kiyooka: "A convenient one pot synthesis of substituted and unsubstituted 2,4-diaryl-5-oxo-5,6,7,8-tetrahydro-2-chromenes"Indian Journal of Chemistry, Section B. 41B(2). 368-371 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. A. Shahid, J. Mursheda, M, Okazaki, Y. Shuto, F. Goto, and S. -i. Kiyooka: "A straightforward, highly stereoselective construction of eight stereogenic centers in (+)-discodermolide C1-C13 segment, based on a strategy of iterative aldol reactions"Tetrahedron Lett.. 43. 6377-6381 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. A. Shahid, Y. -N. Li, M. Okazaki, Y. Shuto, F. Goto, and S. -i. Kiyooka: "A short synthesis of the C15-C21 segment of (+)-discodermolide, based on an asymmetric approach from achiral 2-methyl-13-propanediol to versatile enantiopure stereotriads"Tetrahedron Lett.. 43. 6373-6376 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S. -i. Kiyooka, M. Shiinoki, K. Nakata, and F. Goto: "A straightforward strategy toward the contraction of polypropionate frameworks, based on a sequence of diastereoselective Lewis acid-mediated aldol reaction and diastereoselective radical debromination reaction"Tetrahedron Lett.. 43. 5377-5380 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S. -i. Kiyooka, Y. -N. Li, K. A. Shahid, M. Okazaki, and Y. Shuto: "Versatile, high 2,4-syn dialkyl diastereoselection in the radical debromination of α-bromo-α-methyl-δ-valerolactones with tri-butyltin hydride and a catalytic amount of triethylborane"Tetrahedron Lett.. 42. 7299-7301 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S. -i. Kiyooka, R. Fujiyama, T. Kawai, H. Fujimoto, and K. Goh: "Is diphenylboronium perchlorate in nitromethane ionic"Tetrahedron Lett.. 42. 4151-4153 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S. -i. Kiyooka, K. A. Shahid, K. Murai, Y. -N. Li, M. Okazaki, and Y. Shuto: "Superior substrate control on diastereoselection in boric Lewis acid-promoted aldol reactions. Asymmetric synthesis of a 3,4-syn homologous series of ethyl 3,5-dihydroxy-2,4-dimethyl-5-phenylpentanoates"Tetrahedron: Asymmetry. 12. 2343-2349 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S. -i. Kiyooka and K. A. Shahid: "A divergent synthesis of essentially enantiopure syn- and anti-propionate aldol adducts based on the chiral 1,3,2-oxazaborolidin-5-one-promoted asymmetric aldol reaction followed by diastereoselective radical reduction"Bull. Chem. Soc. Jpn.. 74. 1485-1495 (2001)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 2004-04-14  

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