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1997 Fiscal Year Final Research Report Summary

Synthesis and properties of planar-chiral cyclopentadienyl transition metal complexes.

Research Project

Project/Area Number 07454196
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field 物質変換
Research InstitutionOsaka University

Principal Investigator

TAKAHASHI Shigetoshi  Osaka University, The Institute of Scientific and Industrial Research, Professor, 産業科学研究所, 教授 (70029875)

Co-Investigator(Kenkyū-buntansha) TAKEI Fumie  Osaka University, The Institute of Scientific and Industrial Research, Technical, 産業科学研究所, 教務職員 (30252711)
UNO Mitsunari  Osaka University, The Institute of Scientific and Industrial Research, Assistant, 産業科学研究所, 講師 (20213473)
Project Period (FY) 1995 – 1997
Keywordsplanar chirality / cyclopentadienyl complexes / iron complexes / ruthenium complexes / optically active metal complexes / arene-ruthenium complexes / alkyliron complexes
Research Abstract

The synthesis and properties of planar-chiral cyclopentadienyl-iron and -ruthenium complexes have been studies and the following results are obtained :
(1) (1-Menthoxycarbonyl-2-methyl-4-phenylcyclopentadienyl) iron complexes, [Cp^1Fe (Co) _2I] 1, was synthesized from the reaction of a cyclopentadiene derivative with iron carbonyl followed by the treatment of Na and then iodine. The diastereomer mixture was separated into a pair of diastereomers 1a and 1b by fractional recrystallization from ether/hexane. Complexes 1a and 1b were reacted with phenylacetylene in the presence of a copper catalyst to give [Cp^1Fe (CO) _2 (CCPh) ] 2a and 2b, respectively, which were then treated with phenyl lithium at -78゚C to remove the mentoxy group and successfully converted to optically pure enantiomers 3a and 3b, respectively, (3a : R-form, mp 171.5-172.0゚C,[alpha]=-221゚ ; 3b : S-form, mp 171.5-172.0゚C,[alpha]=+221゚). In addition, dinuclear and trinuclear acetylide complexes consisting of di- and triethynylbenzene and the planar-chiral cyclopentadienyliron moiety were also synthesized.
(2) The diastereo selectivity in the reaction of planar-chiral cyclopentadienyl-ruthenium complexes, (Cp^2Ru (CH_3CN) _3] (PF_6) , with prochiral arenes was investigated and we have found that the reaction proceeds with a selectivity of 50% d.e.
(3) Asymmetric cyclopropanation of olefins with diazoacetic acid catalyzed by planar-chiral complexes was examined and we have found that cationic planar-chiral cyclopentadienyl-iron and-ruthenium complexes catalyze the cyclopropanation of stirene with an enantio selectivity of 50%.

  • Research Products

    (6 results)

All Other

All Publications (6 results)

  • [Publications] Yasushi Morimoto: "Induction of Metal-centered Chirality by Planar Chirality in [Fe{η-C_5H_2Me(R^1)(CO_2R^2)}(COR)(CO)(PR_3)] Complexes." Chemical Communications. 1795-1796 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Hidetoshi Kikuchi: "A New Ruthenium-catalyzed Reaction with Propargyl Alcohol : Cyclopropanation of Norbornene." Chemistry Letters. 1273-1274 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Nobuko Komatsuzaki: "Diastereoselective π-Complexation : Reaction of Planar-chiral Cyclopentadienyl-Ruthenium Complexes with Prochiral Arenes" Chemistry Letters. in press. (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yasushi Morimoto, et al.: "Induction of Metal-centered Chirality by Planar Chirality in [Fe{eta-C_5H_2Me (R^1) (CO_2R^2) } (COR) (CO) (PR_3) ] complexes." Chemical Communications. 1795-1796 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Hidetoshi Kikuchi, et al.: "A New Ruthenium-catalyzed Reaction with Propargyl Alcohol : Cyclopropanation of Norbornene." Chemistry Letters. 1273-1274 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Nobuko Komatsuzaki, et al.: "Diastereoselective pi-Complexation : Reaction of Planar-chiral Cyclopentadienyl-Ruthenium Complexes with Prochiral Arenes" Chemistry Letters. (in press).(1998)

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

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Published: 1999-03-16  

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