1997 Fiscal Year Final Research Report Summary
Synthesis and properties of planar-chiral cyclopentadienyl transition metal complexes.
| Project/Area Number |
07454196
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
物質変換
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| Research Institution | Osaka University |
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Principal Investigator |
TAKAHASHI Shigetoshi Osaka University, The Institute of Scientific and Industrial Research, Professor, 産業科学研究所, 教授 (70029875)
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| 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)
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| Project Period (FY) |
1995 – 1997
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| Keywords | planar chirality / cyclopentadienyl complexes / iron complexes / ruthenium complexes / optically active metal complexes / arene-ruthenium complexes / alkyliron complexes |
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| 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%.
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