1994 Fiscal Year Final Research Report Summary
Structure-Reactivity Relationship for Organic Small Molecule-Metal Complexes
| Project/Area Number |
05453138
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
Synthetic chemistry
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| Research Institution | Osaka University |
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Principal Investigator |
KUROSAWA Hideo Osaka University, Applied Chemistry, Professor, 工学部, 教授 (40029343)
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| Co-Investigator(Kenkyū-buntansha) |
KUNIYASU Hitoshi Osaka University, Applied Chemistry, Assistant Professor, 工学部, 助手 (00252594)
OGOSHI Seneuke Osaka University, Applied Chemistry, Assistant Professor, 工学部, 助手 (30252589)
KAKIUCHI Kiyomi Osaka University, Applied Chemistry, Assistant Professor, 工学部, 助手 (60152592)
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| Project Period (FY) |
1993 – 1994
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| Keywords | pi-Allyl complex / Trimethylenemethane complex / Oxatrimethylenemethane complex |
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| Research Abstract |
The objective of this research project is to establish structure-reactivity relationship in organic small molecule-transition metal complexes, and to apply such relation to selective organic synthesis.
1) Stereochemical control of pi-allylic complexes. Requirements for 1-substituted allyl ligands to assume unusual anti-sterochemistry have been established by means of their coordination to dimetallic moieties. Enantioselective coordination of these ligands to Pd was realized by the use of bis(oxazoline) ligand.
2) Structure and reactivity of trimethylenemethane ligand and its analogs. Trimethylenemethane-palladium intermediate has been generated by means of destannylation of 2-stannylmethylallypalladium complexes, which reacted with aldehydes in a formal [2+3] cyclization manner. Analogous oxotrimethylenemethanepalladium complexes have been prepared, and their structure revealed by X-ray analysis. These complexes reacted with norbornene via [1+2] cycloadditon.
3) Synthesis and structure of mu-Allyl, mu-Propargyl and mu-butadiene dimetallic complexes. A general method for obtaining mu-allyl, mu-propargyl and mu-butadiene Pd-Pd complexes has been developed, which consists of reacting organopalladium(II) complexes with Pd(0) complexes. X-ray structure analysis revealed a characteristic Pd_2X framework which is bridged by organic small ligands.
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