| Project/Area Number |
14078219
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| Research Category |
Grant-in-Aid for Scientific Research on Priority Areas
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| Allocation Type | Single-year Grants |
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| Review Section |
Science and Engineering
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| Research Institution | Okayama University |
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Principal Investigator |
TAKAI Kazuhiko Okayama University, Graduate School of Natural Science and Technology, Division of Chemistry and Biochemistry, Professor, 大学院自然科学研究科, 教授 (00144329)
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| Project Period (FY) |
2002 – 2005
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| Project Status |
Completed (Fiscal Year 2006)
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| Budget Amount *help |
¥28,400,000 (Direct Cost: ¥28,400,000)
Fiscal Year 2005: ¥7,200,000 (Direct Cost: ¥7,200,000)
Fiscal Year 2004: ¥7,200,000 (Direct Cost: ¥7,200,000)
Fiscal Year 2003: ¥7,000,000 (Direct Cost: ¥7,000,000)
Fiscal Year 2002: ¥7,000,000 (Direct Cost: ¥7,000,000)
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| Keywords | Chromium / Tantalum / Rhenium / Alkylidene complex / Alkyne complex / C-H bond activation / Atom-economical process / Iodocyclopronane / 動的錯体 / レニウム錯体 / インデン / フタルイミジン / シリルアセチレン / 配位子交換反応 / 環化三量化反応 / 三置換ベンゼン / 前周期遷移金属 / アルケニルニッケル / クロム-アルキリデン錯体 / タンタル-アルキン錯体 / 三量化反応 / ベンゼン誘導体 / クロム-カルベン錯体 / gem-ジカルベノイド / アレン |
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| Research Abstract |
1. Selective Transformations with Novel Organochromium Species : The family of trans-iodocyclo-propanes are good precursors for constructing cyclopropyl-cyclopropyl and-vinyl carbon skeletons. We have found that iodocyclopropanation of terminal alkenes proceeds with organochromium species generated by chromium(II)-reduction of iodoform in the presence of TEEDA (N,N,N',N'-tetraethylethylenediamine) under high stereocontrol. The transformation proceeds smoothly without the presence of a hydroxy or an alkoxy group near the double bond, which is necessary for the cyclopropanation of iodoalkenes with zinc carbenoids.
2. Synthesis and Reactions of Tantalum η^2-Bis(trimethylsilyl)acetylene Complex : A tantalum-alkyne complex TaCl_3(Me_3SiC≡CSiMe_3)(dme) (1, DME=1,2-dimethoxyethane) is synthesized by treatment of the corresponding alkyne with a low-valent tantalum derived by reduction of TaCl_5 with zinc in a mixed solvent of toluene and DME according to our previously reported procedure. The t
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antalum complex 1 reacts with an internal alkyne to give a corresponding alkyne complex via ligand exchange reaction. The mechanism of the ligand exchange is clarified by kinetic study of the formation of diphenylacetylene complex from 1 and diphenylacetylene.
3. Carbon-Hydrogen Bond Activation with Rhenium Catalysts and Its Application to Organic Synthesis : A rhenium complex, [ReBr(CO)_3(thf)]_2, catalyzes the reaction of an aromatic aldimine with an isocyanate and an acetylene to give a phthalimidine and an indene derivative in a quantitative yield, respectively. The reactions proceed via C-H bond activation, insertion of the isocyanate or the acetylene, intramolecular nucleophilic cyclization to the aldimine of the generated amido-or alkenyl-rhenium species, and reductive elimination. In contrast to ruthenium and rhodium catalysts, which are usually employed in this type of reaction, the rhenium catalyst promotes the insertion of a polar unsaturated molecule. The rhenium-catalyzed reaction of an aromatic ketimine with ethyl acrylate gave an indene derivative in good yield via C-H bond activation. The indene derivatives could also be obtained by the reactions of aromatic ketones with α,β-unsaturated esters in the presence of catalytic amounts of the rhenium complex andp-anisidine. Less
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