| Project/Area Number |
06403024
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| Research Category |
Grant-in-Aid for Scientific Research (A)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Synthetic chemistry
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| Research Institution | Nagoya University |
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Principal Investigator |
YAMAMOTO Hisashi Nagoya University, Graduate School of Engineering, Professor, 工学部, 教授 (10135311)
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| Co-Investigator(Kenkyū-buntansha) |
SAITO Susumu Nagoya University, Graduate School of Engineering, Research Associate, 工学部, 助手 (90273268)
ISHIHARA Kazuaki Nagoya University, Graduate School of Engineering, Assistant Professor, 工学部, 助手 (40221759)
YANAGISAWA Akira Nagoya University, Graduate School of Engineering, Associate Professor, 工学部, 助教授 (60183117)
丸岡 啓二 名古屋大学, 工学部, 助教授 (20135304)
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| Project Period (FY) |
1994 – 1996
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| Project Status |
Completed (Fiscal Year 1996)
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| Budget Amount *help |
¥33,100,000 (Direct Cost: ¥33,100,000)
Fiscal Year 1996: ¥2,500,000 (Direct Cost: ¥2,500,000)
Fiscal Year 1995: ¥5,700,000 (Direct Cost: ¥5,700,000)
Fiscal Year 1994: ¥24,900,000 (Direct Cost: ¥24,900,000)
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| Keywords | Lewis acidic receptor / Aluminum reagent / Designer Lewis acid / Lewis base / Selective organic synthesis / Molecular recognition chemistry / Lewis acid-base complex / ルイス塩基複合体 / 有機アルミニウム / 複合体形成クロマトグラフィー |
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| Research Abstract |
The fascination of molecular recognition chemistry is extending continuously, especially as host-guest systems which mimic biologically occurring compounds exhibiting catalytic activities like enzymes. The discovery of crown ethers and cryptands and their inclusion systems by Prof. Lehn and Cram led them to be the winners of the Nobel Prize, and most of these systems are constituted by hydrogen-bonding networks between host and guest molecules. Comparing with these weak interactions, relatively strong coordination bonding between Lewis acidic receptors and Lewis bases has received less attention for molecular recognition, and has never been used for selective organic synthesis.
In this context, we have developed several bulky organoaluminum reagents which have sterically hindered phenoxide ligands. These bulky aluminum reagents are monomeric in solution, thereby possess strong Lewis acidity to bind a variety of heteroatom-containing substrates such as carbonyl, carboxyl and amide compounds. The complexation is sometimes stereo-, regio-, and chemoselective, leading to selective organic reactions which could not be realized with other ordinary Lewis acicls such as AlCl_3, SnCl_4, BF_3, and TiCl_4. In particular, aluminum tris(2,6-diphenylphenoxide(ATPH) was explored recently for obtaining unprecedented reactivity and selectivity n several reactions. 1. Conjugate addition of carbanions to alpha, beta-unsaturated aldehydes 2. Exo-selective Diels-Alder reactions 3. Stereo-and asymmetric Claisen rearrangement 4.1,6-Addition to aromatic carbonyl substrates.
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