| Project/Area Number |
15205021
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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 |
Environmental chemistry
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| Research Institution | Nagoya University |
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Principal Investigator |
ISHIHARA Kazuaki Nagoya University, Graduate School of Engineering, Professor (40221759)
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| Co-Investigator(Kenkyū-buntansha) |
SAKAKURA Akira Nagoya University, EcoTopia Science Institute, Associate Professor (80334043)
HATANO Manabu Nagoya University, Graduate School of Engineering, Lecturer (20362270)
赤倉 松次郎 愛知教育大学, 教育学部, 助教授 (70303683)
幅上 茂樹 山形大学, 工学部, 助教授 (30252266)
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| Project Period (FY) |
2003 – 2006
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| Project Status |
Completed (Fiscal Year 2006)
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| Budget Amount *help |
¥51,480,000 (Direct Cost: ¥39,600,000、Indirect Cost: ¥11,880,000)
Fiscal Year 2006: ¥10,010,000 (Direct Cost: ¥7,700,000、Indirect Cost: ¥2,310,000)
Fiscal Year 2005: ¥10,010,000 (Direct Cost: ¥7,700,000、Indirect Cost: ¥2,310,000)
Fiscal Year 2004: ¥10,010,000 (Direct Cost: ¥7,700,000、Indirect Cost: ¥2,310,000)
Fiscal Year 2003: ¥21,450,000 (Direct Cost: ¥16,500,000、Indirect Cost: ¥4,950,000)
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| Keywords | catalysis / salt / conjugate / acid-base combination chemistry / asymmetric synthesis / artificial enzymes / hydrophobic effect / cation-π complex / グリーンケミストリー / エステル縮合反応 / 均一触媒 / アンモニウム塩 / 非金属系触媒 / 脱水反応 / 触媒の回収・再利用 |
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| Research Abstract |
The design of small but highly functional artificial catalysts is very important for practical organic synthesis. We have succeeded in the rational design of small and simple catalysts and related reactions based on acid-base combination chemistry. Acid-base combined catalysts can be classified into three types: (1) acid-base combined salt catalysts (Type A), (2) conjugate acid-base catalysts (Type B), and (3) non-conjugate acid-base catalysts (Type C):
1. Acid-base combined salt catalysts (Type A)
1-1. Bronsted acid-base combined salt catalysts (Type A-1): bulky diarylammonium pentafluorobenzenesulfonates as mild and extremely active dehydrative ester condensation catalysts; chiral ammonium alkanesulfonates as asymmetric Diels-Alder catalysts
1-2. Lewis acid-base combined salt catalysts and reagents (Type A-2): magnesium ate complexes derived from Grignard reagents and alkyllithium as highly alkyl-selective reagents to ketones; zinc ate complexes as catalysts for the highly alkyl-selecti
… More
ve addition of Grignard reagents to ketones and aldimines
1-3. Cation-anion pair catalysts (Type A-3): lithium N, N-diisopropylamide in Haller-Bauer and Cannizzaro reactions; chiral lithium binaphtholate aqua complex as a highly effective asymmetric catalyst for trimethylsilylcyanation
1-4. Cation-a complex catalysts (Type A-4): chiral Cu(II)・L-DOPA-derived monopeptide complex as an asymmetric Diels-Alder and Mukaiyama-Michael catalyst
2. Lewis acid-base conjugate catalysts (Type B): molybdenum oxides as highly effective dehydrative cyclization catalysts directed toward the synthesis of oxazolines and thiazolines (Type B-1(monoconjugation)); zinc(II)・3,3'-diphosphinoyl-BINOLates in the asymmetric addition of organozinc reagents to aldehydes (Type B-2 (triconjugation))
3. Bronsted acid-Lewis base non-conjugate asymmetric catalysts (separated type) (Type C): L-histidine-derived sulfonamide as a minimal artificial acylase for the kinetic resolution of racemic alcohols
Thus, we developed new acid-base combined catalysts bearing excellent functions such as dual activation, control of nucleophilicity and basicity, asymmetric induction, hydrophobic effect, and so on. Current research is focused on the development of artificial highly functional catalysts which are superior to natural enzymes. Less
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