| Project/Area Number |
13853003
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| Research Category |
Grant-in-Aid for Scientific Research (S)
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| Allocation Type | Single-year Grants |
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| Research Field |
物質変換
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| Research Institution | KYOTO UNIVERSITY |
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Principal Investigator |
MARUOKA Keiji Kyoto Univ., Grad. Sch. Sci., Professor, 大学院・理学研究科, 教授 (20135304)
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| Co-Investigator(Kenkyū-buntansha) |
OOI Takashi Kyoto Univ., Sch. of Sci., Associate Professor, 大学院・理学研究科, 助教授 (80271708)
大本 清之 京都大学, 大学院・工学研究科, 助手 (50314232)
俣野 善博 京都大学, 大学院・理学研究科, 助手 (40231592)
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| Project Period (FY) |
2001 – 2005
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| Project Status |
Completed (Fiscal Year 2005)
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| Budget Amount *help |
¥123,890,000 (Direct Cost: ¥95,300,000、Indirect Cost: ¥28,590,000)
Fiscal Year 2005: ¥18,590,000 (Direct Cost: ¥14,300,000、Indirect Cost: ¥4,290,000)
Fiscal Year 2004: ¥18,590,000 (Direct Cost: ¥14,300,000、Indirect Cost: ¥4,290,000)
Fiscal Year 2003: ¥24,700,000 (Direct Cost: ¥19,000,000、Indirect Cost: ¥5,700,000)
Fiscal Year 2002: ¥24,700,000 (Direct Cost: ¥19,000,000、Indirect Cost: ¥5,700,000)
Fiscal Year 2001: ¥37,310,000 (Direct Cost: ¥28,700,000、Indirect Cost: ¥8,610,000)
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| Keywords | acid / base catalysts / bidentate Ti(IV) complex / enantioselective allylation / 1, 3-dipolar cycloaddition / phase transfer catalysis / binaphthol / amino acid / Strecker reaction / 精密ルイス酸触媒 / 二点配位型ルイス酸 / 不斉双極子環状付加 / マンザシジンA / 不斉ストレッカー反応 / 不斉マンニッヒ反応 / 精密ルイス酸 / カルボニル / グリシンエステル / 不斉アルキル化反応 / 不斉アルドール反応 / 不斉共役付加反応 / 不斉アリル化 / ティシュチェンコ反応 / 不斉ニトロアルドール反応 / シリル化合物 / Neber転位 / 精密合成 / 不斉合成 / ルイス酸 / 二点配位型 / キラル触媒 / 相間移動触媒 / L-ドーバ |
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| Research Abstract |
In this research project, we focused our attention on the rational design of truly efficient acid/base catalysts for the development of synthetic processes in order to achieve the high reactivity and selectivity, not observable by ordinary, acid/base catalysts. In the sophisticated Lewis acid chemistry, a new, chiral bidentate Ti(IV) complex was successfully designed and can be utilized for simultaneous coordination to aldehyde carbonyls, thereby allowing the precise enantioface discrimination of such carbonyls for a new catalytic, practical enantioselective allylation of aldehydes with allyltributyltin. This chiral bidentate Ti(IV) complex has been successfully applied to asymmetric 1, 3-dipolar cycloaddition of nitrones or diazoacetates. On the other hand, phase transfer catalysis is a very useful approach that typically involves simple experimental operations, mild reaction conditions, inexpensive and environmentally benign reagents and solvents, and the large-scale reactions. Accordingly, structurally rigid, chiral spiro ammoniurn salts derived from commercially available (S)- or (R)-binaphthol have been designed as new C_2-symmetric chiral phase transfer catalysts and successfully applied to the highly efficient, catalytic enantioselective synthesis under mild phase transfer conditions. Quite recently, we have successfully designed simplified, yet very active chiral phase transfer catalysts for practical asymmetric synthesis of α-alkyl- and α,α-dialkylamino acids. In addition, chiral, helical-type phase transfer catalysts were newly designed for effecting asymmetric Strecker reaction for large-scale production of sterically hindered α-alkylamino acids. A bowl-shaped organometallic host, tris(2, 6-diphenylbenzyl)-silyl, -germyl, and -tin compounds can be prepared, and applied to selective organic transformations.
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