| Project/Area Number |
10208201
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| Research Category |
Grant-in-Aid for Scientific Research on Priority Areas (B)
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| Allocation Type | Single-year Grants |
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| Research Institution | KYOTO UNIVERSITY (2000-2001)
Hokkaido University (1998-1999) |
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Principal Investigator |
MARUOKA Keiji Kyoto Univ., Grad. Sch. of Sci., Prof., 理学研究科, 教授 (20135304)
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| Co-Investigator(Kenkyū-buntansha) |
INANAGA Junji Kyushu Univ., Basic Org. Chem. Cent. Assoc. Prof., 基礎有機化学センター, 助教授 (50091244)
KAKUCHI Toyoji Hokkaido Univ., Grad. Sch. of Sci., Assoc. Prof., 地球環境科学研究科, 助教授 (80113538)
OOI Takashi Kyoto Univ., Grad. Sch. of Sci., Assoc. Prof., 理学研究科, 助教授 (80271708)
SHIONOYA Mitsuhiko Tokyo Univ., Grad. Sch. of Sci., Prof., 理学系研究科, 教授 (60187333)
UEMURA Sakae Kyoto Univ., Grad. Sch. of Eng., Prof., 工学研究科, 教授 (70027069)
友岡 克彦 東京工業大学, 工学部, 助教授 (70207629)
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| Project Period (FY) |
1998 – 2000
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| Project Status |
Completed (Fiscal Year 2001)
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| Budget Amount *help |
¥78,900,000 (Direct Cost: ¥78,900,000)
Fiscal Year 2000: ¥25,700,000 (Direct Cost: ¥25,700,000)
Fiscal Year 1999: ¥25,700,000 (Direct Cost: ¥25,700,000)
Fiscal Year 1998: ¥27,500,000 (Direct Cost: ¥27,500,000)
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| Keywords | Lewis acid / base active species / pentacoordinate boron complex / bidentate metal catalyst / dynamic stereochemical control / amino acid / chiral rare-earth metal complex / montmorillonite catalyst / carbanion reaction / 不斉エポキシ化 / 速度論的光学分割 / ルイス酸活性種 / 5配位ホウ素鎖体 / 立体化学制御 / 機能性ルイス酸触媒 / 光学活性希土類鎖体 / 固体触媒 / 5配位典型金属活性種 / 二点配位型有機金属分子 / 機能性ルイス酸 / 精密環化重合 / 希土類ルイス酸塩基触媒 / カルポアニオン反応 |
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| Research Abstract |
In this research project, we focused our attention on the design of truly important synthetic catalysts for the development of Lewis acid/base active species in order to achieve the highly selective stereochemical control. Namely, Maruoka studied unprecedented chelate-type pentacoordinate boron complexes and the bidentate Lewis acid chemistry. In the latter 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. Ooi prepared (2,7-dimethyl-1,8-biphenylenedioxy)bis(dimethylaluminum) and (anthraquinone-1,8-dioxy)bis(triisopropoxytitanium) as bidentate Lewis acids for the simultaneous coordination to carbonyl substrates. The high, simultaneous coordination ability of the bidentate organoaluminum and titanium reagents toward carbony
… More
ls is emphasized in comparison with the corresponding monodentate reagents, and characterized by evaluating the double electrophilic activation of ketonic substrates in several electrophilic reactions. Kakuchi used the ring polymerization of 1,2 : 4,5-dianhydropentitol for the application to the chiral stationary phases and the elucidation of the optical resolution mechanism of amino acids. Inanaga designed chiral rare-earth metal complexes as thermodynamically stable, single active species for applying asymmetric transformations. Uemura developed the Friedel-Crafts-type reactions of alkenes and the oxidation reactions of alcohols by using metal cation-exchanged montmorillonite catalysts. Shionoya synthesized a novel nucleoside for alternative DNA base pairing through metal complexation, and carried out the molecular recognition of terephthalic acids by supramolecular self-assembly of acridine-pendant Zn(II)-cyclen complex. Tomooka developed the enantioselective carboanion reactions and the enantioselective radical reactions for effecting the dynamic stereochemical control of organolithium species. Less
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