| Project/Area Number |
62065005
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| Research Category |
Grant-in-Aid for Specially Promoted Research
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| Allocation Type | Single-year Grants |
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| Research Institution | Nagoya University |
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Principal Investigator |
NOYORI Ryoji Nagoya University, Chemistry, Professor Faculty of Science, 理学部, 教授 (50022554)
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| Co-Investigator(Kenkyū-buntansha) |
KITAMURA Masato Nagoya Uni. Fac. of Science Assoc. Professor, 理学部, 助教授 (50169885)
MARUOKA Keiji Nagoya Uni. Fac. of Engineering Assoc. Professor, 工学部, 助教授 (20135304)
SUZUKI Masaaki Nagoya Uni., Chemical Instrument Center Assoc. Professor, 化学測定機器センター, 助教授 (90093046)
HAYAKAWA Yoshihiro Nagoya Uni., College of General Edcation Assoc. Professor, 教養部, 助教授 (50022702)
YAMAMOTO Hisashi Nagoya Uni., Chemistry, Fac. of Engineering Professor, 工学部, 教授 (10135311)
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| Project Period (FY) |
1987 – 1990
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| Project Status |
Completed (Fiscal Year 1991)
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| Budget Amount *help |
¥202,000,000 (Direct Cost: ¥202,000,000)
Fiscal Year 1990: ¥40,000,000 (Direct Cost: ¥40,000,000)
Fiscal Year 1989: ¥46,000,000 (Direct Cost: ¥46,000,000)
Fiscal Year 1988: ¥56,000,000 (Direct Cost: ¥56,000,000)
Fiscal Year 1987: ¥60,000,000 (Direct Cost: ¥60,000,000)
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| Keywords | BINAL-H / TMSOTf / BINAP / BINAP-Rh / BINAP-Ru / MAD / CAB / Pd(0)Catalyzed deprotection / 有機亜鉛 / アルキル化 / 不斉クライゼン転位 / アリル系保護基 / 超純度DNA合成 / 超原子価スズ化合物 / 分子内エン反応 / アミノアルコール / 有機亜鉛化合物 / アシロキシボラン / 不斉DielsーAlder反応 / BINAP錯体 / プロスタグランジン合成 / DNA固相合成 / 不斉アルキル化 / 有機アルミニウム / 不斉増幅 / 不斉触媒 / O価バラジウム / 2-5A / アントラサイクリン / アリルオキシカルボニル / パラジウム / イソカルバサイクリン / ルテニウム錯体 / 1-βメチルチエナマイシン / ナブロキャン / シトロネロール / ビタミン / プロスタグランジン |
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| Research Abstract |
Research objectives : the following six objectives have been studied. (1) development of new synthetic organic reactions and management of the research (R. Noyori), (2) development of new reactions based on the use of typical elements (H. Yamamoto), (3) synthesis of oligonucleotides (B. Hayakawa), (4) prostaglandin synthesis (M. Suzuki), (5) synthesis of anthracyclin antibiotics (K. Maruoka), (6) synthesis of alkaloids, terpines, and vitamines (M. Kitamura).
Results : successful results are summarized as follows. (1) organozinc aided stereoselective conjugate addition to enones and selective momoalkylation of enolates ; selective propargylation of carbonyls ; catalysis of PG endoperoxides ; asymmetric reduction of carbonyls with BINAL-H ; TMSOTf catalyzed aldol-type reactions ; practical synthesis of BINAP ; BINAP-Rh catalyzed asymmetric hydrogenation of olefins ; BINAP-Ru (II) catalyzed asymmetric hydrogenation of functionalized olefins ; kinetic resolution of allylic alcohols by BINAP
… More
-Ru catalyzed hydrogenation ; asymmetric synthesis of diols by double stereodifferentiation ; kinetic resolution of a racemic hydroxy ketones ; assymmetric synthesis using dynamic kinetic resolution ; asymmetric 1, 3-hydrogen shift catalyzed by BINAP-Rh catalyst ; kinetic resolution of 4-hydroxy-2-cyclopentenone ; catalytic enantioselective alkylation using organozinc reagents and elucidation of the mechanism ; efficient Pd(O)-catalyzed deprotection of allyl- and allyloxycarbonyl protective groups in nucleosides and ncleotides ; synthesis of unsymmetrically (2'-5'), (3'-5') linked oligonucleotides. (2) amphiphilic alkylation using alliminium agents, MAD and MAT : synthesis of steroids, conjugate addition of enones, selective reduction of two different ketones ; organoaluminium-promoted Claisen rearrangement : synthesis of Lardolure and Recifeolide ; CAB catalysis in organic synthesis : asymmetric Diels-Alder reaction, Aldol reaction, enereaction ; stereoselective synthesis of geranyl- and neryl-metal reagents ; synthesis of Ubiquinone 10. (3) synthesis of extremely pure 60 mers of oligonucleotides ; direct synthesis of solid-anchored DNA oligomers. (4) extremely shot-step synthesis of prostaglandin E_2 ; general syntheis of PGs ; synthesis of isocarbacyclin, synthesis of punaglandins ; synthesis of a photoaffinity probe reagent for prostacyclin receptor. (5) asymmetric Hetero-Diels-Alder reaction based on the use of binaphthol modified chiral alunminium agent AL ; efficient in situ generation of chiral Lewis acid ; asymmetric ene and Claisen reactions with AL ; stereoselcctive C-glycosidation ; synthesis of pseudosugars ; efficient synthesis of a partial structure of FK506 ; efficient construction of anthracyclin skeletons. (6) BINAP-Ru catalyzed enantioselective hydrogenation of enamides ; synthesis of a key intermediate for general synthesis of isoquinoline alkaloids ; asymmetric hydrogenation of allylic alcohols ; BINAP-Ru catalyzed asymmetric hydrogenation of bifunctionalized ketones ; asymmetric synthesis of 1beta-methylcarbapenems ; asymmetric synthesis of beta-amino acids ; asymmetric synthesis of camitine, statine, and analogues ; stereoselective synthesis of threonine type compounds. Less
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