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Construction of Asymmetric Space

Research Project

Project/Area Number 05234104
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Research InstitutionThe University of Tokyo

Principal Investigator

KOGA Kenji  University of Tokyo, Faculty of Pharmaceutical Sciences, Professor, 薬学部, 教授 (10012600)

Co-Investigator(Kenkyū-buntansha) NAKAMURA Eiichi  University of Tokyo, Graduate School of Science, Professor, 大学院・理学系研究科, 教授 (00134809)
TOMIOKA Kiyoshi  Osaka University, Institute of Scientific and Industrial Research, Professor, 産業科学研究所, 教授 (50114575)
MUKAIYAMA Teruaki  Science University of Tokyo, Faculty of Science, Professor, 理学部, 教授 (60016003)
FUJI Kaoru  Kyoto University, Institute of Chemical Research, Professor, 化学研究所, 教授 (20027056)
板井 昭子  東京大学, 薬学部, 客員教授 (60012647)
Project Period (FY) 1993 – 1995
Project Status Completed (Fiscal Year 1996)
Budget Amount *help
¥95,700,000 (Direct Cost: ¥95,700,000)
Fiscal Year 1995: ¥27,900,000 (Direct Cost: ¥27,900,000)
Fiscal Year 1994: ¥29,300,000 (Direct Cost: ¥29,300,000)
Fiscal Year 1993: ¥38,500,000 (Direct Cost: ¥38,500,000)
Keywordsasymmetric space / chiral lithium amide / asymmetric deprotonation / asymmetric alkylation / asymmetric protonation / chiral memory / asymmetric addition / stereoselective glycosidation / 不斉α-アルキル化反応 / グリコシル化反応 / キラルホスフィンアミド / 不斉共役付加反応 / イミン / キレーション制御反応 / グリコシル化 / 有機銅 / 不斉アリル化 / ADAM & EVE / 立体選択的グリコシル化反応 / 有機リチウム / 立体選択的アリル化 / 生体高分子
Research Abstract

"Construction of Asymmetric Space" plays a central role in asymmetric synthesis. Investigations have been made on the construction of efficient asymmetric spaces and its applications to design novel methods of asymmetric synthesis and catalytic asymmetric synthesis. Following results were obtained.
1) Multidentate chiral lithium amides and chiral amines that can form efficient chiral spaces by chelation were designed and synthesized. Novel asymmetric reactions, such as asymmetric deprotonation, alkylation, and protonation, were developed using these chiral bases. These asymmetric reactions were further developed to catalytic asymmetric reacation. 2) Evidences for the existence of chiral enolates from optically active alpha-amino acid derivatives by deprotonation were found. The new concept "Chiral Memory" was developed and applied to the synthsis of optically active compounds. 3) To utilize sugar derivatives as useful compounds having efficient chiral spaces, highly stereoselective glycosidation methods giving the product in high yields were developed. 4) Chiral di-ethers and amodophosphine derivatives providing efficient chiral spaces were designed and synthesized. They were proved to be useful for the catalytic asymmetric conjugate addition reactions of organolithium and organocopper reagents. 5) Experimental ant theoretical studies were made on the nature of asymmetric spaces for the purpose to deisgn novel asymmetric synthesis. Highly stereoselective addition reactions were developed using novel organocopper reagents and allylzinc complexes.

Report

(4 results)
  • 1996 Final Research Report Summary
  • 1995 Annual Research Report
  • 1994 Annual Research Report
  • 1993 Annual Research Report
  • Research Products

    (66 results)

All Other

All Publications (66 results)

  • [Publications] K.Koga: "Enantioselective Michael Reaction of Ketone Lithium Enolate Using a Chiral Amine Ligand" Tetrahedron Lett.37. 6343-6346 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] K.Koga: "Solution Structures of a Monodentate Chiral Lithium Amide in the Presence of Lithium Halide" Tetrahedron Lett.37. 7377-7380 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] K.Koga: "An Approach to Catalytic Asymmetric Deprotonation of 4-Substituted Cyclohexanones" Tetrahedron Lett.37. 8195-8198 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] K.Fuji: "Chiral Recognition of Amino Acid Derivatives by 1,1-Binaphthyl-8,8-diol" Tetrahedron Lett.37. 4153-4156 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Mukaiyama: "A Significant Effect of a Lithium Salt in the Stereo-controlled Synthesis of α-D-Ribofuranosides" Chem.Lett.271-272 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] E.Nakamura: "Enantioselective Allylzincation of Cyclic Aldimines in the Presence of Anionic Bis-oxazoline Ligand" J.Am.Chem.Soc.118. 8489-8490 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] K.Koga: "Enantioselective Michael Reacation of Ketone Liathium Enolates Using a Chiral Amine Ligand" Tetrahedron Lett.37. 6343-6346 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] K.Koga: "Solution Structures of a Monodentate Chiral Lithium Amide in the Presence of Lithium Halide" Tetrahedron Lett.37. 7377-7380 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] K.Koga: "An Approach to Catalytic Asymmetric Deprotonation of 4-Substituted Cyclohexanones" Tetrahedron Lett.37. 8195-8198 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] K.Fuji: "Chiral Recognition of Amino Acid Derivatives by 1,1'-Binaphthyl-8,8'-diol" Tetrahedron Lett.37. 4153-4156 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Mukaiyama: "A Siognificant Effect of a Lithium Salt in the Stereocontrolled Synthesis of alpha-D-Ribofurano-sides" Chem.Lett.271-272 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] E.Nakamura: "Enantioselective Allylzincation of Cyclic Aldimines in the Presence of Anionic Bisoxazoline Ligand" J.Am.Chem.soc.118. 8489-8490 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Kenji Koga: "Approaches to Catalytic Asymmetic Formation and Reactions of Lithium Enalates" 有機合成化学協会誌. 53. 1021-1032 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Maki Uragami: "Highly Enantioselective Aldol Roaction Mediated by Mrted Aggregates Derned from a Lithium Ester Enolate and Tetradentate Chiral Lithium Awide" Tetrahedion:Asymmetry. 6. 701-704 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Toshiya TAKAHASHI: "Enantioselective Darsens Reaction:Asymmetric Synthesrs of trans- Glycidic Ester Mediated by Chirol Lithium Amides" Chem.Pharm.Bull.43. 1821-1823 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Kaoru Fuji: "Enantioselective Protonation of Enolates:Novel Chiral Proton Sources and Remarkable Effects of the Countercation" J.Org.Chem.60. 1914-1915 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Kaoru Fuji: "An Enantioselective Synthesrs of (-)-Pseudophrynaminol through Asymmetric Nitroolefination" Synlett.367-368 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Fujie Tanaka: "1、1′-Binaphthalene-2、2′-diol as a Chirol Auxiliary.Diastereoselective Alkylation of Binaphthyl Esters,Complex-Jnluced Pnximity Ellects in Endate Formation.and One step Synthesrs of an Optically Active β-Substituted Roto" J.Am.Chem.Soc.117. 12159-12171 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] T.Mukaiyama: "An Efficient Glycosylation Reaction of 1-Hydroxy Sugars with Various Nucleophiles Using A Catalytic Amaunt of Activator and Heomethyldisiloxane" Stnthesis. 1368-1373 (1994)

    • Related Report
      1995 Annual Research Report
  • [Publications] H.Uchiro: "Trityl Salt Catalyzed Stereoselective Glycosylation of Alcohols with 1-Hyclroxyvibofuranose" Chem.Lett.79-80 (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] H-Uchiro: "A Signrticant Eflect of a Lithium Salt in the Steroocontrolled Syuthesrs of α-D-Ribofuranosicles" Chem-Lett.in press. (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] Kiyoshi Tomioka: "Diastereoselective Throphenol Addition to (S)-N-α、β-Unsaturated Carbonyl-r-trrtyloxymethyl-r-butyrolactams" J.Org.Chem.60. 6188-6190 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Motomu Kanai: "Asymmetric Conjugate Additron of Organomagnesium Caprates Controlled by Stoichiometric Ameunt of Chiral Phosphine" Tetrahedron letters. 36. 4273-4274 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Motomu Kanai: "Catalytic Asymmetric Conjugate Additron of Grignard Reagents Contolled by Copper(I)-Chiral Bidentate Phosphine Complex." Tetrahedron letters. 36. 4275-4278 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] E.Nakamuia: "Selectivities Carbometalation of Olefins.Experimental Results and Theovetical Analysrs" Pure Appl Chem.68. 123-130 (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] S.Mori: "Theoretical Studies no Chelation Controlled Carboryl Additron.Ml2Mg Addition to α-and β-Alkory Ketones and Aldehyces" J.Am.Chem.Soc.117. 5055-5065 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] S.Yamago: "Tertiary Phosphines,P-Chiral Phosphinites and Phosphonic Acid Esters Bearing Fullerene Substituant.Metol Complexes and Redox Proporbes" Tetrahedron. in press.

    • Related Report
      1995 Annual Research Report
  • [Publications] Kenji Koga: "Asymmetric cynthesis mediated by chiral ligands" Pure & Appl. Chem.66. 1487-1492 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Ryuichi Shirai: "Stereoselective Reactions .ZZII. Design and Synthesis of Chral Chelated Lithium Amides for Enantioselective Reactions" Chem. Pharm. Bull.42. 690-693 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Mitsuko Imai: "Catalytic Asymmetric Benzylation of Achiral Lithium Enolates Using a Chiral Ligand for Lithium in the Presonce of an Achiral Ligand" J. Am. Chem. Soc.116. 8829-8830 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Takuya Kumamoto: "Chiral Lithium 2-Aminoalkoxides as Reagents for Enantioselective Michael Reaction" Tetrahedron: Asymmetry. 5. 1431-1432 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Takeo Kawabata: "Direct Asymmetric α-Alkylation of Phenylalanine Derivatives Vsing No External Chiral Sources" J. Am. Chem. Soc.116. 10809-10810 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Kaoru Fuji: "Diastereosdective Diels-Alder Cycloadditions with Chiral 1-(Alkylsulfinyl)-2-nitroalkenes" J. Org. Chem.59. 2211-2218 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Kaoru Fuji: "Enhanced Reactivity of Zine Enolates over Lithium Enolates in Asymmetric Nitroolefination" Chem. Pharm. Bull.42. 999-1001 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Motomu Kanai: "Asymmetric Corjugate Addition of Organocupper -Amido-phosphine Reagents to Cycloalkenones" Tetrahedron Letters. 35. 895-898 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Kiyoshi Tomioka: "Origin ot Regioselectvivty in Electrophilic Reaction of Am Enaldimines" Tetrahedron Letters. 35. 1891-1892 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Manabu Okuda: "Stereo-and Regiochamical Aspects of the Micsunobu Reaction in Synthesis of Chiral Amino Ether Ligands for Asymmctric Reactions" Tetrahedron Letters. 35. 4585-4586 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Naoyuki Shimomura: "Secreoselective Synthesis of α-D and β-D-Ribofuranosides Catalyzed by the Combined Use of Silver Salcs and Their Partners" Bull. Chem. Soc., Jpn.67. 2532-2541 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Koki Matsubara: "An Efficient Method for the Stereoselective Synthesis of 2-Amino-β-D- and α-D-Glyosides from Peracylatel Sugars Using Active Acidic Species" Polish. J. Chem.68. 2365-2382 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Teruaki Mukaiyama: "An Efficient Glycosidation Reaction of 1-Hydroxy Sugars with Varions Suga with Various Nucleophiles Using Catalytic Amount of Activator and Hexa Methyldisilorane" Synthesis. 1368-1373 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] M.Nakamura: "Theoretical Studies of Nuclophilic Additions of Monomeric and Dimeric Organometallics" J. Chem. Soc., Faraday Trans. 29. 1789-1798 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] S.Yamago: "Tertiary Phosphines and P-Chiral Phosphinites Bearing Fullerene Substituent" J. Chem. Soc., Chem. Commun. 2093-2094 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] M.Y.Mizutani: "Efficient Automatic Search Method for Stable Docking Models of Protein and Ligand" J. Mol. Biol. 243. 310-326 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] T.Kawai: "High-Temperature Simulation of Dynamics of Cydohexane" Chem. Pharm. Bull. 42. 1315-1321 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] N.Tomioka: "GREEN: a Program package for Rational Docking Study" J. Comp. -Aided Molecular Design. 8. 347-366 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Tatsuro Yasukata: "Enontioselective Protonation of Achiral Lithium Enolates Using a Chiral Amine in the Presence of Lithium Bromidc" Tetrahedron:Asymmetry. 4. 35-38 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Yoshihiro Hasegawa: "Control of Diastereoselectivity in the Alkylation of chiral Lithium Enolates Mediated by a Chiral Secondary Amime Ligand" Tetrahedron Letters. 34. 1963-1966 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Kazumasa Aoki: "Reinvestigation on the Optical Purities of Optically Active Trimethylsilyl Enol Ethers of 4-Substitnted Cyclohexanones" Chem.Pharm.Bull.41. 994-996 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Masao Sobukawa: "Determination of the Protons Eliminated in the Regioselective Deprotonation of Some Optically Active 3-Keto Steroids" Tetrahedron Letters. 34. 1501-1504 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Kazumasa Aoki: "Enantioselective Deprotonation of 4-Substituted Cyclohexanones by Chiral Lithium Amides Having a Fluorine-containing Group" Tetrahedron Letters. 34. 1505-1508 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Kaoru Fuji: "Asymmetric Creation of Ouaternary Carbon Centers" Chem.Rev.93. 2037-2066 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Kiyoshi Tanaka: "Differentiation of Enantiotopic Carbonyl Groups by Honnor-Wadsworth-Emmous Reaction" Tetrahedron Letters. 34. 4071-4074 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Takeo Kawabata: "An Enantiodivengent Synthesis of threo-β-Amino Alcohols:Preparation of Key Intermediates for Bestatin and the Related Peptides" Tetrahedron Letters. 34. 5127-5130 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Koki Matsubara: "Stereoselective Synthesis of 0-(2-Azido-2-deoxy-α-D-galactopyranosyl)-L-segine and-L-threonine Derivatives by Using the Catalytic Ameunts of Active Acidic species." Chemistry Letters. 581-584 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Koki Matsubara: "Catalytic Stereoselective Synthesis of 2-Amino-2-deoxy-α-D-glucopyrarosides and Galactopyranosides" Chemistry Letters. 2145-2148 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Koki Matsubara: "High-yiddiry Catalytie Synthesis of Glycosyl Azidesfrom Peracylated Sugars" Chemistry Letters. 247-250 (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] Kiyoshi Tomioka: "Asymmetrie Addition of Aryllithiuns to Naphthalere BHA-esters Catalyzed by a chiral Ligand" Tetrahedron Letters. 34. 681-682 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Motomu Kanai: "Solvent Effect and NMR Behaviorer in a Chiral Amidophosphine Mediated Reaction of Organocuprate and Chalcone" J.Chem.Soc.,Chem.Commun.1248-1249 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Kiyoshi Tomioka: "Steric Tuning in Chiral Ligand-Cotalyzed Enantioselective Alkylation of Imines" Tetrahedron:Asymmetry. 4. 1603-1606 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] K.Kubota: "Ligand Control in the Stereoselective Allylzincation of Cydopropenes" J.Am.Chem.Soc.115. 5867-5868 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] M.Arai: "1.2-Asymmetric Induction in the S_N2^1-Allylation of Organocopper and Organozinc Regents" J.Org.Chem.58. 5121-5129 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] M.Nakamura: "Theoretical Studies on the Reaction of Solv Methyllithium Open Dimer with Aldehyde" J.Am.Chem.Soc.115. 11016-11017 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] M.Yamada: "Development of An Efficient Automated Docking Method" Chem.Pharm.Bull.41. 1200-1202 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Y.Nishibata: "Confirmation of Usefulness of a Structure Construetion Program Based on Three-dimensional Receptor Stweture for Rational Lead Generation" J.Med.Chem.36. 2921-2928 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] M.Ohno: "Designed Molecules.Reproducing the Active Conformation of Teleocidins" Tetrahedron Letters. 34. 8119-8122 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] A.Itai: "3D-QSAR in Drug Design,Theory,Methods and Applications" ESCOM Science Publishers B.V.,Leiden,Netherland., (1993)

    • Related Report
      1993 Annual Research Report

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Published: 1993-04-01   Modified: 2016-04-21  

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