• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to project page

1996 Fiscal Year Final Research Report Summary

SELECTIVITY AND REACTIVITY OF ORGANIC REACTIONS CONTROLLED BY THE COMBINED EFFECTS OF GROUND AND TRANSITION STATES

Research Project

Project/Area Number 07304075
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section総合
Research Field Organic chemistry
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

TAKEUCHI Ken'ichi  KYOTO UNIV., ENGINEERING,PROF., 工学研究科, 教授 (50026358)

Co-Investigator(Kenkyū-buntansha) OHNO Atsuyoshi  KYOTO UNIV., INST.CHEM.RES., PROF., 化学研究所, 教授 (70027077)
INAZU Takahiko  KYUSHU UNIV., SCIENCE,PROF., 理学部, 教授 (60037207)
ANDO Wataru  UNIV.TSUKUBA,CHEMISTRY,PROF., 化学系, 教授 (30008429)
ANDO Takashi  SHIGA UNIV.MED.SCI., CHEMISTRY,PROF., 医学部, 教授 (70029867)
AKIBA Kin-ya  HIROSHIMA UNIV., SCIENCE,PROF., 理学部, 教授 (20011538)
Project Period (FY) 1995 – 1996
KeywordsGround State Structure / Transition State Structure / Selectivity and Reactivity / Reaction Intermediate / Carbocations / Carbenes / Organic Stereochemistry / Molecular Orbital Calculations
Research Abstract

The group was devided into following three subgroups. The members whose names are shown in parentheses obtained successful results in the given research projects.
Subgroup (1) for the study of structural factors controlling energies of ground and transition states : Steric control of nucleophilic solvent intervention in solvolysis (K.Takeuchi) ; Electronic structure of tetramethyleneethane (H.Iwamura) ; Stabilization of highly reactive species in novel reaction sites (R.Okazaki) ; Nucleophilic substitution and elimination of vinyl iodonium salts (T.Okuyama) ; Solute-solvent interaction in transition state (Y.Kondo) ; Isomerization via excited transition state of radicalcations of stilbene derivatives (H.Sakuragi) ; Reduction-oxidation behavior of benzyl radicals (Y.Sawaki) ; Kinetic stabilization of highly strained paracyclophanes (T.Tsuji).
Subgroug (2) for the study of stereochemical characteristics of ground and transition state structures : Mechanism of sonochemical activation (T.And … More o) ; Orientation of polar group and stereoselectivity in hydride reduction (A.Ohno) ; Design of strained electron-transfer system (A.Oku) ; High enantio-selective reaction by use of enantiopure nickel catalysts (S.Kanemasa) ; Ground and transition state effects on the selectivity of hydride reduction (S.Tomoda) ; Steric effects in the reactions of alkylcarbenes (H.Tomioka) ; Analysis of steric pathways by use of OMEGA_S (M.Hirota) ; Theoretical prediction of reactivity by including transition state (H.Fujimoto) ; Isotope effect on reaction pathway of nucleophilic reactions to carbonyl group (H.Yamataka).
Subgroup (3) for the study of characteristics of ground and transition state structures involving heteroatoms : Trap of intermediates of Berry pseudorotaion and kinetics of interconversion (K.Akiba) ; Rearrangement of 3,3'-bis (silacyclopropane) and bis (silacyclopropene) (W.Ando) ; Synthesis and properties of azacalixarenes (T.Inazu) ; Nucleophilic substitution of aromatic nitro compounds by use of nonionic strong bases (N.Ono) ; Mn-salen catalyzed asymmetric epoxidation (T.Katsuki) ; Role of heteroatoms in controlling nucleophilic substitution to unsaturated bonds (T.Kitamura) ; Mechanism of alcohol addition to silatriafulvenes (M.Kira) ; Nonclassical aromatic nitration (H.Suzuki) ; Structures and reactions of metallofullerenes (S.Nagase). Less

  • Research Products

    (52 results)

All Other

All Publications (52 results)

  • [Publications] 竹内賢一: "Synthesis of Bifunctional Polycyclic Compounds and Their Application to Mechanistic Studies of Solvolysis Reactions" Bull. Chem. Soc. Jpn.69. 833-851 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 秋葉欣哉: "First Characterization of a 10-P-5 Spirophosphorane with an Apical Carbon-Equatorial Oxygen Ring. Kinetic Studies on Pseudorotation of Stereoisomers" J. Am. Chem. Soc.118. 12866-12867 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 安藤喬志: "Mechanism of Sonochemical Excitation in the Reactions of Lead Tetraacetate with Some Organic Substrates" Ultrasonic Sonochemistry. 3. 223-227 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 安藤亘: "Synthesis and Reaction of Polythiadisilabicyclo [k. l. m] alkanes" J. Organom. Chem.516. 155-165 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 稲津孝彦: "Efficient Synthesis of 2, 11, 20-Triaza [3. 3. 3] (2, 6) pyridinophane" J. Org. Chem.61. 8304-8306 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 岩村秀: "Diazodi (4-pyridyl) methane as a Photo-responsive Spin Source/Magnetic Coupling Unit" Angew. Chem., Int. Ed. Engl.35. 755-757 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 大野惇吉: "NAD (P)^+-NAD (P) H Models. 87. Nonsteric Stereochemistry Controlled by a Carbonyl Group" Bull. Chem. Socl. Jpn.69. 1679-1685 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 岡崎廉治: "Cycloaddition and Oxidation Reactions of a Stable Thioaldehyde, (2, 4, 6-Tri-t-butyl) thiobenzaldehyde" Bull. Chem. Socl. Jpn.69. 719-724 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 奥彬: "Migratory Aptitude of Substituents on Silicon Atoms of Disilylcarbenes" J. Phys. Org. Chem.9. 619-622 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 奥山格: "Ring-Opening Reactions of Cyclic Sulfinate Esters with a Phenolic Leaving Group" Bull. Chem. Soc. Jpn.69. 2639-2644 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 小野昇: "A New Method for Chemical Modification of Conductive Polypyrroles without Destroying Their Conductivity" Adv. Mater.9. 149-153 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 香月勗: "Enantiospecific Ring Expansion of Oxetanes : Stereoselective Synthesis of Tetrahydrofurans from Oxetanes" Heterocycles. 42. 305-317 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 金政修司: "Exclusively endo-Selective Lewis Acid-Catalyzed Hetero Diels-Alder Reactions of (E)-1-Phenylsulfonyl-3-alken-2-ones with Vinyl Ethers" Tetrahedron. 52. 1205-1220 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 北村二雄: "An Efficient Ligand Exchange Reaction of β-(Trifyloxy) vinyliononium Triflates with Aryllithium Reagents Leading to Diarylinonium Triflates" Tetrahedron Lett.37. 3721-3722 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 吉良満夫: "Synthesis and Reactions of Neutral Hepercoordinate Allylsilicon Compounds Having Tropolonato Ligand" Organometallics. 15. 5335-5341 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 近藤泰彦: "Single-ion Enthalpies of Transfer as a Scale of Nucleophilic Reactivity towards Ethyl Iodide in Acetonitrile" J. Chem. Soc., Perkin Trans. 2. 1699-1703 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 櫻木宏親: "Observation of a Novel Fluorescent Dimer of Zinc Tetrasulphonatophthalocyanine" Chem. Lett.345-346 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 沢木泰彦: "Redox Reaction of Benzyl Radicals with Aromatic Radical Ions Photogenerated. The Marcus Inverted Region and the Selective Formation of Carbocations or Carbanions" J. Am. Chem. Soc.118. 7255-7264 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 鈴木仁美: "Ozone-mediated Nitration of Naphthalene and Some Methyl Derivatives with Nitrogen Dioxide. Remarkable Enhancement of the 1-Nitro/2-Nitro Ratio and Mechanistic Implications" J. Chem. Soc., Perkin Trans. 2. 677-683 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 辻孝: "Direct Synthesis of 2-Norbornanone Dithioacetals from 2-Cyclopentenone Dithioacetals and Dienophiles. Synthetic Appication of Thermal Interconversion between Cyclic Dithioacetals and the Ring-opened Vinyl Sulfide Forms" Tetrahedron. 52. 9979-9990 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 富岡秀雄: "Anomalous Effects of Para Substituents on the Stability of Sterically Congested Triplet Diaryl-carbenes. The First Triplet Carbene Surviving over Minutes under Normal Conditions" J. Am. Chem. Soc.118. 8723-8724 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 友田修司: "Nature of the Intramolecular Se...N Non-bonded Interaction of 2-Selenobenzylamine Derivatives. An Experimental Evaluation by H-1, C-13, Se-77, and N-15 NMR Spectroscopy" J. Am. Chem. Soc.118. 8077-8084 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 永瀬茂: "Endohedral Metallofullerenes : New Spherical Cage Molecules with Interesting Properties" Bull. Chem. Soc. Jpn.69. 2131-2142 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 廣田穣: "Estimation of Reactivity by Correlation Analyses Using Ωs and Δ_X B as Substituent Parameters" Bull. Chem. Soc. Jpn.69. 1003-1015 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 藤本博: "Theoretical Study of the Reactions of Allylsilanes with Carbonyl Compounds" J. Am. Chem. Soc.118. 1750-1755 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 山高博: "Stereoelectronic Effects in the Nucleophilic Addition to the sp-Hybridized Carbon of a Ketene and Vinyl Cation : When is a Mesityl Effectively Smaller than a Phenyl Ring?" J. Am. Chem. Soc.118. 12580-12587 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] TAKEUCHI,Ken'ichi et al.: "Synthesis of Bifunctional Polycyclic Compounds and Their Application to Mechanistic Studies of Solvolysis Reactions" Bull.Chem.Soc.Jpn.Vol.69. 833-851 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] AKIBA,Kin-ya et al.: "First Characterization of a 10-P-5 Spirophosphorane with an Apical Carbon-Equatorial Oxygen Ring. Kinetic Studies on Pseudorotation of Stereoisomers" J.Am.Chem.Soc.Vol.118. 12866-12867 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] ANDO,Takashi et al.: "Mechanism of Sonochemical Excitation in the Reactions of Lead Tetraacetate with Some Organic Substrates" Ultrasonic Sonochemistry. Vol.3. 223-227 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] ANDO,Wataru et al.: "Synthesis and Reaction of Polythiadisilabicyclo [k.l.m] alkanes" J.Organom.Chem.Vol.516. 155-165 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] INAZU,Takahiko et al.: "Efficient Synthesis of 2,11,20-Triaza [3.3.3] (2,6) pyridinophane" J.Org.Chem.Vol.61. 8304-8306 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] IWAMURA,HIIZU et al.: "Diazodi (4-pyridyl) methane as a Photo-responsive Spin Sourcel/Magnetic Coupling Unit" Angew.Chem., Int.Ed.Engl.Vol.35. 755-757 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] OHNO,Atsuyoshi et al.: "NAD (P) ^+-NAD (P) H Models. 87. Nonsteric Stereochemistry Controlled by a Carbonyl Group" Bull.Chem.Soc.Jpn.Vol.69. 1679-1685 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] OKAZAKI,Renji et al.: "Cycloaddition and Oxidation Reactions of a Stable Thioaldehyde, (2,4,6-Tri-butyl) thiobenzaldehyde" Bull.Chem.Soc.Jpn.Vol.69. 719-724 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] OKU,Akira: "Migratory Aptitude of Substituents on Silicon Atoms of Disilylcarbenes" J.Phys.Org.Chem.Vol.9. 619-622 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] OKUYAMA,Tadashi et al.: "Ring-Opening Reactions of Cyclic Sulfinate Esters with a Phenolic Leaving Group" Bull.Chem.Soc.Jpn.Vol.69. 2639-2644 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] ONO,Noboru: "A New Method for Chemical Modification of Conductive Polypyrroles wihout Destroying Their Conductivity" Adv.Mater.Vol.9. 149-153 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] KATSUKI,Tsutomu et al.: "Enantiospecific Ring Expansion of Oxetanes : Stereoselective Synthesis of Tetrahydrofurans from Oxetanes Vinyl Ethers" Heterocycles. Vol.42. 305-317 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] KANEMASA,Shuji et al.: "Exclusively endo-Selective Lewis Acid-Catalyzed Hetero Diels-Alder Reactions of (E) -1-Phenylsulfonyl-3-alken-2-ones with Vinyl Ethers" Tetrahedron. Vol.52. 1205-1220 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] KITAMURA,Tsugio et al.: "An Efficient Ligand Exchange Reaction of beta- (Trifyloxy) vinyliononium Triflates with Aryllithium Reagents Leading to Diaryliononium Triflates" Tetrahedron Lett.Vol.37. 3721-3722 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] KIRA,Mitsuo et al.: "Synthesis and Reactions of Neutral Hypercoordinate Allylsilicon Compounds Having Tropolonato Ligand" Organometallics. Vol.15. 5335-5341 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] KONDO,Yasuhiko et al.: "Single-ion Enthalpies of Transfer as a Scale of Nucleophilic Reactivity towards Ethyl Iodide in Acetonitrile" J.Chem.Soc., Perkin Trans. 2. 1699-1703 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] SAKURAGI,Hirochika et al.: "Observation of a Novel Fluorescent Dimer of Zinc Tetrasulphonatophthalocyanine" Chem.Lett.345-346 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] SAWAKI,Yasuhiko et al.: "Redox Reaction of Benzyl Radicals with Aromatic Radical Ions Photogenerated. The Marcus Inverted Region and the Selective Formation of Carbocations or Carbanions" J.Am.Chem.Soc.Vol.118. 7255-7264 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] SUZUKI,Hitomi et al.: "Redox Reaction of Benzyl Radicals with Aromatic Radical Ions Photogenerated. The Marcus Inverted Region and the Selective Formation of Carbocations or Carbanions" J.Chem.Soc., Perkin Trans. 2. 677-683 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] TSUJI,Takashi et al.: "Direct Synthesis of 2-Norbornanone Dithioacetals from 2-Cyclopentenone Dithioacetals and Dienophiles. Synthetic Application of Thermal Interconversion between Cyclic Dithioacetals and the Ring-opened Vinyl Sulfide Forms" Tetrahedron. Vol.52. 9979-9990 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] TOMIOKA,Hideo et al.: "Anomalous Effects of Para Substituents on the Stability of Sterically Congested Triplet Diaryl-carbenes. The First Triplet Carbene Surviving over Minutes under Normal Conditions" J.Am.Chem.Soc.Vol.118. 8723-8724 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] TOMODA,Shuji et al.: "Nature of the Intramolecular Se...N Non-bonded Interaction of 2-Selenobenzylamine Derivatives. An Experimental Evaluation by H-1, C-13, Se-77, and N-15 NMR Spectroscopy" J.Am.Chem.Soc.Vol.118. 8077-8084 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] NAGASE,Shigeru et al.: "Endohedral Metallofullerenes : New Spherical Cage Molecules with Interesting Properties" Bull.Chem.Soc.Jpn.Vol.69. 2131-2142 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] HIROTA,Minoru et al.: "Estimation of Reactivity by Correlation Analyzes Using OMEGA_S and DELTA_xB as Substituent Parameters" Bull.Chem.Soc.Jpn.Vol.69. 1003-1015 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] FUJIMOTO,Hiroshi et al.: "Theoretical Study of the Reactions of Allylsilanes with Carbonyl Compounds" J.Am.Chem.Soc.Vol.118. 1750-1755 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] YAMATAKA,Hiroshi et al.: "Stereoelectronic Effects in the Nucleophilic Addition to the sp-Hybridized Carbon of a Ketene and Vinyl Cation : When is a Mesityl Effectively Smaller than a Phenyl Ring?" J.Am.Chem.Soc.Vol.118. 12580-12587 (1996)

    • Description
      「研究成果報告書概要(欧文)」より

URL: 

Published: 1999-03-09  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi