1996 Fiscal Year Annual Research Report

基底状態と遷移状態の複合効果による有機反応の選択性と反応性の制御

Research Project

Project/Area Number	07304075
Research Institution	KYOTO UNIVERSITY
Principal Investigator	竹内賢一京都大学, 工学研究科, 教授 (50026358)
Co-Investigator(Kenkyū-buntansha)	大野惇吉京都大学, 化学研究所, 教授 (70027077) 稲津孝彦九州大学, 理学部, 教授 (60037207) 安藤亘筑波大学, 化学系, 教授 (30008429) 安藤喬志滋賀医科大学, 医学部, 教授 (70029867) 秋葉欣哉広島大学, 理学部, 教授 (20011538)
Keywords	基底状態構造 / 遷移状態構造 / 選択性と反応性 / 反応中間体 / カルボカチオン / カルベン / 有機立体化学 / 分子軌道法計算
Research Abstract	基底および遷移状態のエネルギーに対する構造因子の班では、次の課題について成果を挙げた。加溶媒分解反応における溶媒求核関与の制御(竹内)、テトラメチレンエタンの電子構造(岩村)、新反応場の設計に基づく高反応性化学種の安定化(岡崎)、ビニルヨードニウム塩の求核置換と脱離(奥山)、遷移状態における溶質-溶媒相互作用(近藤)、スチルベン誘導体ラジカルカチオンの励起状態経由異性化(櫻木)、ベンジルラジカル類の酸化、還元挙動(沢木)、高歪みパラシクロファンの速度論的安定化(辻)。基底状態および遷移状態の構造と反応の立体化学的特性の班では、次の課題について成果を挙げた。ソノケミストリーにおける活性化の機構(安藤喬)、ヒドリド還元における極性基の配向と立体選択性(大野)、高歪み電子移動系の設計(奥)、不斉配位子修飾ニッケル触媒を用いる高エナンチオン選択的反応(金政)、カルボニル還元反応選択性における基底状態と遷移状態(友田)、アルキルカルベンの反応に対する立体効果(富岡)、Ωsを用いた反応の立体的経路の解析(廣田)、遷移状態を考慮した反応性予測(藤本)、カルボニル求核付加反応の反応経路に関する同位体効果(山高)。ヘテロ原子が関与する基底状態構造と遷移状態構造の特性の班では、次の課題について成果を挙げた。Berry Pseudorotationの中間体捕捉と立体異性体間の変換速度(秋葉)、3,3'-ビスシラシクロプロパンおよびビスシラシクロプロペンの転位反応(安藤亘)、アザカリクサレンの合成と性質(稲津)、非イオン性強塩基を用いた芳香族ニトロ化合物の求核置換反応(小野)、アキラルなサレンマンガン錯体用いる不斉エポキシ化(香月)、不飽和結合への求核置換の制御におけるヘテロ元素の役割(北村)、シラトリアフルベンのアルコール付加反応機構(吉良)、非古典的な芳香族ニトロ化反応(鈴木)、金属内包フラーレンの構造と反応(永瀬)。

Research Products
(26 results)

All Other

All Publications (26 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)
[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)
[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)
[Publications] 安藤亘: "Synthesis and Reaction of Polythiadisilabicyclo[k.l.m]alkanes" J.Organom.Chem.516. 155-165 (1996)
[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)
[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)
[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)
[Publications] 岡崎廉治: "Cycloaddition and Oxidation Reactions of a Stable Thioaldehyde,(2,4,6-Tri-t-butyl)thiobenzaldehyde" Bull.Chem.Soc.Jpn.69. 719-724 (1996)
[Publications] 奥彬: "Migratory Aptitude of Substituents on Silicon Atoms of Disilylcarbenes" J.Phys.Org.Chem.9. 619-622 (1996)
[Publications] 奥山格: "Ring-Opening Reactions of Cyclic Sulfinate Esters with a Phenolic Leaving Group" Bull.Chem.Soc.Jpn.69. 2639-2644 (1996)
[Publications] 小野昇: "A New Method for Chemical Modification of Conductive Polypyrroles without Destroying Their Conductivity" Adv.Mater.9. 149-153 (1997)
[Publications] 香月勗: "Enantiospecific Ring Expansion of Oxetanes : Stereoselective Synthesis of Tetrahydrofurans from Oxetanes" Heterocycles. 42. 305-317 (1996)
[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)
[Publications] 北村二雄: "An Efficient Ligand Exchange Reaction of β-(Trifyloxy)vinyliononium Triflates with Aryllithium Reagents Leading to Diaryliononium Triflates" Tetrahedron Lett.37. 3721-3722 (1996)
[Publications] 吉良満夫: "Synthesis and Reactions of Neutral Hypercoordinate Allylsilicon Compounds Having Tropolonato Ligand" Organometallics. 15. 5335-5341 (1996)
[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)
[Publications] 櫻木宏親: "Observation of a Novel Fluorescent Dimer of Zinc Tetrasulphonatophthalocyanine" Chem.Lett.345-346 (1996)
[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)
[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)
[Publications] 辻孝: "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. 52. 9979-9990 (1996)
[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)
[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)
[Publications] 永瀬茂: "Endohedral Metallofullerenes : New Spherical Cage Molecules with Interesting Properties" Bull.Chem.Soc.Jpn.69. 2131-2142 (1996)
[Publications] 廣田穣: "Estimation of Reactivity by Correlation Analyses Using Ωs and ΔχB as Substituent Parameters" Bull.Chem.Soc.Jpn.69. 1003-1015 (1996)
[Publications] 藤本博: "Theoretical Study of the Reactions of Allysilanes with Carbonyl Compounds" J.Am.Chem.Soc.118. 1750-1755 (1996)
[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)

1996 Fiscal Year Annual Research Report

基底状態と遷移状態の複合効果による有機反応の選択性と反応性の制御

Principal Investigator

竹内 賢一 京都大学, 工学研究科, 教授 (50026358)

Research Products

[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)

[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)

[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)

[Publications] 安藤 亘: "Synthesis and Reaction of Polythiadisilabicyclo[k.l.m]alkanes" J.Organom.Chem.516. 155-165 (1996)

[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)

[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)

[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)

[Publications] 岡崎 廉治: "Cycloaddition and Oxidation Reactions of a Stable Thioaldehyde,(2,4,6-Tri-t-butyl)thiobenzaldehyde" Bull.Chem.Soc.Jpn.69. 719-724 (1996)

[Publications] 奥 彬: "Migratory Aptitude of Substituents on Silicon Atoms of Disilylcarbenes" J.Phys.Org.Chem.9. 619-622 (1996)

[Publications] 奥山 格: "Ring-Opening Reactions of Cyclic Sulfinate Esters with a Phenolic Leaving Group" Bull.Chem.Soc.Jpn.69. 2639-2644 (1996)

[Publications] 小野 昇: "A New Method for Chemical Modification of Conductive Polypyrroles without Destroying Their Conductivity" Adv.Mater.9. 149-153 (1997)

[Publications] 香月 勗: "Enantiospecific Ring Expansion of Oxetanes : Stereoselective Synthesis of Tetrahydrofurans from Oxetanes" Heterocycles. 42. 305-317 (1996)

[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)

[Publications] 北村 二雄: "An Efficient Ligand Exchange Reaction of β-(Trifyloxy)vinyliononium Triflates with Aryllithium Reagents Leading to Diaryliononium Triflates" Tetrahedron Lett.37. 3721-3722 (1996)

[Publications] 吉良 満夫: "Synthesis and Reactions of Neutral Hypercoordinate Allylsilicon Compounds Having Tropolonato Ligand" Organometallics. 15. 5335-5341 (1996)

[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)

[Publications] 櫻木 宏親: "Observation of a Novel Fluorescent Dimer of Zinc Tetrasulphonatophthalocyanine" Chem.Lett.345-346 (1996)

[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)

[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)

[Publications] 辻 孝: "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. 52. 9979-9990 (1996)

[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)

[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)

[Publications] 永瀬 茂: "Endohedral Metallofullerenes : New Spherical Cage Molecules with Interesting Properties" Bull.Chem.Soc.Jpn.69. 2131-2142 (1996)

[Publications] 廣田 穣: "Estimation of Reactivity by Correlation Analyses Using Ωs and ΔχB as Substituent Parameters" Bull.Chem.Soc.Jpn.69. 1003-1015 (1996)

[Publications] 藤本 博: "Theoretical Study of the Reactions of Allysilanes with Carbonyl Compounds" J.Am.Chem.Soc.118. 1750-1755 (1996)

[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)

竹内賢一京都大学, 工学研究科, 教授 (50026358)

[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)

[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)

[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)

[Publications] 安藤亘: "Synthesis and Reaction of Polythiadisilabicyclo[k.l.m]alkanes" J.Organom.Chem.516. 155-165 (1996)

[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)

[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)

[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)

[Publications] 岡崎廉治: "Cycloaddition and Oxidation Reactions of a Stable Thioaldehyde,(2,4,6-Tri-t-butyl)thiobenzaldehyde" Bull.Chem.Soc.Jpn.69. 719-724 (1996)

[Publications] 奥彬: "Migratory Aptitude of Substituents on Silicon Atoms of Disilylcarbenes" J.Phys.Org.Chem.9. 619-622 (1996)

[Publications] 奥山格: "Ring-Opening Reactions of Cyclic Sulfinate Esters with a Phenolic Leaving Group" Bull.Chem.Soc.Jpn.69. 2639-2644 (1996)

[Publications] 小野昇: "A New Method for Chemical Modification of Conductive Polypyrroles without Destroying Their Conductivity" Adv.Mater.9. 149-153 (1997)

[Publications] 香月勗: "Enantiospecific Ring Expansion of Oxetanes : Stereoselective Synthesis of Tetrahydrofurans from Oxetanes" Heterocycles. 42. 305-317 (1996)

[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)

[Publications] 北村二雄: "An Efficient Ligand Exchange Reaction of β-(Trifyloxy)vinyliononium Triflates with Aryllithium Reagents Leading to Diaryliononium Triflates" Tetrahedron Lett.37. 3721-3722 (1996)

[Publications] 吉良満夫: "Synthesis and Reactions of Neutral Hypercoordinate Allylsilicon Compounds Having Tropolonato Ligand" Organometallics. 15. 5335-5341 (1996)

[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)

[Publications] 櫻木宏親: "Observation of a Novel Fluorescent Dimer of Zinc Tetrasulphonatophthalocyanine" Chem.Lett.345-346 (1996)

[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)

[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)

[Publications] 辻孝: "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. 52. 9979-9990 (1996)

[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)

[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)

[Publications] 永瀬茂: "Endohedral Metallofullerenes : New Spherical Cage Molecules with Interesting Properties" Bull.Chem.Soc.Jpn.69. 2131-2142 (1996)

[Publications] 廣田穣: "Estimation of Reactivity by Correlation Analyses Using Ωs and ΔχB as Substituent Parameters" Bull.Chem.Soc.Jpn.69. 1003-1015 (1996)

[Publications] 藤本博: "Theoretical Study of the Reactions of Allysilanes with Carbonyl Compounds" J.Am.Chem.Soc.118. 1750-1755 (1996)

[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)