1995 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 Category	Grant-in-Aid for Co-operative Research (A)
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竹内と奥山はソルボリシスのイオン対中間体を安定化する隣接硫黄不飽和結合の効果と、イオン一分子対中間体の性質を解明し、速水と近藤は求核置換反応における求核種イオンと遷移状態での溶質-溶媒相互作用を究明した。櫻木と沢木はオキシルラジカルと炭素ラジカルの反応性に対する立体および電子効果に新たな知見を得た。岩村、岡崎、辻はそれぞれ、デントリマ-型超高スピンポリカルベン、安定芳香族スルフェン酸、光学活性C_<60>誘導体の合成に成功した。基底および遷移状態構造と反応の立体化学安藤(喬)は超音波照射下反応の新しい基質活性化機構を提案した。大野と金政は電子移動反応における錯体形成が反応の立体化学を著しく左右することを見いだした。富岡と奥は一重項カルベンと三重項カルベンの反応性を制御する立体効果を解明した。友田と山高はヒトリド還元でのカルボニル面選択性の起源とカルボニル基への一電子移動の同位体効果を理論計算により解明した。藤本はC-Si-C結合とアルデヒドとの反応の遷移状態構造を分子軌道計算から究明した。廣田は新たに定義した立体パラメーターを種々の反応に適用し成功を収めた。ヘテロ原子が関与する基底および遷移状態構造特性稲津と北村はチオフェン骨格をもつかご形化合物の特異な錯体形成能とチオフェニウムイオンによる立体選択的置換反応を見いだした。小野は新たなピロール合成法を開発した。香月は新規ビピリミジン銅錯体により高エネンチオカルベン挿入反応を開発した。安藤(亘)と吉良はそれぞれ、ゲルミラン生成反応の制御方法と中性5配位アリルケイ素化合物の高反応性を見つけた。秋葉はSbとBiを含むedge反転の遷移状態構造を究明し、永瀬は金属を2個内包したフラーレンの反応性を実験と理論から解明した。鈴木は酸化窒素とオゾンによるニトロ化が電子移動で進むことを明らかにした。

Research Products

(27 results)

All Other

All Publications (27 results)

[Publications] 竹内賢一: "Solvolysis of 2-Thioxo Bridgehead Compounds as Compared with their 2-Oxo Homologs : Evidence for Marked π-Conjugation in 2-Thioxo Carbocation" Tetrahedron Lett.37(印刷中). (1996)
[Publications] 秋葉欣哉: "Experimental Investigation on Edge Inversion at Trivalent Bismuth and Antimony : Great Acceleration by Intra-and Intermolecular Nucleophilic Coordination" J. Am. Chem. Soc.117. 3922-3932 (1995)
[Publications] 安藤喬志: "Standardization of Ultrasonic Power for Sonochemical Reactions" Ultrasonics Sonochem. 3(印刷中). (1996)
[Publications] 安藤亘: "Reaction of a Germylene with Ethylene : A Stable Digermacyclobutane is a Germirane Intermediate." Oraganometallics. 14. 2139-2141 (1995)
[Publications] 稲津孝彦: ""Cation-π Interactions" Detected by Mass Spectrometry ; Selective Recognition of Alkali Metal Cations by a π-Basic Molecular Cavity" Angew. Chem. Int Ed. Engl.34. 1364-1366 (1995)
[Publications] 岩村秀: "Design and Synthesis of a "Starburst" -Type Nonadiazo Compound and a Magnetic Characterization of Its Photoproduct" Chem. Eur. J.2. 105-110 (1996)
[Publications] 大野惇吉: "NAD(P)+-NAD(P)H Models. 84. Stereochemistry Controlled by the Electronic Effect from a Sulfinyl Group" Heteroatom chemistry. 6. 51-56 (1995)
[Publications] 岡崎廉治: "Synthesis of a Stable Arenesulfenic Acid Bearing a Bowl-shaped Macrobicyclic Cyclophane Skeleton" Angew. Chem. Int. Ed. Engl.34. 1124-1126 (1995)
[Publications] 奥彬: "Oxidative Ring-Opening Reaction of Cyclopropanone Acetals with Carbonyl Compounds via Photoinduced Electron Transfer" J. Org. Chem.60. 3065-3073 (1995)
[Publications] 奥山格: "solvolysis of cyclohexenyliodonium Salt, a New Precursor for the Vinyl Cation : A Remarkable Nucleofugality of the Phenyliodonio Group and Evidence for Internal Retrum" J. Am. Chem. Soc.117. 3360-3367 (1995)
[Publications] 小野昇: "A New Synthesis of Pyrroles Fused with Aromatic Rings" J. Chem. Soc., Perkin Trans. 1. (印刷中). (1996)
[Publications] 香月勗: "Enantiospecific Ring Expansion of Oxetanes ; Stereoselective synthesis of Tetrahydrofurans" Heterocycles. 42. 305-317 (1996)
[Publications] 金政修司: "Metal Ion-Mediated Diastereoface-Selective Nitrone Cycloadditions. Reaction Mechanism for the Reversal of Regioselectivity" Tetrahedron Lett.36. 5019-5022 (1995)
[Publications] 北村二雄: "Complete Retention of Configuration in the Nucleophilic Substitution of 1-Phenylbenzo〔b〕-thiophenium Salts by Alkoxide Anions" J.Chem. Soc., Chem. Commun.1375-1376 (1995)
[Publications] 吉良満夫: "Synthesis and Structure of Hexacoordinate Organosilicon Compounds Having Tropolonate Ligands" Chem. Lett.659-660 (1995)
[Publications] 近藤泰彦: "Solvation of Carboxylate Ions and of Transition-State Anions for the Reaction of Carboxylate Ion with Ethyl Iodide in Acetonitrile-Methanol Mixtures" J. Chem. Soc., Perkin Trans. 2. 1049-1054 (1995)
[Publications] 櫻木宏親: "Structural and Solvent Effects upon Decarboxylation of 2, 6-Disubsituted Benzoyloxyl Radicals. A Laser Flash Photolysis Study of Bis (2, 6-disubstituted-benzoyl) Peroxides" Tetrahedron. 51. 11967-11978 (1995)
[Publications] 沢木泰彦: "Reactivity of Nitroso Oxides : Effect of Polar Substituents and Reaction Mechanism" J. Chem. Soc., Perkin Trans. 2. (印刷中). (1996)
[Publications] 鈴木仁美: "Ozone-mediated Nitration of Naphthalene and Some Methyl Derivatives with Nitrogen Dioxide" J. Chem. Soc., Perkin Trans. 2. (印刷中). (1996)
[Publications] 辻孝: "Reaction of C_<60>-Cyclopentenone Acetals. A Convenient Access to Chiral C_<60> Derivatives" J. Chem. Soc., Chem. Commun.1769-1770 (1995)
[Publications] 高岡秀雄: "Chemistry of 1-Alkylfluorenylidenes. Steric Effects on Arylcarbene Reactivities" J. Am. Chem. Soc.117. 4483-4498 (1995)
[Publications] 友田修司: "ヒドリド還元におけるカルボニル面選択性の起源" 現代化学増刊26「有機反応論の進展開」. 163-171 (1995)
[Publications] 永瀬茂: "Synthesis of the First Adducts of the Dimetallofullerenes La_2C_<80> and Sc_2C_<84> by Addition of a Disilirane" Angew. Chem. Int. Ed. Engl.34. 2139-2141 (1995)
[Publications] 速水醇一: "溶液反応に溶媒はどのようにかかわっているか" 現代化学増刊26「有機反応論の新展開」. 57-63 (1995)
[Publications] 廣田穣: "Steric Substituent Constant Omega-s Based on Molecular Mechanics Calculations. II. Directionally Weighted Steric Constants and Their Application" J. Phys. Org. Chem.8. 791-798 (1995)
[Publications] 藤本博: "Theoretical Study of the Reaction of Allylsilanes with Carbonyl Compounds" J. Am. Chem. Soc.118(印刷中). (1996)
[Publications] 山高博: "Gas Phase Carbon and Deuterium Isotope Effects on Electron Affinity of Benzophenone : A Combined Experimental and Theoretical Study" J. Am. Chem. Soc.117. 5829-5831 (1995)

1995 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: "Solvolysis of 2-Thioxo Bridgehead Compounds as Compared with their 2-Oxo Homologs : Evidence for Marked π-Conjugation in 2-Thioxo Carbocation" Tetrahedron Lett.37(印刷中). (1996)

[Publications] 秋葉欣哉: "Experimental Investigation on Edge Inversion at Trivalent Bismuth and Antimony : Great Acceleration by Intra-and Intermolecular Nucleophilic Coordination" J. Am. Chem. Soc.117. 3922-3932 (1995)

[Publications] 安藤喬志: "Standardization of Ultrasonic Power for Sonochemical Reactions" Ultrasonics Sonochem. 3(印刷中). (1996)

[Publications] 安藤亘: "Reaction of a Germylene with Ethylene : A Stable Digermacyclobutane is a Germirane Intermediate." Oraganometallics. 14. 2139-2141 (1995)

[Publications] 稲津孝彦: ""Cation-π Interactions" Detected by Mass Spectrometry ; Selective Recognition of Alkali Metal Cations by a π-Basic Molecular Cavity" Angew. Chem. Int Ed. Engl.34. 1364-1366 (1995)

[Publications] 岩村秀: "Design and Synthesis of a "Starburst" -Type Nonadiazo Compound and a Magnetic Characterization of Its Photoproduct" Chem. Eur. J.2. 105-110 (1996)

[Publications] 大野惇吉: "NAD(P)+-NAD(P)H Models. 84. Stereochemistry Controlled by the Electronic Effect from a Sulfinyl Group" Heteroatom chemistry. 6. 51-56 (1995)

[Publications] 岡崎廉治: "Synthesis of a Stable Arenesulfenic Acid Bearing a Bowl-shaped Macrobicyclic Cyclophane Skeleton" Angew. Chem. Int. Ed. Engl.34. 1124-1126 (1995)

[Publications] 奥彬: "Oxidative Ring-Opening Reaction of Cyclopropanone Acetals with Carbonyl Compounds via Photoinduced Electron Transfer" J. Org. Chem.60. 3065-3073 (1995)

[Publications] 奥山格: "solvolysis of cyclohexenyliodonium Salt, a New Precursor for the Vinyl Cation : A Remarkable Nucleofugality of the Phenyliodonio Group and Evidence for Internal Retrum" J. Am. Chem. Soc.117. 3360-3367 (1995)

[Publications] 小野昇: "A New Synthesis of Pyrroles Fused with Aromatic Rings" J. Chem. Soc., Perkin Trans. 1. (印刷中). (1996)

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

[Publications] 金政修司: "Metal Ion-Mediated Diastereoface-Selective Nitrone Cycloadditions. Reaction Mechanism for the Reversal of Regioselectivity" Tetrahedron Lett.36. 5019-5022 (1995)

[Publications] 北村二雄: "Complete Retention of Configuration in the Nucleophilic Substitution of 1-Phenylbenzo〔b〕-thiophenium Salts by Alkoxide Anions" J.Chem. Soc., Chem. Commun.1375-1376 (1995)

[Publications] 吉良満夫: "Synthesis and Structure of Hexacoordinate Organosilicon Compounds Having Tropolonate Ligands" Chem. Lett.659-660 (1995)

[Publications] 近藤泰彦: "Solvation of Carboxylate Ions and of Transition-State Anions for the Reaction of Carboxylate Ion with Ethyl Iodide in Acetonitrile-Methanol Mixtures" J. Chem. Soc., Perkin Trans. 2. 1049-1054 (1995)

[Publications] 櫻木宏親: "Structural and Solvent Effects upon Decarboxylation of 2, 6-Disubsituted Benzoyloxyl Radicals. A Laser Flash Photolysis Study of Bis (2, 6-disubstituted-benzoyl) Peroxides" Tetrahedron. 51. 11967-11978 (1995)

[Publications] 沢木泰彦: "Reactivity of Nitroso Oxides : Effect of Polar Substituents and Reaction Mechanism" J. Chem. Soc., Perkin Trans. 2. (印刷中). (1996)

[Publications] 鈴木仁美: "Ozone-mediated Nitration of Naphthalene and Some Methyl Derivatives with Nitrogen Dioxide" J. Chem. Soc., Perkin Trans. 2. (印刷中). (1996)

[Publications] 辻孝: "Reaction of C_<60>-Cyclopentenone Acetals. A Convenient Access to Chiral C_<60> Derivatives" J. Chem. Soc., Chem. Commun.1769-1770 (1995)

[Publications] 高岡秀雄: "Chemistry of 1-Alkylfluorenylidenes. Steric Effects on Arylcarbene Reactivities" J. Am. Chem. Soc.117. 4483-4498 (1995)

[Publications] 友田修司: "ヒドリド還元におけるカルボニル面選択性の起源" 現代化学増刊26「有機反応論の進展開」. 163-171 (1995)

[Publications] 永瀬茂: "Synthesis of the First Adducts of the Dimetallofullerenes La_2C_<80> and Sc_2C_<84> by Addition of a Disilirane" Angew. Chem. Int. Ed. Engl.34. 2139-2141 (1995)

[Publications] 速水醇一: "溶液反応に溶媒はどのようにかかわっているか" 現代化学増刊26「有機反応論の新展開」. 57-63 (1995)

[Publications] 廣田穣: "Steric Substituent Constant Omega-s Based on Molecular Mechanics Calculations. II. Directionally Weighted Steric Constants and Their Application" J. Phys. Org. Chem.8. 791-798 (1995)

[Publications] 藤本博: "Theoretical Study of the Reaction of Allylsilanes with Carbonyl Compounds" J. Am. Chem. Soc.118(印刷中). (1996)

[Publications] 山高博: "Gas Phase Carbon and Deuterium Isotope Effects on Electron Affinity of Benzophenone : A Combined Experimental and Theoretical Study" J. Am. Chem. Soc.117. 5829-5831 (1995)

竹内賢一京都大学, 工学研究科, 教授 (50026358)