1990 年度実績報告書

有機反応経路の精密解析と反応の予測と設計への応用

研究課題

研究課題/領域番号	02303004
研究機関	横浜国立大学
研究代表者	廣田穰横浜国立大学, 工学部, 教授 (00017881)
研究分担者	安藤亘筑波大学, 化学系, 教授 (30008429) 丸山和博京都大学, 理学部, 教授 (90025263) 岩村秀東京大学, 理学部, 教授 (10011496) 都野雄甫分子科学研究所, 九州大学理学部, 教授 (10029845) 諸熊奎治分子科学, 研究所, 教授 (40111083)
キーワード	有機反応 / 反応機構 / 反応速度論 / 反応の立体的経路 / 反応中間体 / ヘテロ原子化合物 / ラジカル / 炭素カチオン
研究概要	<有機反応の電子的要因に関する理論の精密化と反応予測>___ーのグル-プでは、アリル化合物とMe_2CuLi_2のπ錯体の立体選択的反応の予測(諸熊)や、2価活性種XH_2とラジカルXH_3(X=C,Si,Ge,Sn,Pb)の反応性に対する高周期のXの効果の予測(永瀬)、溶媒和形成プロセスの理論的解明(西本)を分子軌道法に基づいて行った。また、速度論的な立場から、ベンジル誘導体の加溶媒分解の解析から共鳴要求度が反応機構の変動にも関わらず一定であること(都野)、ベンズアルデヒドと錫、鉛、亜鉛のアリル化合物との反応の遷移状態の構造(花房)、メトキシメチルフェニルスルホキシドの酸触媒開裂反応の反応機構(奥山)に関する新知見を得た。 <有機反応の立体因子の定量的解析と反応予測への応用>___ーのグル-プでは、一方では立体効果の評価に分子力学を応用して、新しい立体置換基定数Ωsを定義し(廣田)、PBNのスピントラップ反応(榊原)やD_3ートリスホモキュバン二量体等の立体的混雑オレフィンに対するハロゲンの求電子反応(大沢)の立体的経路の解明を行った。他方では、立体圧縮援助反応の概念に対する実験的証明(手塚)、高歪化合物(西田)、アゾアレ-ン類のZ/E熱異性化に対する圧力効果(浅野)など実験的な立場から反応の立体的経路の解明を行った。 <反応中間体の構造と相互作用>___ーのグル-プは、(i)ビニルカチオン(谷口)、αーケトカチオン(竹内)およびポリラジカル(岩村)の構造と新しい性質の設計についての研究、(ii)キノンとベンジル錫・アリル錫との光反応(丸山)や分子間では見られない分子内特有な二発色団間の光環化付加反応(桜木)の発見及び機構の解明、(iii)液・固相不均一相反応に特異な機構の解明と選択的反応の設計への応用(安藤喬)について成果を収めた。 <複雑な有機分子系の反応挙動の解析>___ーのグル-プでも有機珪素化合物(吉良)、超原子価化合物(秋葉)、高周期ヘテロ原子化合物(岡崎)、シクロファン(稲津)、生体関連化合物(大野)の分野で成果を収めた。

研究成果
(24件)

すべてその他

すべて文献書誌 (24件)

[文献書誌] Tamiki Komatsuzaki: "A New Steric Substituent Parameter OmegaーS.Sophistication of Calculation and Correlation with the Kinetic Data of Several Reactions." Chemistry Letters. 1913-1916 (1990)
[文献書誌] Yukino Abe: "Spin Trapping of OxygenーCentered Radicals by Substituted NーBenzylideneーtーbutylamine NーOxides." Journal of Chemical Society,Perkin Trans.2. (1990)
[文献書誌] Nobuaki Koga: "Orign of Exo Selectivity in Norbornene.An ab initio MO Study." Journal of Physical Organic Cemistry. 3. 519-553 (1990)
[文献書誌] Shigeru Nagase: "Do Distibene and Dibismuthene Feature Double Bonding? A theoretical Comparison with Diphosphene and Diarsene." J.Chem.Soc.,Chem.Commun.1724-1726 (1990)
[文献書誌] Kazuhiko Honda: "Monte Carlo Simulation of Liquid Water and an Evaluation of the Thermodynamic Properties." Molecualr Simulation. (1990)
[文献書誌] A.P.Marchand: "Synthesis and Reactions of mesoーand dlーD_3ーTrishomocubylideneーD_3ーtrihomocubane." Journal of American Chemical Society. 112. 3521-3529 (1990)
[文献書誌] Yuho Tsuno: "Substituent Effects.XXI.Solvolysis of Benzyl Tosylates." Bulletin of the Chemical Society of Japan. 63. 1146-1153 (1990)
[文献書誌] H.Yamataka: "On the Reaction Pathway and Stereochemistry of Allylic Tin ReagentーBenzaldehyde Condensation.A Substituent Effect Study." Chemistry Letters. 1711-1714 (1990)
[文献書誌] Kazuhiro Maruyama: "Photochemically Induced Single Electron Transfer Reaction of Benzils with Allylstannane.Direct Observation of Reactive Intermediates by ESR Method." Bulletin of the Chemical Society of Japan. 63. 2218-2223 (1990)
[文献書誌] K.Cosstick: "PressureーInduced Retardation of Stereoisomerization.A Possible Case of a Threshold Value in the Viscosity Effect." Chemistry Letters. (1990)
[文献書誌] Itaru Okuyama: "AcidーCatalyzed Cleavage of Methoxymethyl Phenyl Sulfoxide.Solvent Effects and mode of Bond Cleavage." Bulletin of the Chemical Society of Japan. 63. 3111-3116 (1990)
[文献書誌] Ryoji Noyori: "Chiral Metal Complexes as Discriminating Molecular Catalysts." Science. 248. 1194-1199 (1990)
[文献書誌] Takahiro Tezuka: "Involvement of the Intramolecular Ionic Reaction in the Steric CompressionーAssisted Reaction (STECAR) Concept.Rearrangement of Benzyl αーAzo Benzoate into Lactam." Tetrahedron Letters. 31. 7633-7636 (1990)
[文献書誌] T.Kitamura: "Vinylidencyclohexadienone Acetals as Precursors of Arylvinyl Cations" Journal of American Chemical Society. 112. (1990)
[文献書誌] Kenーichi Takeuchi: "Stability of 2ーOxo and 2ーMethylene Bridgehead Carbocations in Solvolysis:Further Evidence for the Unimportance of πーConjugative Stabilization in Tertiary αーKeto Cations." Journal of Organic Chemistry. 55. 6063-6065 (1990)
[文献書誌] Hirochika Sakuragi: "Photochemical and Photophysical Behavior of pーMethoxyphenylalkenyl Phenanthrenecarboxylates.I.Structure and Competitive Formation of Intramolecular Cycloaddition Products." Bulletin of the Chemical Society of Japan. 63. 1049-1057 (1990)
[文献書誌] Ikuo Fujita: "Design,Preparation,and Electron Spin Resonance Detection of a GroundーState Undecet (S=5) Hydrocarbon." Journal of American Chemical Society. 112. 4074-4075 (1990)
[文献書誌] T.Kimura: "SupportーControlled Switching of SulfurーNitrogen Nucleophilicity for Inorganic SolidーSupported Alkaline Earth Metal Thiocyanate Reagents." J.Chem.Soc.,Chem.Commun.1213-1214 (1990)
[文献書誌] Mitsuo Kira: "Regiospecific and Diastereoselective Allylation of Aldimines with Crotyltrifluorosilanes Activated by Fluoride Ions." Chemistry Letters. 277-280 (1990)
[文献書誌] Wataru Ando: "Singlet Oxygenation of Oxadisiliranes: Synthesis and Crystal Structure of 1,2,3,4,5ーtrioxadisilolanes.ー" Tetrahedron Letters. 31. 4177-4180 (1990)
[文献書誌] Katsuo Ohkata: "Restricted Rotation of Pyrimidine Ring in Symmetrical 10ーSー3 Sulfuranes:Evaluation of Hypervalent NーSーN Bond Energy." Tetrahedron Letters. 31. 1605-1608 (1990)
[文献書誌] Katsuya Sako: "Conformational Analysis of [3.3]Paracyclophane." Chemische Berichite. 123. 639-642 (1990)
[文献書誌] N.Tokitoh: "Unusual 1,3ーRearrangement of Trimethylsilyl Group in the Reaction of 2,4,6ーTris[bis(trimethylsilyl)methyl]phenyllithium." Tetrahedron Letters. 32. (1990)
[文献書誌] Atsuyosi Ohno: "NAD(P)^+ーNAD(P)H Models.74.EntropyーControlled Kinetics,Stereochemistry,and Tunneling Effect." Bulletin of the Chemical Society of Japan. 64. 87-90 (1990)

1990 年度 実績報告書

有機反応経路の精密解析と反応の予測と設計への応用

研究代表者

廣田 穰 横浜国立大学, 工学部, 教授 (00017881)

研究成果

[文献書誌] Tamiki Komatsuzaki: "A New Steric Substituent Parameter OmegaーS.Sophistication of Calculation and Correlation with the Kinetic Data of Several Reactions." Chemistry Letters. 1913-1916 (1990)

[文献書誌] Yukino Abe: "Spin Trapping of OxygenーCentered Radicals by Substituted NーBenzylideneーtーbutylamine NーOxides." Journal of Chemical Society,Perkin Trans.2. (1990)

[文献書誌] Nobuaki Koga: "Orign of Exo Selectivity in Norbornene.An ab initio MO Study." Journal of Physical Organic Cemistry. 3. 519-553 (1990)

[文献書誌] Shigeru Nagase: "Do Distibene and Dibismuthene Feature Double Bonding? A theoretical Comparison with Diphosphene and Diarsene." J.Chem.Soc.,Chem.Commun.1724-1726 (1990)

[文献書誌] Kazuhiko Honda: "Monte Carlo Simulation of Liquid Water and an Evaluation of the Thermodynamic Properties." Molecualr Simulation. (1990)

[文献書誌] A.P.Marchand: "Synthesis and Reactions of mesoーand dlーD_3ーTrishomocubylideneーD_3ーtrihomocubane." Journal of American Chemical Society. 112. 3521-3529 (1990)

[文献書誌] Yuho Tsuno: "Substituent Effects.XXI.Solvolysis of Benzyl Tosylates." Bulletin of the Chemical Society of Japan. 63. 1146-1153 (1990)

[文献書誌] H.Yamataka: "On the Reaction Pathway and Stereochemistry of Allylic Tin ReagentーBenzaldehyde Condensation.A Substituent Effect Study." Chemistry Letters. 1711-1714 (1990)

[文献書誌] Kazuhiro Maruyama: "Photochemically Induced Single Electron Transfer Reaction of Benzils with Allylstannane.Direct Observation of Reactive Intermediates by ESR Method." Bulletin of the Chemical Society of Japan. 63. 2218-2223 (1990)

[文献書誌] K.Cosstick: "PressureーInduced Retardation of Stereoisomerization.A Possible Case of a Threshold Value in the Viscosity Effect." Chemistry Letters. (1990)

[文献書誌] Itaru Okuyama: "AcidーCatalyzed Cleavage of Methoxymethyl Phenyl Sulfoxide.Solvent Effects and mode of Bond Cleavage." Bulletin of the Chemical Society of Japan. 63. 3111-3116 (1990)

[文献書誌] Ryoji Noyori: "Chiral Metal Complexes as Discriminating Molecular Catalysts." Science. 248. 1194-1199 (1990)

[文献書誌] Takahiro Tezuka: "Involvement of the Intramolecular Ionic Reaction in the Steric CompressionーAssisted Reaction (STECAR) Concept.Rearrangement of Benzyl αーAzo Benzoate into Lactam." Tetrahedron Letters. 31. 7633-7636 (1990)

[文献書誌] T.Kitamura: "Vinylidencyclohexadienone Acetals as Precursors of Arylvinyl Cations" Journal of American Chemical Society. 112. (1990)

[文献書誌] Kenーichi Takeuchi: "Stability of 2ーOxo and 2ーMethylene Bridgehead Carbocations in Solvolysis:Further Evidence for the Unimportance of πーConjugative Stabilization in Tertiary αーKeto Cations." Journal of Organic Chemistry. 55. 6063-6065 (1990)

[文献書誌] Hirochika Sakuragi: "Photochemical and Photophysical Behavior of pーMethoxyphenylalkenyl Phenanthrenecarboxylates.I.Structure and Competitive Formation of Intramolecular Cycloaddition Products." Bulletin of the Chemical Society of Japan. 63. 1049-1057 (1990)

[文献書誌] Ikuo Fujita: "Design,Preparation,and Electron Spin Resonance Detection of a GroundーState Undecet (S=5) Hydrocarbon." Journal of American Chemical Society. 112. 4074-4075 (1990)

[文献書誌] T.Kimura: "SupportーControlled Switching of SulfurーNitrogen Nucleophilicity for Inorganic SolidーSupported Alkaline Earth Metal Thiocyanate Reagents." J.Chem.Soc.,Chem.Commun.1213-1214 (1990)

[文献書誌] Mitsuo Kira: "Regiospecific and Diastereoselective Allylation of Aldimines with Crotyltrifluorosilanes Activated by Fluoride Ions." Chemistry Letters. 277-280 (1990)

[文献書誌] Wataru Ando: "Singlet Oxygenation of Oxadisiliranes: Synthesis and Crystal Structure of 1,2,3,4,5ーtrioxadisilolanes.ー" Tetrahedron Letters. 31. 4177-4180 (1990)

[文献書誌] Katsuo Ohkata: "Restricted Rotation of Pyrimidine Ring in Symmetrical 10ーSー3 Sulfuranes:Evaluation of Hypervalent NーSーN Bond Energy." Tetrahedron Letters. 31. 1605-1608 (1990)

[文献書誌] Katsuya Sako: "Conformational Analysis of [3.3]Paracyclophane." Chemische Berichite. 123. 639-642 (1990)

[文献書誌] N.Tokitoh: "Unusual 1,3ーRearrangement of Trimethylsilyl Group in the Reaction of 2,4,6ーTris[bis(trimethylsilyl)methyl]phenyllithium." Tetrahedron Letters. 32. (1990)

[文献書誌] Atsuyosi Ohno: "NAD(P)^+ーNAD(P)H Models.74.EntropyーControlled Kinetics,Stereochemistry,and Tunneling Effect." Bulletin of the Chemical Society of Japan. 64. 87-90 (1990)

1990 年度実績報告書

廣田穰横浜国立大学, 工学部, 教授 (00017881)