1991 Fiscal Year Annual Research Report

有機反応経路の精密解析と反応の予測と設計への応用

Research Project

Project/Area Number	02303004
Research Institution	Yokohama National University
Principal Investigator	廣田穰横浜国立大学, 工学部, 教授 (00017881)
Co-Investigator(Kenkyū-buntansha)	岡崎廉治東京大学, 理学部, 教授 (70011567) 安藤亘筑波大学, 化学系, 教授 (30008429) 竹内賢一京都大学, 工学部, 教授 (50026358) 都野雄甫分子科学研究所, 教授 (10029845) 諸熊奎治分子科学研究所, 教授 (40111083)
Keywords	反応機構 / 電子的効果 / 立体効果 / 反応設計 / 有機反応
Research Abstract	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のグル-プでは、モノシクロメチレンシクロプロパンの熱反応(諸熊)や、フラ-レン類の反応性(永瀬)、一酸化炭素から二酸化炭素と炭素を生成する反応(西本)の理論的解明と予測を行った。速度論的立場からは、ベンジル誘導体の加溶媒分解の共鳴要求度と反応機構の関連性(都野)、芳香族アルデヒドやケトンの求核付加反応の遷移状態の構造(山高)、2ーメチルー2ープロパンスルフェン酸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を定議し(廣田)、ヘテロ原子を含む系への分子力学の応用(榊原)、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の立体的経路の解明(大沢)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)、スピロ[2.4]ヘプタン骨格を持つ高歪化合物(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)、触媒的不整反応経路(野依)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のグル-プは、(i)αーアニシルビニルカチオン(谷口)、2ー位にエチリデン基をもつカゴ型橋頭化合物(竹内)およびトリプチセン類(山本)の構造と新しい性質の設計についての研究、(ii)ケトンとグリニヤ-ル試薬との反応(永田)の発見及び機構の解明、(iii)超音波照射による反応機構の変化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解析のグル-プは、シラエテン等の有機珪素化合物(吉良)、3員環ジシラントトリアゾリンジオンとの反応(安藤亘)、超原子価化合物(秋葉)、ポリハロアルキルスルホキシドの反応(鈴木)、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。

Research Products

(24 results)

All Other

All Publications (24 results)

[Publications] T.Komatsuzaki,I.Akai,K.Sakakibara,M.Hirota: "A New Steric Substituent Constant Ωs.Characteristic Feature and Comparison with Some Other Steric Constants." Tetrahedron. 48. (1992)
[Publications] H.Suezawa,N.Horiike,S.Yamazaki,H.Kamachi,M.Hirota: "Multinuclear NMR Spectroscopic Studies on Ionic Interactions.Interactions between Nitrogen Cations and Halide Ions." Journal of Physical Chemistry. 95. 10787-10796 (1991)
[Publications] S.Araki,K.Sakakibara,M.Hirota,M.Nishio,S.Tsuzuki,K.Tanabe: "Theoretical Study of CHーπ Interaction.Significant Enhancement of CD Spectra Due to the Participation of CHーπ Interaction." Tetrahedron Letters. 32. 6587-6590 (1991)
[Publications] E.Nakamura,S.Yamago,S.Ejiri,A.E.Dorigo,K.Morokuma: "Reversible Generation of Trimethylenemethanes by Mild Thermolysis of Dialkoxymethylenecyclopropanes." Journal of American Chemical Society. 113. 3183-3184 (1991)
[Publications] S.Nagase,K.Kobayashi: "Si_<60> and Si_<60>X(X=Ne,F^- and Na^+)" Chemical Physics Letters. 187. 291-294 (1991)
[Publications] O.S.Lee,E.Osawa: "An Explanation for the Contrasting Reactivities of mesoー and d,1ーD_3ーTrishomocubylideneーD_3ーtrishomocubane towards Electrophiles" Bulletin of the Korean Chemical.Society. (1992)
[Publications] M.Fujio,K.Nakashima,E.Tokunaga,Y.Tsuji,Y.Tsuno: "The Unexalted Resonance Scale of Substituent Effect in the Benzylic Solvolysis" Tetrahedron Letters. 33. 345-348 (1992)
[Publications] H.Yamataka,N.Miyano,T.Hanafusa: "Comparative Mechanistic Study of the Reactions of Benzophenone with nーBuMgBr and nーBuLi" Journal of Organic Chomistry. 56. 2573-2575 (1991)
[Publications] K.Cosstick,T.Asano,N.Ohno: "PressureーInduced Retardation of Steric Isomerizations in Highly Viscous Media" Proceedings of XIII AIRAPT Interantional Conference on High Pressure Science and Technology. (1992)
[Publications] I.Okuyama: "Flash Photolytic Generation of a Dithio Carbocation from 1,3ーDithiolane Derivatives and Its Reaction with Nucleophiles" Bulletin of the Chemical Society Japan. 64. 2751-2756 (1991)
[Publications] M.Kitamura,M.Tokunaga,T.Ohkuma,R.Noyori: "Convenient Preparation of BINAPーRuthenium(II) Complexes Catalyzing Asymmetric Hydrogenation of Functionalized Ketones" Tetrahedron Letters. 32. 4163-4166 (1991)
[Publications] T.Tezuka,Y.Isahaya: "The STECAR (Steric Compressionーassisted Reaction) Concept.Ionic Deoxygenation Reaction via Intramolecular Proton Shift in Bornyl αーazoーhydroperoxide to give Camphor Hydrazone." Tetrahedron Letters. 32. 4955-4958 (1991)
[Publications] S.Nishida,N.Asanuma,T.Tsuji,T.Imai: "Unique Thermal Isomerization of the DielsーAlder Adduct of 1,1ーDicyclopropylspiro[2,4]heptaー4,6ーdiene with TCNE" Chemistry Letters. 495-498 (1991)
[Publications] T.Kitamura,T.Kabashima,I.Nakahara,T.Fukuda,H.Taniguchi: "Ipso Substitution of Triarylvinyl Cations by Alkoxide Anions" Journal of American Chemical Society. 113. 7255-7261 (1991)
[Publications] K.Takeuchi,Y.Ohga,T.Kitagawa: "Marked Leaving Group Strain in (Z)ー2ーEthylidenebicyclo[2.2.2]octー1ーyl Triflate and its Significant Relief in (Z)ー2ーEthylidenebicyclo[3.2.2]nonー1ーyl Mesylate" Journal of Organic Chemistry. 56. 5007-5008 (1991)
[Publications] Toshi Nagata: "Synthesis and Fluorescence Properties of Selectively Metallated.Diporphyrins with ElectronーAccepting Moieties" Bulletin of the Chemical Society of Japan. 64. 3005-3016 (1991)
[Publications] T.Ando,P.Bauchat,A.Foucaud,M.Fujita,T.Kimura,H.Sohmiya: "Sonochemical Switcing from Ionic to Radical Pathways in the Reaction of Styrene and transーβーMethylstyrene with Lead Tetraacetate" Tetrahedron Letters. 32. 6379-6382 (1991)
[Publications] M.Kira,T.Maruyama,H.Sakurai: "Sterochemistry and Mechanism for the Addition of Alcohols to a Cyclic Silene" Journal of Americal Chemial Society. 113. 3986-3987 (1991)
[Publications] W.Ando,M.Kako,T.Akasaka: "Direct Observation of an Azetidinium Imide Intermediate in (π^2+σ^2) Addition of 1,2,4ーTriazolineー3,5ーdione to Disilirane" Journal of American Chemical Society. 113. 6286-6288 (1991)
[Publications] K.Ohkata,M.Ohnishi,K.Yoshinaga,K.Akiba,J.C.Rongipne,J.C.Martin: "Apical and Equatorial Methoxy Ligands on Sulfuranes:Effect on Rates of Pyridine Methylation" Journal of American Chemical Society. 113. 9270-9276 (1991)
[Publications] H.Takemura,T.Shinmyozu,T.Inazu: "Syntheses and Properties of Highly Symmetrical Cage Compounds:Pyridine Analogues of Hexaーmーxylylenetetramine" Journal of American Chemical Society. 113. 1323-1331 (1991)
[Publications] H.Uno,K.Sakamoto,H.Suzuki: "Nucleophilic Desulfinylation ofーαーFluoroーβー(alkoxy and silyloxy) Sulfoxides.Effects of the βーOxy Substituents on Protonation,1,2ーHydrogenーMigration,and Nucleophilic Addition to the Fluorocarbenoid Centers." Bulletin of the Chemical Society of Japan. 65. 218-227 (1992)
[Publications] N.Tokitoh,H.Suzuki,T.Matsumoto,Y.Matsuhashi,R.Okazaki,M.Goto: "1,2,3,4,5ーTetrathiamethallolanes of Group 14 Metals,RR'MS_4(M=Si,Ge,Sn):Synthesis and Crystal Structures" Journal of American Chemical Society. 113. 7047-7049 (1991)
[Publications] A.Ohno,M.Okamura,T.kashiwagi,Y.Mikata,T.Maruyama: "Stereospecificity Observed in Baseーcatalyzed Electrochemical Oxidation" Tetrahedron Letters. 32. 1475-1478 (1991)

1991 Fiscal Year Annual Research Report

有機反応経路の精密解析と反応の予測と設計への応用

Principal Investigator

廣田 穰 横浜国立大学, 工学部, 教授 (00017881)

Research Products

[Publications] T.Komatsuzaki,I.Akai,K.Sakakibara,M.Hirota: "A New Steric Substituent Constant Ωs.Characteristic Feature and Comparison with Some Other Steric Constants." Tetrahedron. 48. (1992)

[Publications] H.Suezawa,N.Horiike,S.Yamazaki,H.Kamachi,M.Hirota: "Multinuclear NMR Spectroscopic Studies on Ionic Interactions.Interactions between Nitrogen Cations and Halide Ions." Journal of Physical Chemistry. 95. 10787-10796 (1991)

[Publications] S.Araki,K.Sakakibara,M.Hirota,M.Nishio,S.Tsuzuki,K.Tanabe: "Theoretical Study of CHーπ Interaction.Significant Enhancement of CD Spectra Due to the Participation of CHーπ Interaction." Tetrahedron Letters. 32. 6587-6590 (1991)

[Publications] E.Nakamura,S.Yamago,S.Ejiri,A.E.Dorigo,K.Morokuma: "Reversible Generation of Trimethylenemethanes by Mild Thermolysis of Dialkoxymethylenecyclopropanes." Journal of American Chemical Society. 113. 3183-3184 (1991)

[Publications] S.Nagase,K.Kobayashi: "Si_<60> and Si_<60>X(X=Ne,F^- and Na^+)" Chemical Physics Letters. 187. 291-294 (1991)

[Publications] O.S.Lee,E.Osawa: "An Explanation for the Contrasting Reactivities of mesoー and d,1ーD_3ーTrishomocubylideneーD_3ーtrishomocubane towards Electrophiles" Bulletin of the Korean Chemical.Society. (1992)

[Publications] M.Fujio,K.Nakashima,E.Tokunaga,Y.Tsuji,Y.Tsuno: "The Unexalted Resonance Scale of Substituent Effect in the Benzylic Solvolysis" Tetrahedron Letters. 33. 345-348 (1992)

[Publications] H.Yamataka,N.Miyano,T.Hanafusa: "Comparative Mechanistic Study of the Reactions of Benzophenone with nーBuMgBr and nーBuLi" Journal of Organic Chomistry. 56. 2573-2575 (1991)

[Publications] K.Cosstick,T.Asano,N.Ohno: "PressureーInduced Retardation of Steric Isomerizations in Highly Viscous Media" Proceedings of XIII AIRAPT Interantional Conference on High Pressure Science and Technology. (1992)

[Publications] I.Okuyama: "Flash Photolytic Generation of a Dithio Carbocation from 1,3ーDithiolane Derivatives and Its Reaction with Nucleophiles" Bulletin of the Chemical Society Japan. 64. 2751-2756 (1991)

[Publications] M.Kitamura,M.Tokunaga,T.Ohkuma,R.Noyori: "Convenient Preparation of BINAPーRuthenium(II) Complexes Catalyzing Asymmetric Hydrogenation of Functionalized Ketones" Tetrahedron Letters. 32. 4163-4166 (1991)

[Publications] T.Tezuka,Y.Isahaya: "The STECAR (Steric Compressionーassisted Reaction) Concept.Ionic Deoxygenation Reaction via Intramolecular Proton Shift in Bornyl αーazoーhydroperoxide to give Camphor Hydrazone." Tetrahedron Letters. 32. 4955-4958 (1991)

[Publications] S.Nishida,N.Asanuma,T.Tsuji,T.Imai: "Unique Thermal Isomerization of the DielsーAlder Adduct of 1,1ーDicyclopropylspiro[2,4]heptaー4,6ーdiene with TCNE" Chemistry Letters. 495-498 (1991)

[Publications] T.Kitamura,T.Kabashima,I.Nakahara,T.Fukuda,H.Taniguchi: "Ipso Substitution of Triarylvinyl Cations by Alkoxide Anions" Journal of American Chemical Society. 113. 7255-7261 (1991)

[Publications] K.Takeuchi,Y.Ohga,T.Kitagawa: "Marked Leaving Group Strain in (Z)ー2ーEthylidenebicyclo[2.2.2]octー1ーyl Triflate and its Significant Relief in (Z)ー2ーEthylidenebicyclo[3.2.2]nonー1ーyl Mesylate" Journal of Organic Chemistry. 56. 5007-5008 (1991)

[Publications] Toshi Nagata: "Synthesis and Fluorescence Properties of Selectively Metallated.Diporphyrins with ElectronーAccepting Moieties" Bulletin of the Chemical Society of Japan. 64. 3005-3016 (1991)

[Publications] T.Ando,P.Bauchat,A.Foucaud,M.Fujita,T.Kimura,H.Sohmiya: "Sonochemical Switcing from Ionic to Radical Pathways in the Reaction of Styrene and transーβーMethylstyrene with Lead Tetraacetate" Tetrahedron Letters. 32. 6379-6382 (1991)

[Publications] M.Kira,T.Maruyama,H.Sakurai: "Sterochemistry and Mechanism for the Addition of Alcohols to a Cyclic Silene" Journal of Americal Chemial Society. 113. 3986-3987 (1991)

[Publications] W.Ando,M.Kako,T.Akasaka: "Direct Observation of an Azetidinium Imide Intermediate in (π^2+σ^2) Addition of 1,2,4ーTriazolineー3,5ーdione to Disilirane" Journal of American Chemical Society. 113. 6286-6288 (1991)

[Publications] K.Ohkata,M.Ohnishi,K.Yoshinaga,K.Akiba,J.C.Rongipne,J.C.Martin: "Apical and Equatorial Methoxy Ligands on Sulfuranes:Effect on Rates of Pyridine Methylation" Journal of American Chemical Society. 113. 9270-9276 (1991)

[Publications] H.Takemura,T.Shinmyozu,T.Inazu: "Syntheses and Properties of Highly Symmetrical Cage Compounds:Pyridine Analogues of Hexaーmーxylylenetetramine" Journal of American Chemical Society. 113. 1323-1331 (1991)

[Publications] N.Tokitoh,H.Suzuki,T.Matsumoto,Y.Matsuhashi,R.Okazaki,M.Goto: "1,2,3,4,5ーTetrathiamethallolanes of Group 14 Metals,RR'MS_4(M=Si,Ge,Sn):Synthesis and Crystal Structures" Journal of American Chemical Society. 113. 7047-7049 (1991)

[Publications] A.Ohno,M.Okamura,T.kashiwagi,Y.Mikata,T.Maruyama: "Stereospecificity Observed in Baseーcatalyzed Electrochemical Oxidation" Tetrahedron Letters. 32. 1475-1478 (1991)

廣田穰横浜国立大学, 工学部, 教授 (00017881)