1992 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	広田穰横浜国立大学, 工学部, 教授 (00017881)
研究分担者	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	反応機構 / 電子的効果 / 立体効果 / 反応設計 / 有機反応 / ヘテロ原子効果 / 理論有機化学
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のグループでは、ペンタ-1,4-ジェンの環化反応の経路(諸熊)や、フラーレン類への付加反応の反応経路(永瀬)、イオンの溶媒和(西本)の理論的解明と予測を行った。反応速度論の立場からは、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)、芳香族アルデヒトやケトンの求核付加反応の同位効果と遷移状態の構造(山高)、基質-試薬錯体間の相互作用(速水)、高粘度媒体中での反応に対する圧力効果(浅野)、スルフェン酸の水溶液中での反応(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ープでは、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を定義しヘテロ原子を含む置換基に応用し(広田・榊原)、トリスホモキュバン二量体等の立体的混雑オフイ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、STECARの概念に対する実験的証明(手塚)、BINAP-Ru(II)による不整水素化反応経路(野依)、高歪化合物の構造と反応の関連性(西田)など実験的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ープは、(i)α-アリールビニルカチオン(谷口)、ビシクロ環系のα-ケトカチオン(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)電子移動により開始される反応(永田)の機構解明、(iii)超音波照射による反応のスイッチング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ープは、シリセニウムイオン等の有機珪素化合物(吉良)、ポリシラ環状アセチレン及びオレフィン(安藤亘)、超原子価化合物(秋葉)、キラルなビスムチン(鈴木)、高周期ヘテロ原子化合物(岡崎)、〔3.3〕メタシクロファン(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] T. Komatsuzaki, I. Akai, K. Sakakibara, M. Hirota: "A New Steric Substituent Constans Ωs. Characteristic Feature and Comparison with Some Other Steric Constans." Tetrahedron. 48. 1539-1556 (1992)
[文献書誌] I. Akai, K. Sakakibara M. Hirota: "The Ωs Constant for Polar Substituents. Reinvestigation on the Separation of the Steric and the Polar Effects." Chemistry Letters. 1992. 1317-1320 (1992)
[文献書誌] E. Nakamura, Y. Muyachi N. Koga, K. Morokuma: "Theoratical Studies of Heteroatom-Directed Carbometallation. Addition of MeCu, Me2Cu-and MeLi to Acetylenes." Journal of American Chemical Society. 114. 6686-6694 (1992)
[文献書誌] S. Nagase, K. Kobayashi M. Nagashima: "The Heavier Group 14 Andlogues of the Bicyclo[1.1.0]butane Radical Cations. A Theoretical Study." Journal of Physical Chemistry. 96. 9189-9194 (1992)
[文献書誌] O. S. Lee, E. Osawa: "An Explanation for the Contrasting Reactivities of meso-and d,l-DaDtDtレ3aCtDtレ-Trishomocubylidene-DaDtDtレ3aCtDtレ-trishomocubane towards Electrophiles" Bulletin of the Korean Chemical Society. 13. 59-64 (1992)
[文献書誌] K. Honda, K. Kitaura, K. Nishimoto: "Theoretical Study of Structure and thermodynamic Properties of Liquid Hydrogen Fluoride." Bulletin of the Chemical Society of Japan. 65. 3122-3134 (1992)
[文献書誌] 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)
[文献書誌] H. Yamataka, K. Nagareda K. Ando, T. Hanafusa: "Relative Reactivity and Stereoselectivity in the Wittin Reactions of Substitued Benzaldehydes with Benzylidenetriphenylphosphorane." Journal of Organic Chemistry. 57. 2865-2870 (1992)
[文献書誌] Toshi Nagata: "Synthesis and Characterization of Doubly-Stapped porohyrins." Bulletin of the Chemical Society of Japan. 65. 385-391 (1992)
[文献書誌] I. K. Lednev, M. V. Alfimov Y. Kuriyama, T. Arai, H. Sakuragi, K. Tokumaru: "Photosensitized cis-trans Isomerization of Stilbene via Cation Radical Mechanism in Micellar Solution." Journal of Photochemistry & Photobiology A: Chem.63. 201-209 (1992)
[文献書誌] G. Yamamoto, H. Higuchi, H. Yamamoto, J. Ojima: "1H and 13C Spectral Behavior and Isomerism in bisdehydro[15] annulenones." Bulletin of Chemical Society of Japan. 65. 2388-2394 (1992)
[文献書誌] W. Ando, F. Hojo, S. Sekigawa, N. Nakajima, T. Shimizu: "First Isolation of Six-Member Cyclic Acetylene: Synthesis and Reaction of Tetrasilacyclohexynes." Oraganometallics. 11. 1009-1020 (1992)
[文献書誌] 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" Joural of American Chemical Society. 113. 9270-9276 (1991)
[文献書誌] Y. Matano, M. Kinoshita H. Suzuki: "Synthesis and Reactions of Some Crowed Triorganyl Bismuthines." Bulletin of the Chemical Society of Japan. 65. 3504-3511 (1992)
[文献書誌] H. Takemura, T. Shinmyozu, T. Inazu: "Syntheses and Properties of Highly Symmetrical Cage Compounds: Pyridine Analogues of Hexa-m-xylylenetetramine" Joural of American Chemical Society. 113. 1323-1331 (1991)
[文献書誌] A. Ohno, M. Okamura, T. Kashiwagi, Y. Mikata, N. Yamazaki: "Stereospecific Electrochemical Oxidation of NAD(P)H Analogs Mediated by Radical Cation of Anilines." Chemistry Letters. 1992. 1247-1250 (1992)
[文献書誌] T. Kawamoto, M.Tomishima F. Yoneda, J. Hayami: "Synthesis and Reaction of Novel 5-Deazaflavins with Axial Chirarity at Pyrimidine Ring Moiety." Tetrahedron Letters. 33. 3169-3172 (1992)
[文献書誌] K. Cosstick, T. Asano N. Ohno: "Prssure-Induced Retardation of Steric Isomerzations in Highly Viscous Media" Proceedings of XIII AIRAPT Interantional Conference on High Pressure Science and Technology. 556-558 (1992)
[文献書誌] T. Okuyama, T. Fueno: "Dual Reactivity of Methoxymethy I Benzenesulfenate in Nucleophilic Substitution." Bulletin of the Chemical Society Japan.65. 2672-2683 (1992)
[文献書誌] M. Kitamura, M. Tokunaga, R. Noyori: "Practical Synthesis of BINAP-Ruthenium(II)." Journal of Organic Chemistry. 57. 4053-4054 (1992)
[文献書誌] T. Tezuka, Y. Isahaya: "The STECAR (Steric Compression-assisted Reaction) Concept. Ionic Deoxygenation Raction via Intramolecular Proton Shift in Bornyl α-azo-hydroperoxide to give Camphor Hydrazone." Tetrahedron Letters. 32. 4955-4958 (1991)
[文献書誌] S. Nishida, N. Asanuma T. Tsuji, T. Imai M. Murakami: "Reactions of Spiro[2.4]hept-4-ene Dreivatives with tetracyanoethylene. Occurrence of the Type II reaction in Some Disubstituted Substates." Journal of Organic Chemistry. 57. 4658-4663 (1992)
[文献書誌] T. Kutamura,T. Takachi, H. Kawamoto H. Taniguchi: "Electophile-Induced Intramolecular Cyclization of ortho-(Aryloxy)-phenylalkynes to Dibenzo[b,f]oxepines." Journal of Chemical Society, Perkin Trans. 1. 1992. 1969-1975 (1992)
[文献書誌] K. Takeuchi, Y. Ohga, T. Kitagawa, M. Yoshida, A. Tsugeno: "Solvolysis of 2-Methylene Bridgehead Derivatives: A Model for Gradual Variation of π-Conjugation in Carbocation." Journal of Organic Chemistry. 57. 280-289 (1992)

1992 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

広田 穰 横浜国立大学, 工学部, 教授 (00017881)

研究成果

[文献書誌] T. Komatsuzaki, I. Akai, K. Sakakibara, M. Hirota: "A New Steric Substituent Constans Ωs. Characteristic Feature and Comparison with Some Other Steric Constans." Tetrahedron. 48. 1539-1556 (1992)

[文献書誌] I. Akai, K. Sakakibara M. Hirota: "The Ωs Constant for Polar Substituents. Reinvestigation on the Separation of the Steric and the Polar Effects." Chemistry Letters. 1992. 1317-1320 (1992)

[文献書誌] E. Nakamura, Y. Muyachi N. Koga, K. Morokuma: "Theoratical Studies of Heteroatom-Directed Carbometallation. Addition of MeCu, Me2Cu-and MeLi to Acetylenes." Journal of American Chemical Society. 114. 6686-6694 (1992)

[文献書誌] S. Nagase, K. Kobayashi M. Nagashima: "The Heavier Group 14 Andlogues of the Bicyclo[1.1.0]butane Radical Cations. A Theoretical Study." Journal of Physical Chemistry. 96. 9189-9194 (1992)

[文献書誌] O. S. Lee, E. Osawa: "An Explanation for the Contrasting Reactivities of meso-and d,l-DaDtDtレ3aCtDtレ-Trishomocubylidene-DaDtDtレ3aCtDtレ-trishomocubane towards Electrophiles" Bulletin of the Korean Chemical Society. 13. 59-64 (1992)

[文献書誌] K. Honda, K. Kitaura, K. Nishimoto: "Theoretical Study of Structure and thermodynamic Properties of Liquid Hydrogen Fluoride." Bulletin of the Chemical Society of Japan. 65. 3122-3134 (1992)

[文献書誌] 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)

[文献書誌] H. Yamataka, K. Nagareda K. Ando, T. Hanafusa: "Relative Reactivity and Stereoselectivity in the Wittin Reactions of Substitued Benzaldehydes with Benzylidenetriphenylphosphorane." Journal of Organic Chemistry. 57. 2865-2870 (1992)

[文献書誌] Toshi Nagata: "Synthesis and Characterization of Doubly-Stapped porohyrins." Bulletin of the Chemical Society of Japan. 65. 385-391 (1992)

[文献書誌] I. K. Lednev, M. V. Alfimov Y. Kuriyama, T. Arai, H. Sakuragi, K. Tokumaru: "Photosensitized cis-trans Isomerization of Stilbene via Cation Radical Mechanism in Micellar Solution." Journal of Photochemistry & Photobiology A: Chem.63. 201-209 (1992)

[文献書誌] G. Yamamoto, H. Higuchi, H. Yamamoto, J. Ojima: "1H and 13C Spectral Behavior and Isomerism in bisdehydro[15] annulenones." Bulletin of Chemical Society of Japan. 65. 2388-2394 (1992)

[文献書誌] W. Ando, F. Hojo, S. Sekigawa, N. Nakajima, T. Shimizu: "First Isolation of Six-Member Cyclic Acetylene: Synthesis and Reaction of Tetrasilacyclohexynes." Oraganometallics. 11. 1009-1020 (1992)

[文献書誌] 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" Joural of American Chemical Society. 113. 9270-9276 (1991)

[文献書誌] Y. Matano, M. Kinoshita H. Suzuki: "Synthesis and Reactions of Some Crowed Triorganyl Bismuthines." Bulletin of the Chemical Society of Japan. 65. 3504-3511 (1992)

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

[文献書誌] A. Ohno, M. Okamura, T. Kashiwagi, Y. Mikata, N. Yamazaki: "Stereospecific Electrochemical Oxidation of NAD(P)H Analogs Mediated by Radical Cation of Anilines." Chemistry Letters. 1992. 1247-1250 (1992)

[文献書誌] T. Kawamoto, M.Tomishima F. Yoneda, J. Hayami: "Synthesis and Reaction of Novel 5-Deazaflavins with Axial Chirarity at Pyrimidine Ring Moiety." Tetrahedron Letters. 33. 3169-3172 (1992)

[文献書誌] K. Cosstick, T. Asano N. Ohno: "Prssure-Induced Retardation of Steric Isomerzations in Highly Viscous Media" Proceedings of XIII AIRAPT Interantional Conference on High Pressure Science and Technology. 556-558 (1992)

[文献書誌] T. Okuyama, T. Fueno: "Dual Reactivity of Methoxymethy I Benzenesulfenate in Nucleophilic Substitution." Bulletin of the Chemical Society Japan.65. 2672-2683 (1992)

[文献書誌] M. Kitamura, M. Tokunaga, R. Noyori: "Practical Synthesis of BINAP-Ruthenium(II)." Journal of Organic Chemistry. 57. 4053-4054 (1992)

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

[文献書誌] S. Nishida, N. Asanuma T. Tsuji, T. Imai M. Murakami: "Reactions of Spiro[2.4]hept-4-ene Dreivatives with tetracyanoethylene. Occurrence of the Type II reaction in Some Disubstituted Substates." Journal of Organic Chemistry. 57. 4658-4663 (1992)

[文献書誌] T. Kutamura,T. Takachi, H. Kawamoto H. Taniguchi: "Electophile-Induced Intramolecular Cyclization of ortho-(Aryloxy)-phenylalkynes to Dibenzo[b,f]oxepines." Journal of Chemical Society, Perkin Trans. 1. 1992. 1969-1975 (1992)

[文献書誌] K. Takeuchi, Y. Ohga, T. Kitagawa, M. Yoshida, A. Tsugeno: "Solvolysis of 2-Methylene Bridgehead Derivatives: A Model for Gradual Variation of π-Conjugation in Carbocation." Journal of Organic Chemistry. 57. 280-289 (1992)

1992 年度実績報告書

広田穰横浜国立大学, 工学部, 教授 (00017881)