1990 Fiscal Year Annual Research Report

特異な分子場の設計に基づく物質変換

Research Project

Project/Area Number	02303003
Research Institution	The University of Tokyo
Principal Investigator	岡崎廉治東京大学, 理学部, 教授 (70011567)
Co-Investigator(Kenkyū-buntansha)	富岡秀雄三重大学, 工学部, 教授 (20024599) 高谷秀正京都大学, 工学部, 教授 (40022644) 小林啓二東京大学, 教養学部, 教授 (50012456) 宇根山健治岡山大学, 工学部, 教授 (00033150) 青山安宏長岡技術科学大学, 工学部, 教授 (00038093)
Keywords	分子場 / 反応場 / 固相反応 / マトリックス / 生体反応モデル / 不斉反応
Research Abstract	本研究は大きく4つのグル-プに分けて行なわれた。第1グル-プは特異な集合分子場の設計による物質変換について研究した。αーオキソアミドの固相光反応、チエノアセンやジアセチレンなどが作る包接結晶場での反応、結晶中に発生させたナイトレンの異常な安定性、含硫フェナレン誘導体での電荷移動錯体の発現、トロポチオンの結晶場での反応などが検討され、結晶のような秩序場での特異な反応性の実現の可能性などが示された。第2グル-プは生体分子場のモデルの設計と物質変換について研究した。糖、ポルフィリン誘導体を用いた多点相互作用場の設計、キノン側鎖をもつポルフィリン誘導体による光合成電子移動のモデル化、不斉場をもつ鉄ーポルフィリン錯体による不斉エポキシ化などについて検討し、ポルフィリンなどの場を活用することにより優れた生体反応場のモデル化が可能であることが明らかとなった。第3グル-プは特異な単分子場の設計による物質変換を研究した。極低温マトリックス中に発生させたカルベン、ニトレンの反応性、5配位ケイ素を反応場とする選択的物質変換、BINAPーRu錯体を用いた遷移金属上でのキラル触媒場の創出、ジカルコゲノラト遷移金属錯体での異常反応、かさ高いベンゼン誘導体、トリプチセンなどを用いる速度論的安定化による高反応性化学種の合成、電場下での反応制御などが検討され、単一の分子であっても工夫をこらした分子設計が特異な反応場を提供することが示された。第4グル-プは分子場設計の理論的考察を行った。X線結晶回折装置に改良を行えることにより、キラルなコバロキシム錯体の結晶相反応が時分割測定で追跡できることが示され、また非経験的分子軌道法計算が高周期元素(たとえばSi,Ge,Sn,Pb)骨格の特性を予言するのに非常に有効であることが明らかとなった。このような物理化学的側面からの研究が分子場設計に必要不可欠であることが分かった。

Research Products

(17 results)

All Other

All Publications (17 results)

[Publications] M.A.Cremonini,L.Lunazzi,G.Placucci,R.Okazaki,and G.Yamamoto: "Conformation and Stereodynamics of a Highly Hindered Ethane,1,2ーBis(2,4,6ーtriーtertーbutylphenyl)ethane,and of the Corresponding Ethyl Radical." J.Am.Chem.Soc.112. 2915-2921 (1990)
[Publications] Y.Aoyama,M.Asakawa,A.Yamagishi,H.Toi,and H.Ogoshi: "Simultaneous Hydrogen Bonding and Metal Coordination Interactions in TwoーPoint Fixation of Amino Acids with a Bifunctional Metalloporphyrin Receptor." J.Am.Chem.Soc.112. 3145-3151 (1990)
[Publications] H.Aoyama,Y.Arata,and Y.Omote: "Intramolecular Photocycloaddition of NーBenzylstyrylacetamides.[2+2] Addition of Styrenes to Benzenes." J.Chem.Soc.,Chem.Commun.736-737 (1990)
[Publications] T.Akasaka,M.Kako,S.Nagase,A.Yabe,and W.Ando: "Spectroscopic Studies on Chargeーtransfer Photoーoxygenation of Disiliranes." J.Am.Chem.Soc.112. 7804-7806 (1990)
[Publications] T.Akiyama,K.Nakamura,M.Tamada,H.Ushijima,M.Kajitani,K.Shimizu,and A.Sugimori: "Intramolecular Interactions between Two Nonーconjugated Metal Complex Moieties in Alkyleneーbridged Ferrocene and (ηーCycloーpentadienyl)(1,2ーdicyanoー1,2ーethylenedithiolato)cobalt(III)" Chem.Lett.1990. 1255-1258 (1990)
[Publications] K.Uneyama and S.Watanabe: "Electrochemical Hydrotrifluoromethylation of Fumaronitrile." J.Org.Chem.55. 3909-3912 (1990)
[Publications] Y.Ohashi,A.Sekine,E.Shimizu,K.Hori,and A.Uchida: "Free Factors Controlling the Reaction Rate in Solid State Photoisomerization." Mol.Cryst.Liq.Cryst.186. 37-44 (1990)
[Publications] M.Kira,K.Sato,and H.Sakurai: "Highly Stereoselective Allylation of Aldehydes with Pentacoordinate Allylsilicates in Hydroxylic Media.Discrimination between Linear and αーbranched Alkanals." J.Am.Chem.Soc.112. 257-260 (1990)
[Publications] S.Matsumiya,A.Izuoka,T.Sugawara,and N.Nakamura: "Role of 2ーCarboxyl Substituent in the Tautomerization between Two Equivalent Enol Forms of 3ーHydroxyphenalenone." J.Phys.Org.Chem.3. 485-488 (1990)
[Publications] N.Fukuda,K.Majima,Y.Matsumura,and H.Takaya: "Synthesis of New Chiral Bis(triarylphosphine) Ligands Based on Asymmetric Hydrogenation of 4,5ーDiarylー2ーoxocyclopentanecarboxyーlates." Tetrahedron Lett.31. 7185-7188 (1990)
[Publications] K.Tanaka,S.Kishigami,and F.Toda: "A New Method for Coupling Aromatic Aldehydes and Ketones To Produce αーGlycols Using ZnーZnCl_2 in Aqueous Solution and in the Solid State." J.Org.Chem.55. 2981-2983 (1990)
[Publications] S.Murata,H.Tomioka,T.Kawase,and M.Oda: "Reaction of Bicyclo[6.3.0]undecaー2,4,6,8,11ーpentaenー10ーylidene in OxygenーDoped Matrices:Characterization of the First Carbonyl Oxide with a πーDonating Ring System." J.Org.Chem.55. 4502-4504 (1990)
[Publications] S.Tomoda and M.Iwaoka: "Synthesis and Structures of Host Molecules Containing a SeーSe bond.Intramolecular Hypervalent Nature of Selenium Atoms in the Crystal State." J.Chem.Soc.Chem.Commun.1990. 231-233 (1990)
[Publications] S.Nagase,S.Suzuki,and T.Kurakake: "Do Distibene(HSb=SbH) and Dibismuthene(HBi=BiH) feature Double Bonding?Theoretical Comparison with Diphosphene(HP=PH) and Diarsene(HAs=AsH)." J.Chem.Soc.Chem.Commun.1990. 1724-1726 (1990)
[Publications] K.Nakasuji,A.Oda,J.Toyoda,and I.Murata: "Synthesis and Properties of 3,9ーDithiaperylene:A Third Isomer of PeriーCondensed WeitzーType Donors based on the Perylene Skeleton." J.Chem.Soc.,Chem.Commun.1990. 367-368 (1990)
[Publications] Y.Naruta,F.Tani,and K.Maruyama: "Catalytic and Asymmetric Oxidation of Sulphides with Iron Complexes of Chiral‘Twin Coronet'Porphyrins." J.Chem.Soc.,Chem.Commun.1378-1380 (1990)
[Publications] T.Machiguchi and S.Yamabe: "A PhenylーGroup Participation in the Antisymmetric Orbital Interaction for [8+2] Cycloaddition of Tropothione with Diphenylketene." Tetrahedron Lett.29. 4169-4172 (1990)

1990 Fiscal Year Annual Research Report

特異な分子場の設計に基づく物質変換

Principal Investigator

岡崎 廉治 東京大学, 理学部, 教授 (70011567)

Research Products

[Publications] M.A.Cremonini,L.Lunazzi,G.Placucci,R.Okazaki,and G.Yamamoto: "Conformation and Stereodynamics of a Highly Hindered Ethane,1,2ーBis(2,4,6ーtriーtertーbutylphenyl)ethane,and of the Corresponding Ethyl Radical." J.Am.Chem.Soc.112. 2915-2921 (1990)

[Publications] Y.Aoyama,M.Asakawa,A.Yamagishi,H.Toi,and H.Ogoshi: "Simultaneous Hydrogen Bonding and Metal Coordination Interactions in TwoーPoint Fixation of Amino Acids with a Bifunctional Metalloporphyrin Receptor." J.Am.Chem.Soc.112. 3145-3151 (1990)

[Publications] H.Aoyama,Y.Arata,and Y.Omote: "Intramolecular Photocycloaddition of NーBenzylstyrylacetamides.[2+2] Addition of Styrenes to Benzenes." J.Chem.Soc.,Chem.Commun.736-737 (1990)

[Publications] T.Akasaka,M.Kako,S.Nagase,A.Yabe,and W.Ando: "Spectroscopic Studies on Chargeーtransfer Photoーoxygenation of Disiliranes." J.Am.Chem.Soc.112. 7804-7806 (1990)

[Publications] K.Uneyama and S.Watanabe: "Electrochemical Hydrotrifluoromethylation of Fumaronitrile." J.Org.Chem.55. 3909-3912 (1990)

[Publications] Y.Ohashi,A.Sekine,E.Shimizu,K.Hori,and A.Uchida: "Free Factors Controlling the Reaction Rate in Solid State Photoisomerization." Mol.Cryst.Liq.Cryst.186. 37-44 (1990)

[Publications] M.Kira,K.Sato,and H.Sakurai: "Highly Stereoselective Allylation of Aldehydes with Pentacoordinate Allylsilicates in Hydroxylic Media.Discrimination between Linear and αーbranched Alkanals." J.Am.Chem.Soc.112. 257-260 (1990)

[Publications] S.Matsumiya,A.Izuoka,T.Sugawara,and N.Nakamura: "Role of 2ーCarboxyl Substituent in the Tautomerization between Two Equivalent Enol Forms of 3ーHydroxyphenalenone." J.Phys.Org.Chem.3. 485-488 (1990)

[Publications] N.Fukuda,K.Majima,Y.Matsumura,and H.Takaya: "Synthesis of New Chiral Bis(triarylphosphine) Ligands Based on Asymmetric Hydrogenation of 4,5ーDiarylー2ーoxocyclopentanecarboxyーlates." Tetrahedron Lett.31. 7185-7188 (1990)

[Publications] K.Tanaka,S.Kishigami,and F.Toda: "A New Method for Coupling Aromatic Aldehydes and Ketones To Produce αーGlycols Using ZnーZnCl_2 in Aqueous Solution and in the Solid State." J.Org.Chem.55. 2981-2983 (1990)

[Publications] S.Murata,H.Tomioka,T.Kawase,and M.Oda: "Reaction of Bicyclo[6.3.0]undecaー2,4,6,8,11ーpentaenー10ーylidene in OxygenーDoped Matrices:Characterization of the First Carbonyl Oxide with a πーDonating Ring System." J.Org.Chem.55. 4502-4504 (1990)

[Publications] S.Tomoda and M.Iwaoka: "Synthesis and Structures of Host Molecules Containing a SeーSe bond.Intramolecular Hypervalent Nature of Selenium Atoms in the Crystal State." J.Chem.Soc.Chem.Commun.1990. 231-233 (1990)

[Publications] S.Nagase,S.Suzuki,and T.Kurakake: "Do Distibene(HSb=SbH) and Dibismuthene(HBi=BiH) feature Double Bonding?Theoretical Comparison with Diphosphene(HP=PH) and Diarsene(HAs=AsH)." J.Chem.Soc.Chem.Commun.1990. 1724-1726 (1990)

[Publications] K.Nakasuji,A.Oda,J.Toyoda,and I.Murata: "Synthesis and Properties of 3,9ーDithiaperylene:A Third Isomer of PeriーCondensed WeitzーType Donors based on the Perylene Skeleton." J.Chem.Soc.,Chem.Commun.1990. 367-368 (1990)

[Publications] Y.Naruta,F.Tani,and K.Maruyama: "Catalytic and Asymmetric Oxidation of Sulphides with Iron Complexes of Chiral‘Twin Coronet'Porphyrins." J.Chem.Soc.,Chem.Commun.1378-1380 (1990)

[Publications] T.Machiguchi and S.Yamabe: "A PhenylーGroup Participation in the Antisymmetric Orbital Interaction for [8+2] Cycloaddition of Tropothione with Diphenylketene." Tetrahedron Lett.29. 4169-4172 (1990)

岡崎廉治東京大学, 理学部, 教授 (70011567)