1994 Fiscal Year Annual Research Report

活性異常分子-合成と反応制御-

Research Project

Project/Area Number	05303003
Research Institution	University of Tsukuba
Principal Investigator	安藤亘筑波大学, 化学系, 教授 (30008429)
Co-Investigator(Kenkyū-buntansha)	宮仕勉東北大学, 理学部, 教授 (20004442) 富岡秀雄三重大学, 工学部, 教授 (20024599) 鈴木仁美京都大学, 理学部, 教授 (50025342) 小田雅司大阪大学, 理学部, 教授 (60004438) 古川尚道筑波大学, 化学系, 教授 (80015966)
Keywords	活性分子 / 異常原子価 / 高歪み化合物 / 活性種 / 反芳香族性 / ラジカルイオン / π-共役 / カルベン
Research Abstract	本研究は、歪み、電荷、原子価、π-共役等により異常な性質を発現する活性分子の合成安定化と反応について研究することを目的とする。本年度は研究分担者を次の3つのグループに分け、各々のグループ内での緊密な連係の基に研究を進めた。12月箱根で開催した全体会議において、各グループ間の情報交換や共同研究の打ち合わせを行なった。特に基礎研究と応用研究の成果をお互いに良く情報交換し、効率の良い研究を推進した。(1)新しい異常原子価反応活性種の創出と新規反応性の開拓、(2)高歪化合物の合成とその化学的挙動(3)異常な電荷やπ-共役系を有する分子の合成と機能性材料合成の応用。本研究は既に班員各自が各々の専門分野で発展させてきた研究テーマを継続しながら新たに班員間の共同研究を推進する。さらに、得られた研究成果を基に、理論、合成、反応等の各分野の研究者が一致協力して研究を推進すれば、著しい発展が期待できるテーマを選んで重点的に研究を進め、萌芽的な新たな可能性についても合わせて検討した。本研究対象である活性異常分子は高歪みや反芳香族性、原子価欠損等の化合物であり、有機化学の理論、構造、反応の各分野にまたがって広く興味と関心を集めており、各分野の第一線の研究者達を集めた本研究によって得られた成果は世界に大きなインパクトを与えた。

Research Products

(18 results)

All Other

All Publications (18 results)

[Publications] T.Akaska,B.Mitsuda,W.Ando,K.Kobayashi,S.Nagase: "Adduct of C_<60> at the Equatorial Belt:Photochemical Cycloaddition with Disilirane" J.Amer.Chem.Soc.116. 2627-2628 (1994)
[Publications] N.Furukawa: "The Pummerer and the Thio-Claisen-type Rearrangements of Naphtho[1.8-bc]-1.5-dithiocin Monooxide and N-p-Tosylsulfilimine" Heteroatom Chem.(in press).
[Publications] H.Kurata,T.Kawase,M.Oda: "Alkali Metal Reduction of Oligo-6-(2-thienyl)pentafulvenes.Synthesis of Oligothienylenemethines Attached with Cyclopentadienede Croups" Chemistry Lett.2219-2222 (1994)
[Publications] Y.Matano,N.Azuma,H.Suzuki: "Synthesis,X-Ray Structure and Reactions of (2-Oxoalkyl)triarylbismuthonium Salts" J.Chem.Soc.Perkin Trans.1. 1739-1747 (1994)
[Publications] H.Tomioka,H.Okada,T.Watanabe,K.Hirai: "An Extremely Long-Lived Triplet Carbene;Reactivity,Optical Absorption Spectrum,and Kinetics of Highly Congested Diarylcarbenes" Angew.Chem.Int.Ed.Engl.33. 873-875 (1994)
[Publications] Y.Takahashi,S.M.,K.W.T.Suzuki,T.Miyashi: "Cycloreversion of Arene Endoperoxides Induced by Electron Transfer" J.Chem.Soc.Chem.Commun.13-14 (1994)
[Publications] Y.Nagao: "New Intramolecular Spiro-Endo-Mpde Ring Closure of Allenyl (Methoxy-Substituted Phenyl)alkyl Ketones" Tetrahedron Lett.(in press).
[Publications] M.Iyoda: "Synthesis of Pentacarbonyl(1-oxazulen-2-ylidene)chromium(0) and -tungsten(0)complexes" Tetrahedron Lett.36(in press). (1995)
[Publications] S.Nagase,K.Kobayashi: "Theoretical Study of the Dimetallefullerene SC_2 C_<84>" Chem.Phys.Lett.231. 319-324 (1994)
[Publications] S.Inoue,T.Jigami,H.N.,T.O.,F.Ogura: "2,2^1-Bitelluropgene and 2,2^1:5^1,2^<11>-Tertellurophene as Novel High Homologues of Telluropgene" Tetrahedron Lett.35. 8009-8012 (1994)
[Publications] M.Unno,A.Kyushin,H.Matsumoto: "Ring-Opening Reaction of Octakis(1,1,2-trimethylpropyl)octasilacubane:Chlorination with PCl_5 Leading to Stereoisomeric 4,8-Dichloroota-" Organometallics. 13. 4633-4640 (1994)
[Publications] A.Miyashita,M.Hotta,Y.Saida: "Selective sp C-H bond activation of alkylaromatics promoted by platinum complexes" J.Organo.Chem.473. 353-358 (1994)
[Publications] M.Kajitani,A.Sugimori: "Photochemical Reactions of Several Adducts of Metalladithiolens and Metalladithiazoles-Dissocioation and Rearrangement" Coord.Chem.Revs.132. 175-180 (1994)
[Publications] M.Kimura,Y.Sawaki: "Electrocatalyzed Reaction of Aldehydes with Trialkoxysilanes" Denki Kagaku. 62. 1119-1124 (1994)
[Publications] A.Sekiguchi: "官能性シクロテトラゲルマンおよびはしご形ポリゲルマンの合成と構造" 日本化学会誌. 248-252 (1994)
[Publications] H.Suzuki,N.Tokitoh,R.Okazaki: "A Novel Reactivity of a Silylene:The First Examples of [1+2]Cycloaddition with Aromatic Compounds" J.Am.Chem.Soc.116. 11572-11573 (1994)
[Publications] S.Murahashi,Y.Imada,H.Ohtake: "Tungstate-Catalyzed Cecarboxylative Oxidation of N-Alkyl-a-amino Acids:An efficient Method for Regioselective Synthesis" J.Org.Chem.59. 6170-6172 (1994)
[Publications] S.Murahashi,T.Naota: "Pergamon Press,Oxford,E.W.Abel,F.G.A.Stone,G.Wilkinson,eds" Comprehensive Orgfanometallic Chemistry II. (in press).

1994 Fiscal Year Annual Research Report

活性異常分子-合成と反応制御-

Principal Investigator

安藤 亘 筑波大学, 化学系, 教授 (30008429)

Research Products

[Publications] T.Akaska,B.Mitsuda,W.Ando,K.Kobayashi,S.Nagase: "Adduct of C_<60> at the Equatorial Belt:Photochemical Cycloaddition with Disilirane" J.Amer.Chem.Soc.116. 2627-2628 (1994)

[Publications] N.Furukawa: "The Pummerer and the Thio-Claisen-type Rearrangements of Naphtho[1.8-bc]-1.5-dithiocin Monooxide and N-p-Tosylsulfilimine" Heteroatom Chem.(in press).

[Publications] H.Kurata,T.Kawase,M.Oda: "Alkali Metal Reduction of Oligo-6-(2-thienyl)pentafulvenes.Synthesis of Oligothienylenemethines Attached with Cyclopentadienede Croups" Chemistry Lett.2219-2222 (1994)

[Publications] Y.Matano,N.Azuma,H.Suzuki: "Synthesis,X-Ray Structure and Reactions of (2-Oxoalkyl)triarylbismuthonium Salts" J.Chem.Soc.Perkin Trans.1. 1739-1747 (1994)

[Publications] H.Tomioka,H.Okada,T.Watanabe,K.Hirai: "An Extremely Long-Lived Triplet Carbene;Reactivity,Optical Absorption Spectrum,and Kinetics of Highly Congested Diarylcarbenes" Angew.Chem.Int.Ed.Engl.33. 873-875 (1994)

[Publications] Y.Takahashi,S.M.,K.W.T.Suzuki,T.Miyashi: "Cycloreversion of Arene Endoperoxides Induced by Electron Transfer" J.Chem.Soc.Chem.Commun.13-14 (1994)

[Publications] Y.Nagao: "New Intramolecular Spiro-Endo-Mpde Ring Closure of Allenyl (Methoxy-Substituted Phenyl)alkyl Ketones" Tetrahedron Lett.(in press).

[Publications] M.Iyoda: "Synthesis of Pentacarbonyl(1-oxazulen-2-ylidene)chromium(0) and -tungsten(0)complexes" Tetrahedron Lett.36(in press). (1995)

[Publications] S.Nagase,K.Kobayashi: "Theoretical Study of the Dimetallefullerene SC_2 C_<84>" Chem.Phys.Lett.231. 319-324 (1994)

[Publications] S.Inoue,T.Jigami,H.N.,T.O.,F.Ogura: "2,2^1-Bitelluropgene and 2,2^1:5^1,2^<11>-Tertellurophene as Novel High Homologues of Telluropgene" Tetrahedron Lett.35. 8009-8012 (1994)

[Publications] M.Unno,A.Kyushin,H.Matsumoto: "Ring-Opening Reaction of Octakis(1,1,2-trimethylpropyl)octasilacubane:Chlorination with PCl_5 Leading to Stereoisomeric 4,8-Dichloroota-" Organometallics. 13. 4633-4640 (1994)

[Publications] A.Miyashita,M.Hotta,Y.Saida: "Selective sp C-H bond activation of alkylaromatics promoted by platinum complexes" J.Organo.Chem.473. 353-358 (1994)

[Publications] M.Kajitani,A.Sugimori: "Photochemical Reactions of Several Adducts of Metalladithiolens and Metalladithiazoles-Dissocioation and Rearrangement" Coord.Chem.Revs.132. 175-180 (1994)

[Publications] M.Kimura,Y.Sawaki: "Electrocatalyzed Reaction of Aldehydes with Trialkoxysilanes" Denki Kagaku. 62. 1119-1124 (1994)

[Publications] A.Sekiguchi: "官能性シクロテトラゲルマンおよびはしご形ポリゲルマンの合成と構造" 日本化学会誌. 248-252 (1994)

[Publications] H.Suzuki,N.Tokitoh,R.Okazaki: "A Novel Reactivity of a Silylene:The First Examples of [1+2]Cycloaddition with Aromatic Compounds" J.Am.Chem.Soc.116. 11572-11573 (1994)

[Publications] S.Murahashi,Y.Imada,H.Ohtake: "Tungstate-Catalyzed Cecarboxylative Oxidation of N-Alkyl-a-amino Acids:An efficient Method for Regioselective Synthesis" J.Org.Chem.59. 6170-6172 (1994)

[Publications] S.Murahashi,T.Naota: "Pergamon Press,Oxford,E.W.Abel,F.G.A.Stone,G.Wilkinson,eds" Comprehensive Orgfanometallic Chemistry II. (in press).

安藤亘筑波大学, 化学系, 教授 (30008429)