1994 Fiscal Year Annual Research Report

高次有機反応場の設計と制御に関する基礎研究

Research Project

Project/Area Number	06353002
Research Institution	University of Tsukuba
Principal Investigator	安藤亘筑波大学, 化学系, 教授 (30008429)
Co-Investigator(Kenkyū-buntansha)	山本嘉則東北大学, 理学部, 教授 (60029519) 園田昇大阪大学, 工学部, 教授 (20083983) 沢木泰彦名古屋大学, 工学部, 教授 (30023120) 木村栄一広島大学, 医学部, 教授 (30034010) 岡崎廉治東京大学, 理学部, 教授 (70011567)
Keywords	反応場 / 高次有機反応 / 有機素反応 / 有機金属反応 / 励起反応
Research Abstract	本研究は、複合系での高次有機反応場の研究に重要性に鑑み、特に重点的に高次有機反応場としての有機素反応場、励起反応場、有機金属反応場、立体制御反応場での複合反応の各研究課題について調査研究を行ない、その成果を基に将来の重点領域研究の研究領域として高次有機反応場の研究を発展させることを目的とした。単に個人の研究の寄せ集めでなく、緊密な連係の下に研究を重点的に推進するために、次の3つの副主題によりグループ分けして研究を推し進めると共に、全体の研究会議及びグループ相互の人的交流を蜜に行なった。 (1)有機素反応場の解析:有機素反応場の基礎的知見を得るため、有機反応に対する立体効果と電子効果を解明し、物性・反応性に及ぼす影響を定量的に評価した。さらに、三次元構造を有する分子化合物による立体保護場の設計と制御の研究を行なった。又、回転異性場や電子立体反応場を構築し、構造と反応性の相関を基礎的な解明や、立体制御された反応場を用いた高選択性合成反応を開発した。 (2)励起反応場の設計と制御:励起反応場を構築させるために、活性有機分子や異常原子価活性分子を創出し反応場として用いた。 (3)有機金属反応場の設計と制御:高次金属構造を有する反応場を新たに設計し、これを用いて新反応性及び新選択性を創出した。さらに、これらの具体的な研究成果を基に、企画調査を行なった。 1)各々の研究領域に属する研究分担者は、研究の現状と展望について調査し、研究企画を立てた。 2)9月末名古屋で開催した全体会議において、広い立場での研究組織、領域について討論を行ない、新しい国際的に対応できる研究分野の創成のための準備を行なった。

Research Products

(21 results)

All Other

All Publications (21 results)

[Publications] W.Ando,H.Ohgaki,Y.Kabe: "Stable Germirane Derivatives" Angew.Chem.Int.Ed.Engl.106. 723-725 (1994)
[Publications] H.Suzuki,N.Tokitoh,R.Okazaki: "A Novel Reactivity of a Silylene:The First Exmpies of [1+2]Cycloaddition with Aromatic Compounds" J.Am.Chem Soc.116. 11572-11573 (1994)
[Publications] T Koike,E.Kimura: "The Catalytic Carboxyester Hydrolysis by a New Zinc(II)Complex:A Novel Model for Indirect Activation of the Serine Nucleophile by Zinc(II)・・" J.Am.Chem.Soc.117. in press (1995)
[Publications] T.Imae,T.Takagi,Y.Sawaki: "Photocyclodimerization of Cimamic Acid on Reaction Matrix:Structural effect of Molecular Assemblies" J.Coolid Interface Sci.169. in press (1995)
[Publications] S.Tsunoi,I.Ryu,N.Sonoda: "Remote Carbonylation.The Synthesis of δ-Lactones from Saturated alcohls and Carbon Monoxide" J.Am.Chem.Soc.116. 5473-5474 (1994)
[Publications] Y.Yamamoto,M,Al-Masum,N.Asao: "Palladium Catalyzed Addition of Activated Mcthylone and Methyne Compounds to Allenes" J.Am.Chem.Soc.116. 6019-6020 (1994)
[Publications] C.Zen,Y.Suesawa,M.Hirota: "Further Investigations on Polar Substituent Effects on the NMR Chemical Shifts of N-Acylanilines and Related Compounds.Correlation・・" Bull.Chem.Soc.Jpn.67. 1664-1673 (1994)
[Publications] R.Seki,T.Tezuka,T.Yaasita: "α-Azohydroperoxide,a New Photosynthetic Inhibitor" Weed Research Japan. 38. 159-166 (1993)
[Publications] Y.Ohga,K.Takeuchi: "Solvolyses of Bicyclo[2,2,2]oct-1-yl and 1-Adamantyl Systems Containg an Ethylidene Substituent on the 2-Position" J.Org.Chem.59. 4056-4067 (1994)
[Publications] H.Tago,S.Ishigami,M.F.,T.I.,M.Yokoyama: "Synthesis of C-Nucleosides via Redical Coupling Reaction" J.Chem.Soc.,Perkin Tras.1. 2931-2942 (1994)
[Publications] K.Narasaka: "Oxidation Generation of α-Radicals of Carbonyl Compounds from the α-Stannyl Derivatives and Theur Reactions with Electron-Rich Olefins." Bull.Chem.Soc.68. 322-329 (1995)
[Publications] T.Kawamoto,T.Taga,K.B.,F.Y.,J.Hayami: "Stereochemistry of asymmetric“(net)hydride trnsfer"in an intercoenzyme model reaction sysstem" Tetrahedron Lett.35(accepted). (1994)
[Publications] N.Hayashi,Y.mazaki,K.Kobayshio: "Solid-State Photosolvolysis of Clathrate Crystals Including Ethanol as a Guest Component" Tetrahedron Lett. 35. 5883-5886 (1994)
[Publications] Y.Tohyama,K.Tanino,L.Kuwajima: "Highly Stereoselective Ene Reaction of Aldimines with 2-(Alkylthio)allyl Silyl ethers" J.Org.Chem.59. 59-60 (1994)
[Publications] M.V.Sigalov,S.Toyata,M.Oki,B.A.Trofimov: "Addition of Hydrogen Halides to 1,2-Dialky pyrrolium Cations" Bull.Chem.Soc.Jpn.67. 1872-1878 (1994)
[Publications] T.Ogawa,T.Ikegami,T.Hikasa,H.Suzuki: "Enhanced Nucleohilicity of Tris(2,6-dimethoxyphenyl)bismuthine as Studied by X-ray Crystallography,^<17>O-NMR and Theoretical Calculation" J.Chem.Soc.Perkin Trans.1. 3479-3483 (1994)
[Publications] A.Kato,A.Sugimori: "A Novel Metallacycie 1,2,5,3-Cobaltadithiazole.Formation Structure,and Properties of (η-Cyclopentadienyl)(1-phenylmetanimine-N.1-dithiolato)cobalt" J.Org.Chem.473. 313-321 (1994)
[Publications] H.Suzuki,N.Tokitoh,S.Nagase,R.Okazaki: "The First Genuine Silicon-Sulfur Double Bond Compound:Synthesis and Crystal Stracture of a Kinetically Stabilized Silanethione" J.Am.Chem.Soc.116. 11578-11579 (1994)
[Publications] S.Koseki,H.Tomioka,A Toyata: "FORS MCSF Study on Nitrenophenyl-Methylene C_6H_4CHN" J.Phys.Chem.98. 13203-13209 (1994)
[Publications] M.Yoshifuji,: "2,4-Di-t-butyl-6-methoxyphenyldithioxophosphorane as a Probe for the Mechanistic Studies of Lawesson's Reagent" Tetrahedron Lett.35. 4379-4382 (1994)
[Publications] M.A.Sekiguchi: "Lithium and Sokium Complexes of aTetasilylethylene Dianion" Organomitallics. 14(in press). (1995)

1994 Fiscal Year Annual Research Report

高次有機反応場の設計と制御に関する基礎研究

Principal Investigator

安藤 亘 筑波大学, 化学系, 教授 (30008429)

Research Products

[Publications] W.Ando,H.Ohgaki,Y.Kabe: "Stable Germirane Derivatives" Angew.Chem.Int.Ed.Engl.106. 723-725 (1994)

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

[Publications] T Koike,E.Kimura: "The Catalytic Carboxyester Hydrolysis by a New Zinc(II)Complex:A Novel Model for Indirect Activation of the Serine Nucleophile by Zinc(II)・・" J.Am.Chem.Soc.117. in press (1995)

[Publications] T.Imae,T.Takagi,Y.Sawaki: "Photocyclodimerization of Cimamic Acid on Reaction Matrix:Structural effect of Molecular Assemblies" J.Coolid Interface Sci.169. in press (1995)

[Publications] S.Tsunoi,I.Ryu,N.Sonoda: "Remote Carbonylation.The Synthesis of δ-Lactones from Saturated alcohls and Carbon Monoxide" J.Am.Chem.Soc.116. 5473-5474 (1994)

[Publications] Y.Yamamoto,M,Al-Masum,N.Asao: "Palladium Catalyzed Addition of Activated Mcthylone and Methyne Compounds to Allenes" J.Am.Chem.Soc.116. 6019-6020 (1994)

[Publications] C.Zen,Y.Suesawa,M.Hirota: "Further Investigations on Polar Substituent Effects on the NMR Chemical Shifts of N-Acylanilines and Related Compounds.Correlation・・" Bull.Chem.Soc.Jpn.67. 1664-1673 (1994)

[Publications] R.Seki,T.Tezuka,T.Yaasita: "α-Azohydroperoxide,a New Photosynthetic Inhibitor" Weed Research Japan. 38. 159-166 (1993)

[Publications] Y.Ohga,K.Takeuchi: "Solvolyses of Bicyclo[2,2,2]oct-1-yl and 1-Adamantyl Systems Containg an Ethylidene Substituent on the 2-Position" J.Org.Chem.59. 4056-4067 (1994)

[Publications] H.Tago,S.Ishigami,M.F.,T.I.,M.Yokoyama: "Synthesis of C-Nucleosides via Redical Coupling Reaction" J.Chem.Soc.,Perkin Tras.1. 2931-2942 (1994)

[Publications] K.Narasaka: "Oxidation Generation of α-Radicals of Carbonyl Compounds from the α-Stannyl Derivatives and Theur Reactions with Electron-Rich Olefins." Bull.Chem.Soc.68. 322-329 (1995)

[Publications] T.Kawamoto,T.Taga,K.B.,F.Y.,J.Hayami: "Stereochemistry of asymmetric“(net)hydride trnsfer"in an intercoenzyme model reaction sysstem" Tetrahedron Lett.35(accepted). (1994)

[Publications] N.Hayashi,Y.mazaki,K.Kobayshio: "Solid-State Photosolvolysis of Clathrate Crystals Including Ethanol as a Guest Component" Tetrahedron Lett. 35. 5883-5886 (1994)

[Publications] Y.Tohyama,K.Tanino,L.Kuwajima: "Highly Stereoselective Ene Reaction of Aldimines with 2-(Alkylthio)allyl Silyl ethers" J.Org.Chem.59. 59-60 (1994)

[Publications] M.V.Sigalov,S.Toyata,M.Oki,B.A.Trofimov: "Addition of Hydrogen Halides to 1,2-Dialky pyrrolium Cations" Bull.Chem.Soc.Jpn.67. 1872-1878 (1994)

[Publications] T.Ogawa,T.Ikegami,T.Hikasa,H.Suzuki: "Enhanced Nucleohilicity of Tris(2,6-dimethoxyphenyl)bismuthine as Studied by X-ray Crystallography,^<17>O-NMR and Theoretical Calculation" J.Chem.Soc.Perkin Trans.1. 3479-3483 (1994)

[Publications] A.Kato,A.Sugimori: "A Novel Metallacycie 1,2,5,3-Cobaltadithiazole.Formation Structure,and Properties of (η-Cyclopentadienyl)(1-phenylmetanimine-N.1-dithiolato)cobalt" J.Org.Chem.473. 313-321 (1994)

[Publications] H.Suzuki,N.Tokitoh,S.Nagase,R.Okazaki: "The First Genuine Silicon-Sulfur Double Bond Compound:Synthesis and Crystal Stracture of a Kinetically Stabilized Silanethione" J.Am.Chem.Soc.116. 11578-11579 (1994)

[Publications] S.Koseki,H.Tomioka,A Toyata: "FORS MCSF Study on Nitrenophenyl-Methylene C_6H_4CHN" J.Phys.Chem.98. 13203-13209 (1994)

[Publications] M.Yoshifuji,: "2,4-Di-t-butyl-6-methoxyphenyldithioxophosphorane as a Probe for the Mechanistic Studies of Lawesson's Reagent" Tetrahedron Lett.35. 4379-4382 (1994)

[Publications] M.A.Sekiguchi: "Lithium and Sokium Complexes of aTetasilylethylene Dianion" Organomitallics. 14(in press). (1995)

安藤亘筑波大学, 化学系, 教授 (30008429)