1993 Fiscal Year Annual Research Report

有機典型金属分子の創製

Research Project

Project/Area Number	05236102
Research Institution	The University of Tokyo
Principal Investigator	岡崎廉治東京大学, 大学院・理学系研究科, 教授 (70011567)
Co-Investigator(Kenkyū-buntansha)	山本陽介広島大学, 理学部, 助教授 (50158317) 右田俊彦東海大学, 開発工学部, 教授 (40008412) 細見彰筑波大学, 化学系, 教授 (00004440) 馬場章夫大阪大学, 工学部, 助教授 (20144438) 野依良治名古屋大学, 理学部, 教授 (50022554)
Keywords	速度論的安定化 / 不斉触媒反応 / 高配位化合物 / 有機ゲルマニウム化合物 / オルトキノジメタン / 有機ビスマス化合物
Research Abstract	本研究では12-15族の典型金属について下記の研究を行った。 (1)新たに開発したかさ高い置換基2,4,6-トリス[ビス(トリメチルシリル)メチル]フェニル基(Tb基)の速度論的安定化を利用し、新規環状ポリスルフィドTb(Tip)MS_4(Tip=2,4,6-トリイソプロピルフェニル;M=Ge,Sn)を合成した。また、そのPh_3Pによる脱硫により、Tb(Tip)M=S(M=Sn,Ge)を初めて安定に合成した(岡崎)。(2)光学活性な三級アミノアルコールである3-exo-ジメチルアミノイソボルネオールを用いるジアルキル亜鉛によるアルデヒド類の触媒的不斉アルキル化反応において、不斉源の鏡像体過剰率とエンチオ面選択性との間に観測される特異な非線形現象を定量的に考察した(野依)。(3)スズ-酸素結合を有する化合物の新しい活性化法を見出し、特に高配位スズエノラートを中心に合成化学分野への新規応用を可能とした。また、有機インジウムとリン、ヒ素、あるいは硫黄の錯体を各種合成し、優れた電気的特性を有する新薄膜製造方法を提案した(馬場)。(4)常法では得難く、単離が難しい高反応性の反応中間体を合成等価体として利用できる有機ケイ素反応剤として、メチル(トリメチルシリルメチル)アセチレンカルボキシラートの合成を行い、含複素環オルトキノジメタンの新規合成反応剤となることを明らかにした(細見)。(5)いくつかの1-アザ-5-ゲルマ-5-オルガノビシクロ[3.3.3]ウンデカンはPd触媒存在下ハロゲン化物とカップリング反応を行なうこと、またアリルトリブチルゲルマンはアリルスズ化合物と同様にAIBN存在下、陰性基をもつハロゲン化物のハロゲンをアリル基で置換しうることを明らかにした(右田)。(6)2座配位子ヘキサフルオロクミルアルコールリガンドの導入により、熱的に安定な6配位ビスマスアニオンを合成した。また、アニオンと水の反応で生じた6配位アルコールは室温では速やかに炭化水素脱離反応を起こすことを見出し、その脱離しやすさの置換基効果を検討した(山本)。

Research Products

(34 results)

All Other

All Publications (34 results)

[Publications] K.Shibata: "Formation and Reactions of a Kinetically Stabilized Diaryl-plumbylene" Tetrahedron Lett.34. 1495-1498 (1993)
[Publications] K.Shibata: "X-ray Structural Analysis of Hexakis[2-(3,5-di-t-butylphenyl)-2-methylpropyl]diplumbane" Tetrahedron Lett.34. 1499-1500 (1993)
[Publications] R.Okazaki: "Synthesis of Small-ring Sulfur Compounds Containing Germanium and Tin" Phosphorus,Sulfur,and Silicon. 74. 397-398 (1993)
[Publications] N.Tokitoh: "The First Stable 1,2-Thiastannete and 1,2-Selenastannete:Their Syntheses and Crystal Structures" J.Chem.Soc.,Chem.Commun.407-409 (1993)
[Publications] N.Tokitoh: "The First Stable Stannanethione in Solution Derived from a Kinetically Stabilized Diarystannylene" J.Am.Chem.Soc.115. 2065-2066 (1993)
[Publications] Y.Matsuhashi: "Synthesis and Structure of 1,2,3,4,5-Tetrachalcogenastannolanes" Organometallics.12. 1351-1358 (1993)
[Publications] Y.Matsuhashi: "Formation and Reactions of Stannanethiones and Stannaneselones" Organometallics. 12. 2573-2583 (1993)
[Publications] N.Tokitoh: "Synthesis of Novel Metal-Chalcogen Mixed Clusters by the Reactions of 1,2,3,4,5-Tetrachalcogenastannolanes with Os_2(CO)_<12>:The First Examples of Transition-Metal Complexes Bridged by Stannanethione and Stannaneselone" Organometallics. 12. 2894-2896 (1993)
[Publications] N.Tokitoh: "Synthesis and Crystal Structure of the First Stable Diaryl-germanethione" J.Am.Chem.Soc.115. 8855-8856 (1993)
[Publications] N.Tokitoh: "Synthesis,Structure,and Reactivity of Extremely Hindered Disilenes:The First Example of Thermal Dissociation of a Disilene into a Silylene" J.Am.Chem.Soc.115. 10428-10429 (1993)
[Publications] 野依良治: "不斉触媒の自己および非自己認識" 化学増刊. 123. 35-42 (1993)
[Publications] 野依良治: "不斉触媒反応とエナンチオマーの相互認識" 現代化学増刊. 21. 233-250 (1992)
[Publications] I.Shibata: "Double Alkylation of Tin Enolate Derived from Diketene and Bis-(tributyltin)Oxide" Chem.Lett.1953-1956 (1993)
[Publications] I.Shibata: "Novel Michael Addition Promoted by Tributylstannylcarbamate.Synthesis of Diacylcyclopropanes" Tetrahedron Lett.(in press).
[Publications] M.Yasuda: "Chemoselective Coupling of α-Bromo Aldehydes with a Tin Enolete Derived from the Ring Opening of Diketene by Bis(tributyltin)Oxide" J.Org.Chem.(in press).
[Publications] R.Nomora: "Alternative Single-source Precursor for Growth of Indium Pnictide Thin Layers" J.Mater.Chem.(in press).
[Publications] M.Hojo: "Synthesis and Reactions of Methyl(Trimethylsilylmethyl)acetylenecarboxylate.A General Method for the Generation of Di-exo-methyleneisoxazolines and Novel Access to Fused" Tetrahedron Lett.34. 485-488 (1993)
[Publications] C.Kashima: "Synthesis of β-Keto Esters by the Reformatsky Reaction of 3-Acyloxazolidin-2-onos and-thiazolidine-2-thiones" J.Org.Chem.58. 793-794 (1993)
[Publications] C.Kashima: "Preparation of Sterically More Crowded 1,5-Disubstituted Imidazoles by the Regioselective N-Alkylation" Heterocycles. 35. 433-440 (1993)
[Publications] T.Nishio: "Photochemical Reactions of Benzothiazole-2-thiones" J.Chem.Soc.,Perkin Trans 1. 2197-2200 (1993)
[Publications] M.Hojo: "A New Access to Carbonyl Ylides by the Silicon-Based 1,3-Elimination and their[3+2]Cycloadditions to Alkenes and Alkynes:One-Step Synthesis of Dihydrofurans and Tetrahydrofurans" Tetrahedron Lett.34. 5943-5946 (1993)
[Publications] H.Aoyama: "A Novel Synthesis of 4-Spirocyclopropyl b-Lactams" Tetrahedron Lett.34. 5951-5952 (1993)
[Publications] M.Hojo: "Samarium Diiodide-Promoted Reductive Cleavage of Carbon-Sulfur Bond:A Novel Stereo-selective Generation of Functionalized Vinylsamarium Species and Synthesis of β-Thiobutenolides" J.Org.Chem.58. 6541-6542 (1993)
[Publications] M.Hojo: "New Access to Di-exo-methylenecyclobutanes via[2+2]Cycloaddition of 3-Methylthio-4-trimethylsilylmethyl-1,2-butadiene with Alkenes Mediated by a Lewis Acid" Tetrahedron Lett.34. 8123-8126 (1993)
[Publications] C.Kashima: "Stereoselective N-Acylation of a New Chiral Auxiliary Compound;3-Phenyl-1-menthopyrazole" Tetrahedron Lett.34. 8305-8308 (1993)
[Publications] M.Kosugi: "Palladium Catalyzed Consecutive One-Pot Reaction of Acetylenes with Allyl Bromide and Organotin Compounds" Bull.Chem.Soc.Japan. 66. 3058-3061 (1993)
[Publications] M.Kosugi: "Synthesis of cis-Olefins via Palladium-Catalyzed Coupling of Organic Halides,Norbornene,and Organotin Compounds" Bull.Chem.Soc.Japan. 66. 3522-3524 (1993)
[Publications] T.Nakano: "A Convenient Synthesis of α,α'-Bis(substitutedbenzylidene)cycloalkanones" Chem.Lett.2157-2158 (1993)
[Publications] X.Chen: "Synthesis,Halogenolysis,and Crystal Structure of.Hypervalent Organobismuth Compounds(10-Bi-5)" Organometallics. 12. 1857-1864 (1993)
[Publications] Y.Yamamoto: "Synthesis and Structure of Six-Coordinated Organobismuth Compounds with Bidentate Ligands(12-Bi-6)" Organometallics. 12. 3297-3303 (1993)
[Publications] K.-y.Akiba: "[4+2]Type Cycloaddition of Aldimines Bearing α-Hydrogens with 2-Siloxy-1,3-butadienes Catalyzed by Trimethylsily Triflate" Synlett.657-659 (1993)
[Publications] S.Yoshida: "Crystal and Molecular Structures of Bismuth Compounds of a Spiro-o-Sulfuran Type" Acta Crystallographica,Sect.B. (in press).
[Publications] K.-y Akiba: "Syntheses of Organoantimony and Organobismuth Compounds" The Chemistry of Organic Arsenic,Antimony and Bismuth Compounds,ed by S.Patai,John Wiley and Sons. (in press).
[Publications] Y.Yamamoto: "Syntheses of Organoarsenic Compounds" The Chemistry of Organic Arsenic,Antimony and Bismuth Compounds,ed by S.Patai,John Wiley and Sons. (in press).

1993 Fiscal Year Annual Research Report

有機典型金属分子の創製

Principal Investigator

岡崎 廉治 東京大学, 大学院・理学系研究科, 教授 (70011567)

Research Products

[Publications] K.Shibata: "Formation and Reactions of a Kinetically Stabilized Diaryl-plumbylene" Tetrahedron Lett.34. 1495-1498 (1993)

[Publications] K.Shibata: "X-ray Structural Analysis of Hexakis[2-(3,5-di-t-butylphenyl)-2-methylpropyl]diplumbane" Tetrahedron Lett.34. 1499-1500 (1993)

[Publications] R.Okazaki: "Synthesis of Small-ring Sulfur Compounds Containing Germanium and Tin" Phosphorus,Sulfur,and Silicon. 74. 397-398 (1993)

[Publications] N.Tokitoh: "The First Stable 1,2-Thiastannete and 1,2-Selenastannete:Their Syntheses and Crystal Structures" J.Chem.Soc.,Chem.Commun.407-409 (1993)

[Publications] N.Tokitoh: "The First Stable Stannanethione in Solution Derived from a Kinetically Stabilized Diarystannylene" J.Am.Chem.Soc.115. 2065-2066 (1993)

[Publications] Y.Matsuhashi: "Synthesis and Structure of 1,2,3,4,5-Tetrachalcogenastannolanes" Organometallics.12. 1351-1358 (1993)

[Publications] Y.Matsuhashi: "Formation and Reactions of Stannanethiones and Stannaneselones" Organometallics. 12. 2573-2583 (1993)

[Publications] N.Tokitoh: "Synthesis of Novel Metal-Chalcogen Mixed Clusters by the Reactions of 1,2,3,4,5-Tetrachalcogenastannolanes with Os_2(CO)_<12>:The First Examples of Transition-Metal Complexes Bridged by Stannanethione and Stannaneselone" Organometallics. 12. 2894-2896 (1993)

[Publications] N.Tokitoh: "Synthesis and Crystal Structure of the First Stable Diaryl-germanethione" J.Am.Chem.Soc.115. 8855-8856 (1993)

[Publications] N.Tokitoh: "Synthesis,Structure,and Reactivity of Extremely Hindered Disilenes:The First Example of Thermal Dissociation of a Disilene into a Silylene" J.Am.Chem.Soc.115. 10428-10429 (1993)

[Publications] 野依良治: "不斉触媒の自己および非自己認識" 化学増刊. 123. 35-42 (1993)

[Publications] 野依良治: "不斉触媒反応とエナンチオマーの相互認識" 現代化学増刊. 21. 233-250 (1992)

[Publications] I.Shibata: "Double Alkylation of Tin Enolate Derived from Diketene and Bis-(tributyltin)Oxide" Chem.Lett.1953-1956 (1993)

[Publications] I.Shibata: "Novel Michael Addition Promoted by Tributylstannylcarbamate.Synthesis of Diacylcyclopropanes" Tetrahedron Lett.(in press).

[Publications] M.Yasuda: "Chemoselective Coupling of α-Bromo Aldehydes with a Tin Enolete Derived from the Ring Opening of Diketene by Bis(tributyltin)Oxide" J.Org.Chem.(in press).

[Publications] R.Nomora: "Alternative Single-source Precursor for Growth of Indium Pnictide Thin Layers" J.Mater.Chem.(in press).

[Publications] M.Hojo: "Synthesis and Reactions of Methyl(Trimethylsilylmethyl)acetylenecarboxylate.A General Method for the Generation of Di-exo-methyleneisoxazolines and Novel Access to Fused" Tetrahedron Lett.34. 485-488 (1993)

[Publications] C.Kashima: "Synthesis of β-Keto Esters by the Reformatsky Reaction of 3-Acyloxazolidin-2-onos and-thiazolidine-2-thiones" J.Org.Chem.58. 793-794 (1993)

[Publications] C.Kashima: "Preparation of Sterically More Crowded 1,5-Disubstituted Imidazoles by the Regioselective N-Alkylation" Heterocycles. 35. 433-440 (1993)

[Publications] T.Nishio: "Photochemical Reactions of Benzothiazole-2-thiones" J.Chem.Soc.,Perkin Trans 1. 2197-2200 (1993)

[Publications] M.Hojo: "A New Access to Carbonyl Ylides by the Silicon-Based 1,3-Elimination and their[3+2]Cycloadditions to Alkenes and Alkynes:One-Step Synthesis of Dihydrofurans and Tetrahydrofurans" Tetrahedron Lett.34. 5943-5946 (1993)

[Publications] H.Aoyama: "A Novel Synthesis of 4-Spirocyclopropyl b-Lactams" Tetrahedron Lett.34. 5951-5952 (1993)

[Publications] M.Hojo: "Samarium Diiodide-Promoted Reductive Cleavage of Carbon-Sulfur Bond:A Novel Stereo-selective Generation of Functionalized Vinylsamarium Species and Synthesis of β-Thiobutenolides" J.Org.Chem.58. 6541-6542 (1993)

[Publications] M.Hojo: "New Access to Di-exo-methylenecyclobutanes via[2+2]Cycloaddition of 3-Methylthio-4-trimethylsilylmethyl-1,2-butadiene with Alkenes Mediated by a Lewis Acid" Tetrahedron Lett.34. 8123-8126 (1993)

[Publications] C.Kashima: "Stereoselective N-Acylation of a New Chiral Auxiliary Compound;3-Phenyl-1-menthopyrazole" Tetrahedron Lett.34. 8305-8308 (1993)

[Publications] M.Kosugi: "Palladium Catalyzed Consecutive One-Pot Reaction of Acetylenes with Allyl Bromide and Organotin Compounds" Bull.Chem.Soc.Japan. 66. 3058-3061 (1993)

[Publications] M.Kosugi: "Synthesis of cis-Olefins via Palladium-Catalyzed Coupling of Organic Halides,Norbornene,and Organotin Compounds" Bull.Chem.Soc.Japan. 66. 3522-3524 (1993)

[Publications] T.Nakano: "A Convenient Synthesis of α,α'-Bis(substitutedbenzylidene)cycloalkanones" Chem.Lett.2157-2158 (1993)

[Publications] X.Chen: "Synthesis,Halogenolysis,and Crystal Structure of.Hypervalent Organobismuth Compounds(10-Bi-5)" Organometallics. 12. 1857-1864 (1993)

[Publications] Y.Yamamoto: "Synthesis and Structure of Six-Coordinated Organobismuth Compounds with Bidentate Ligands(12-Bi-6)" Organometallics. 12. 3297-3303 (1993)

[Publications] K.-y.Akiba: "[4+2]Type Cycloaddition of Aldimines Bearing α-Hydrogens with 2-Siloxy-1,3-butadienes Catalyzed by Trimethylsily Triflate" Synlett.657-659 (1993)

[Publications] S.Yoshida: "Crystal and Molecular Structures of Bismuth Compounds of a Spiro-o-Sulfuran Type" Acta Crystallographica,Sect.B. (in press).

[Publications] K.-y Akiba: "Syntheses of Organoantimony and Organobismuth Compounds" The Chemistry of Organic Arsenic,Antimony and Bismuth Compounds,ed by S.Patai,John Wiley and Sons. (in press).

[Publications] Y.Yamamoto: "Syntheses of Organoarsenic Compounds" The Chemistry of Organic Arsenic,Antimony and Bismuth Compounds,ed by S.Patai,John Wiley and Sons. (in press).

岡崎廉治東京大学, 大学院・理学系研究科, 教授 (70011567)