有機金属分子の触媒作用

• 研究課題/領域番号: 05236106
• 研究種目: 重点領域研究
• 配分区分: 補助金
• 研究機関: 早稲田大学
• 研究代表者: 山本 明夫 早稲田大学, 理工学部, 教授 (30016711)
• 研究分担者: 田丸 良直 長崎大学, 工学部, 教授 (80026319) ; 高谷 秀正 京都大学, 大学院・工学研究科, 教授 (40022644) ; 薗頭 健吉 福井工業大学, 教授 (30029847) ; 小宮 三四郎 東京農工大学, 工学部, 教授 (00111667) ; 伊藤 嘉彦 京都大学, 大学院・工学研究科, 教授 (40026018) ; 野崎 京子 京都大学, 大学院・工学研究科, 助手 (60222197)
• 研究期間 (年度): 1993 – 1996
• 研究課題ステータス: 完了 (1996年度)
• 配分額: 68,800千円 (直接経費: 68,800千円); 1995年度: 23,400千円 (直接経費: 23,400千円); 1994年度: 23,400千円 (直接経費: 23,400千円); 1993年度: 22,000千円 (直接経費: 22,000千円)
• キーワード: 有機金属化合物 / 触媒作用 / パラジウム / オレフィン / 配位子 / 不斉合成 / ルテニウム / 白金 / 一酸化炭素 / カルボニル化 / ロジウム

研究概要

本研究では、触媒反応の活性種のモデルとなるような各種の有機遷移金属錯体を合成し、その化学的性質を調べることにより、既知の触媒反応の機構に関する理解を深めると共に、新規触媒反応を開発することを目的として研究を行った。山本は各種のホスフィン及びホスファイトを配位子とする中性及びカチオン性の有機パラジウム及びルテニウム錯体を合成し、これら錯体のオレフィン、一酸化炭素、イソシアニド等不飽和化合物に対する反応性を研究し、配位不飽和な錯体の性質が反応性に及ぼす影響を明かにすると共に、パラジウム錯体を用いる、アルコール類の新しいカルボニル化反応、イミン類の還元反応を見出し、その反応機構を明かにした。伊藤は、安定な螺旋構造を有するパラジウム錯体を合成し、螺旋型ポリマーの液晶としての性質等を研究した。小宮は、C-H結合の活性化により活性なルテニウム錯体を合成し、触媒的C-C結合生成反応の機構に関する知見を得た。薗頭は、フェロセニル型配位子を有する新規白金錯体を合成してその反応を研究すると共に、ジアルキニルフェロセンの触媒的カルボニル化反応を開発した。故高谷および野崎は、キラルホスフィンホスファイト配位子を有するパラジウム錯体を用いプロピレンと一酸化炭素からイソタクチックポリケトンを合成することに成功した。田丸は、パラジウム錯体を触媒として用い、有機亜鉛化合物との組み合わせにより不飽和アルコール類を合成する新規な方法を開発した。

研究成果

• [文献書誌] A.Yamamoto: "Activation of C-O and C-N Bondsin Allylic Alchols and Amines by Palladium Complexes Promoted by CO_2.Synthetic Application to Allylation of Nucleophiles,Carbonylation,and Allylamine" Bull.Chem.Soc.Jpn.69. 1065-1078 (1996)
  • 説明: 「研究成果報告書概要(和文)」より
• [文献書誌] Y.Ito: "New Synthesis of(E)-Allylsilanes with High Enantiopurity Via Diastereoselective Intramolecular Bis-Silylation of Chiral Allylic Alcohols" J.Am.Chem.Soc.118. 3061-3062 (1996)
  • 説明: 「研究成果報告書概要(和文)」より
• [文献書誌] S.Komiya: "Synthesis and Reactivity of Organoplatinum-rhenium Heterobimetallic Complexes Having Sulfur Ligands" J.Mol.Cat.107. 323-328 (1996)
  • 説明: 「研究成果報告書概要(和文)」より
• [文献書誌] K.Sonogashira: "Reactions of σ-Ferrocenylplatinum Complexes with Carbon Monoxide and Isocyanide" J.Organometal.Chem.511. 47-57 (1996)
  • 説明: 「研究成果報告書概要(和文)」より
• [文献書誌] H.Takaya: "Palladium-Catalyzed Acylcyanation of Terminal Arylacetylenes.Synthesis of 1,3-Diaryl-3-cyano-2-propen-1-ones and Tetrasubstituted Furans" Bull.Chem.Soc.Jpn.69. 1629-1637 (1996)
  • 説明: 「研究成果報告書概要(和文)」より
• [文献書誌] Y.Tamaru: "Propargylation of Carbonyl Compounds via Umpolung of Propargylpalladium with Diethylzinc" Angew.Chem.,Int.Ed.Engl.35. 878-880 (1996)
  • 説明: 「研究成果報告書概要(和文)」より
• [文献書誌] A.Yamamoto: "Activation of C-O and C-N Bonds in Allylic Alchols and Amines by Palladium Complexes Promoted by CO_2. Synthetic Application to Allylation of Nucleophiles, Carbonylation, and Allylamine Disproportionation" Bull.Chem.Soc.Jpn.69. 1065-1078 (1996)
  • 説明: 「研究成果報告書概要(欧文)」より
• [文献書誌] Y.Ito: "New Synthesis of (E) -Allylsilanes with High Enantiopurity via Diastereoselective Intramolecular Bis-Silylation of Chiral Allylic Alcohols" J.Am.Chem.Soc.118. 3061-3062 (1996)
  • 説明: 「研究成果報告書概要(欧文)」より
• [文献書誌] S.Komiya: "Synthesis and Reactivity of Organoplatinum-rhenium Heterobimetallic Complexes Having Sulfur Ligands" J.Mol.Cat.107. 323-328 (1996)
  • 説明: 「研究成果報告書概要(欧文)」より
• [文献書誌] K.Sonogashira: "Reactions of sigma-Ferrocenylplatinum Complexes with Carbon Monoxide and Isocyanide" J.Organometal.Chem.511. 47-57 (1996)
  • 説明: 「研究成果報告書概要(欧文)」より
• [文献書誌] H.Takaya: "Palladium-Catalyzed Acylcyanation of Terminal Arylacetylenes. Synthesis of 1,3-Diaryl-3-cyano-2-propen-1-ones and Tetrasubstituted Furans" Bull.Chem.Soc.Jpn.69. 1629-1637 (1996)
  • 説明: 「研究成果報告書概要(欧文)」より
• [文献書誌] Y.Tamaru: "Propargylation of Carbonyl Compounds via Umpolung of Propargylpalladium with Diethylzinc" Angew.Chem.Int.Ed.Engl.35. 878-880 (1996)
  • 説明: 「研究成果報告書概要(欧文)」より
• [文献書誌] A.Yamamoto: "Activation of C-O and C-N Bonds in Allylic Alcohols and Amines by Palladium Complexes Promoted by CO_2. Synthetic Applications to Allylation of Nucleophiles, Carbonylation, and Allylamine Disproportionation." Bull. Chem. Soc. Jpn.(in press). (1996)
• [文献書誌] Y. Ito: "New Synthesis of Quinoxaline Derivatives Based on Palladium Catalyzed Oligomerization of 1,2-Diisocyanoarenes." Heterocycles,. 42. 597-615 (1996)
• [文献書誌] K. Sonogashira: "Reaction of 1,1'-Ferrocenediylbis [chloro{(1,2,5,6-η)-1,5-cyclooctadiene} -platinum] with Triarylphosphine and Molecular Oxygen." Angew. Chem. Int. Ed. Engl.34. 319-321 (1995)
• [文献書誌] S. Komiya: "Synthesis and Reactivity of Organoplatinum-rhenium Heterobimetallic Complexes Having Sulfur Ligand." J. Mol. Catal.(in press). (1996)
• [文献書誌] K. Nozaki: "Asymmetric Hydroformylation of Conjugated Dienes Catalyzed by [(R)-2-diphenylphosphino-1, 1'-din aphthalen-2'-yl] [(S)-1, 1'-dinaphthalen-2, 2'-diyl] phosphite-rhodium (I)." Chem. Commun.155-156 (1996)
• [文献書誌] Y. Tamaru: "π-アリルパラジウムとの反応における有機亜鉛の特異な反応挙動:カルボニル化による非対称ケトンの合成とπ-アリルパラジウムの極性転換反応" 有機合成化学協会誌. 53. 1102-1113 (1995)
• [文献書誌] Futoshi Kawataka: "Synthesis and Thermolysis Behavior of Monoethylpalladium Complexes,EtPd(X)(PMe3)2(X=Electronegative Ligands)" Organometallics. 13. 3517-3524 (1994)
• [文献書誌] Yoshihiko Kayaki: "Remarkable Rate Enhancement in CO Insertion into Pd-C Bond by Generating Cationic Organopalladium Complexes 〔PdR(s)L2〕+BF4-(R=Alky1 Group,s=Acctone,L=Phosphine Ligands)form Neutral Monoorganopalladium Complexes 〔PdR(X)L2〕(X=Halide)" Chem.Lett.2171-2174 (1994)
• [文献書誌] Thomas Rappert: "Synthesis of Cationic Imine- and Amine-Coordinated Hydridoruthenium Complexes Relevant to Reductive Amination" Chem.Lett.2211-2214 (1994)
• [文献書誌] Thomas Rappert: "Synthesis and Properties of Cationic Hydrido(tertiary phosphine)ruthenium(II)Complex" Organometallics. 13. 4984-4993 (1994)
• [文献書誌] Akio Yamamoto: "Palladium-Catalyzed Double and Single Carbonylation of Aryl Halides and Allylic Comounds" Bull.Chem.Soc.Jpn.68. 433-446 (1995)
• [文献書誌] Futoshi Kawataka: "Synthesis and Properties of Cationic Organopalladium Complexes.Remarkable Rate Enhancement in Olefin Insertion into Paladium-Aryl Bond by Generation of a Cationic Palladium Complex from trans-PdPh(Br)(PMe3)2" Bull.Chem.Soc.Jpn.68. 654-660 (1995)
• [文献書誌] K.Onitsuka: "Synthesis and Properties of Ferrocenylethynyl Transition Metal Complex of Platinum,Palladium and Nickel" Bull.Chem.Soc.Jpn.67. 2611-2613 (1994)
• [文献書誌] K.Onitsuka: "Synthesis,and Molecular Structure and Reactions of a Novel μ-σ、π-Cyclopentadienediyl Platinum-Manganese Complex" Chem.Lett. 2067-2070 (1994)
• [文献書誌] K.Onitsuka: "Synthesis and Structure of Novel Metallacycle Complexes of Ruthenium Derived from 1,1'-Dialkynylferrocene" Chem.Lett. 2276-2282 (1994)
• [文献書誌] T.Yoshida: "Reaction of 1,1'-Ferrocenediylbis〔chloro-{(1,2,5,6-η)-1,5-cyclolctadiene}plantinum〕with Triarvlphosphane and Molecular Oxygen" Angew.Chem.Int.Ed.Engl.34. 319-321 (1995)
• [文献書誌] K.Onitsuka: "Insertion reaction of isocyanide into the Pt-C bonds of 2,5-thicnylene-bridged diplatium complexes and 2-thienyl platinum complexes:molecular structure of Cl(Et_3P)_2PtC=(NC_6H_4OMe-p)C_4H_2SC=(NC_6H_4OMe-p)Pt(PEt_3)_2ClCH_2Cl_2" J.Organomet.Chem. (in press). (1994)
• [文献書誌] K.Onitsuka: "C-H Bond Activation of the Ferrocenyl Group in the Reaction of σ-Ferrocenylplatinum Complex with Dimethyl Acetylenedicarboxylate" Chem.Lett. (in press). (1994)
• [文献書誌] S.Komiya: "C-O Bond Cleavage and Oxidative Addition of Allyl Carboxylate to Ruthenium(O).Isolation of (π-allyl)(trifluoroacetato)tris(triethylphosphine)rutheium(II)" J.Organometa.Chem. 471. C6-C7 (1994)
• [文献書誌] A.Fukuoka: "Synthesis and Structure of Heterodinuclear Platimum-Tungsten and-Molybdenum Complexes with Alkyl and Ligands:A Mechanistic Study of the Migration of Alkyl and Groups from Platinum to Tungsten and Molybdenum" Organometallics. 13. 4033-4044 (1994)
• [文献書誌] S.Komiya: "Synthesis and Structure of a Carbon Dioxide Complex of Iron(O)Containing 1,2-Bis(diethylphosphino)ethane Ligands" J.Chem.Soc.,Chem.Commun.1114-1116 (1994)
• [文献書誌] A.Fukuoka: "Synthesis and Structure of Novel Organo(siloxo)platimum Complexes.Facile Reduction by Dihydrogen." Chem.Lett.1641-1644 (1994)
• [文献書誌] T.Sone: "Synthesis,Structure and Reactivities of cis-Dimethyl(ηl-allyl)gold(III)Complexes." Bull.Chem.Jpn. (in press).
• [文献書誌] S.Komiya: "Organometallic Dinuclear Complexes of Transition Metals.Alkyl Transfer from Platinum,Palladium and Gold to Transition Metals" Trends in Organometallic Chemistry. (in press).
• [文献書誌] M.Suginome: "Syntheses and Interconvertion of 〔Bis(silyl)alkene〕palladium(O)and Bis(silyl)palladium(II)Complex:A Mechanistic Model for Palladium-Catalyzed Bis(silylation)" Organometallics. 13. 2900-2902 (1994)
• [文献書誌] M.Suginome: "Novel Activation of Two Si-Si s-Bonds in a Molecule by tert-Alkyl Isocyanide-Palladium Complex" Organometallics. 13. 4148-4150 (1994)
• [文献書誌] M.Hada: "Palladium-Catalyzed Intermolecular Cyanosilylation of Alkynes Leading to Stereoselective Syntheses of α,β-Unsaturated Nitriles" Tetrahedron Lett.35. 8635-8638 (1994)
• [文献書誌] M.Hada: "Theoretical Study on the Reaction Mechanism and Redioselectivity of Silastannation of Acetvlenes with a Palladium Catalvst" J.Am.Chem.Soc.116. 8754-8765 (1994)
• [文献書誌] K.Nozaki: "A Chiral Bimetallic Lewis Acid:A Cooperative Binding of Two Amine Molecules to a Chiral Diboronic Ester." Angew.Chem,Int.Ed.Engl.33. 2452-2454 (1994)
• [文献書誌] K.Nozaki: "Acylcyanation of Terminal Acetylenes:Palladium Catalyzed Addition of Aryloyl Cyanides to Aryl acetylenes" J.Org.Chem.59. 2679-2681 (1994)
• [文献書誌] K.Mashima: "Cationic BINAP-Ru(II)Halide Complexes:Highly Efficient Catalysts for Strereoselective Asymmetric Hydrogenation of a-and β-Functionalized Ketones" J.Org.Chem.59. 3064-3076 (1994)
• [文献書誌] X.Zhang: "Enatioselective Hydrogenation of Acyclic Aromatic Ketones Catalyzed by BINAP-Ir(I)-Aminophosphine Systems" Tetrahedron Asymmetry. 5. 1179-1182 (1994)
• [文献書誌] R.Yamaguchi: "Facile Introduction of Michael Acceptors into Nitrogen Heterocycles.A New Efficient Route to Fused α-Methylene-γ-lactams" Chem.Lett.1809-1812 (1994)
• [文献書誌] X.Zhang: "Highly Enantioselective Hydrogenation of α、β-Unsaturated Carboxylic Acids Catalyzed by H8-BINAP-Ru(II)Complexes" Synlett. 501-503 (1994)
• [文献書誌] K.Ono: "Palladium Catalyzed Arylation of N-Alkyl 0-Aryl Carbamates:Synthesis of Cinnamyl Alcohols via Heck Arylation" Tetrahedron Lett.35. 4133-4136 (1994)
• [文献書誌] Y.Tamaru: "Highly Regio-and Strereoselective Diels-Alder Reaction of Monothiomaleimide,an Ambident C=S and C=C Dienophile" J.Chem.Soc.,Chem,Commun.2365-2366 (1994)
• [文献書誌] M.Kimura: "Palladium(2+)catalyzed 5-Endo-Trigonal Cyclization of 2-Hydroxy-3-butenylamines:Synthesis of Five-Membered Nitrogen Heterocycles" J.Chem.Soc.,Chem,Commun.2531-2533 (1994)
• [文献書誌] Y.Tamaru: "Convenient Synthesis of 4-Methylene-1,3-oxazolidin-2-ones and 4-Methylene-1,3-oxazin-2-ones via Transition-metal Catalyzed Intramolecular Addition of Nitrogen Atom to Acetylenic Triple Bond" Bull.Chem.Soc.Jpn.67. 2838-2849 (1994)
• [文献書誌] M.Kimura: "Silver(I)Catalyzed Aminocylization of 2,3-Butadienyl and 3,4-Pentadienyl Carbamates:An Efficient and Stereoselective Synthesis of 4-Vinyl-2-oxazolidinones and 4-Vinyltetrahydro-1,3-oxazin-2-ones" Bull.Chem.Soc.Jpn.(in press).
• [文献書誌] Y.Tamura: "Highly Stereoselective Allylation of Aldehyde:Generation of Stereochemically Defined Allylzinc Species via Alky-Allyl Exchange Reaction between π-Allylpalladium and Diethylzinc" Bull.Chem.Soc.Jpn.(in press).
• [文献書誌] Isao Shimizu: "Palladium-Catalyzed Reactions of Alkenyloxiranes with Carbon Monoxides" Tetrahedron Lett.,34. 13. 2135-2138 (1993)
• [文献書誌] Radhey S.Srivastava: "Synthesis,characterization,and carbonylation reactions of methylpalladium amide,carbamate,and alkyl carbonate complexes" J.Organomet.Chem.,451. 221-229 (1993)
• [文献書誌] Yoo-Joo Kim: "Preparation and properties of alkyl palladium(II) and -platinum(II) alkynyl complexes" Chem.Lett.247-250 (1993)
• [文献書誌] Masato Sakamoto: "Synthesis of the First Carbon Dioxide Coordinated Palladium(0) complexes,Pd(eta^2-CO_2)(PMePh_2)_2" Organometallics,13. 407-409 (1994)