1994 年度実績報告書

有機金属分子の融媒作用

研究課題

研究課題/領域番号	05236106
研究機関	早稲田大学
研究代表者	山本明夫早稲田大学, 理工学研究科, 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, 工学部, 教授 (40022644) 薗頭健吉大阪市立大学, 工学部, 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, 工学部, 教授 (40026018)
キーワード	有機金属化合物 / 触媒作用 / パラジウム / ロジウム / 不斉合成 / オレフィン
研究概要	本研究では、各種の新規な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触媒反応の素反応に関する理解を深め、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、各種のホスフィン配位子を有する一連のアルキルおよびアリールパラジウム錯体を合成し、オレフィン、CO、イソシアニド等の不飽和化合物との反応を検討した結果、カチオン性パラジウム錯体が高い反応性を示すことを見出だした。また新規ルテニウム錯体を合成しその性質を研究した。伊藤は、光学活性パラジウム錯体を触媒としてジイソシアニドベンゼンを重合させることにより、螺旋状ポリマーの合成に成功し、このポリマーを分割することによって新しい光学活性螺旋状ホスフィン配位子の合成に成功した。小宮はルテニウム錯体を用いるアルドール反応およびマイケル反応に関連して、その中間体と見なすことのできる新規のルテニウムおよび鉄エノラート錯体を合成し、反応機構に関する重要な情報を得た。薗頭は、新規のフェロセニル白金およびコバルト錯体を合成し、その触媒反応を検討した。高谷は、新規キラル配位子BINAPHOSを用いて、ロジウム錯体触媒による各種オレフィンのヒドロフォルミル化反応を行い、高い鏡像体過剰率(ee)で不斉ホルミル化を実現した。また、BINAPを不斉配位子とすオレフィンおよびアルデヒドの新規不斉還元反応を見出した。田丸は、主としてパラジウム錯体を触媒として用い、アリル亜鉛化合物との組み合わせにより、極性転換反応を利用して、各種不飽和アルコール類の選択的合成反応を開発した。

研究成果

(34件)

すべてその他

すべて文献書誌 (34件)

[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).

1994 年度 実績報告書

有機金属分子の融媒作用

研究代表者

山本 明夫 早稲田大学, 理工学研究科, 教授 (30016711)

研究成果

[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] 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).

1994 年度実績報告書

山本明夫早稲田大学, 理工学研究科, 教授 (30016711)