1994 Fiscal Year Annual Research Report

有機金属分子の融媒作用

Research Project

Project/Area Number	05236106
Research Institution	Waseda University
Principal Investigator	山本明夫早稲田大学, 理工学研究科, 教授 (30016711)
Co-Investigator(Kenkyū-buntansha)	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)
Keywords	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
Research Abstract	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。

Research Products

(34 results)

All Other

All Publications (34 results)

[Publications] Futoshi Kawataka: "Synthesis and Thermolysis Behavior of Monoethylpalladium Complexes,EtPd(X)(PMe3)2(X=Electronegative Ligands)" Organometallics. 13. 3517-3524 (1994)
[Publications] 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)
[Publications] Thomas Rappert: "Synthesis of Cationic Imine- and Amine-Coordinated Hydridoruthenium Complexes Relevant to Reductive Amination" Chem.Lett.2211-2214 (1994)
[Publications] Thomas Rappert: "Synthesis and Properties of Cationic Hydrido(tertiary phosphine)ruthenium(II)Complex" Organometallics. 13. 4984-4993 (1994)
[Publications] Akio Yamamoto: "Palladium-Catalyzed Double and Single Carbonylation of Aryl Halides and Allylic Comounds" Bull.Chem.Soc.Jpn.68. 433-446 (1995)
[Publications] 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)
[Publications] K.Onitsuka: "Synthesis and Properties of Ferrocenylethynyl Transition Metal Complex of Platinum,Palladium and Nickel" Bull.Chem.Soc.Jpn.67. 2611-2613 (1994)
[Publications] K.Onitsuka: "Synthesis,and Molecular Structure and Reactions of a Novel μ-σ、π-Cyclopentadienediyl Platinum-Manganese Complex" Chem.Lett. 2067-2070 (1994)
[Publications] K.Onitsuka: "Synthesis and Structure of Novel Metallacycle Complexes of Ruthenium Derived from 1,1'-Dialkynylferrocene" Chem.Lett. 2276-2282 (1994)
[Publications] 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)
[Publications] 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)
[Publications] 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)
[Publications] 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)
[Publications] 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)
[Publications] 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)
[Publications] A.Fukuoka: "Synthesis and Structure of Novel Organo(siloxo)platimum Complexes.Facile Reduction by Dihydrogen." Chem.Lett.1641-1644 (1994)
[Publications] T.Sone: "Synthesis,Structure and Reactivities of cis-Dimethyl(ηl-allyl)gold(III)Complexes." Bull.Chem.Jpn. (in press).
[Publications] S.Komiya: "Organometallic Dinuclear Complexes of Transition Metals.Alkyl Transfer from Platinum,Palladium and Gold to Transition Metals" Trends in Organometallic Chemistry. (in press).
[Publications] 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)
[Publications] M.Suginome: "Novel Activation of Two Si-Si s-Bonds in a Molecule by tert-Alkyl Isocyanide-Palladium Complex" Organometallics. 13. 4148-4150 (1994)
[Publications] M.Hada: "Palladium-Catalyzed Intermolecular Cyanosilylation of Alkynes Leading to Stereoselective Syntheses of α,β-Unsaturated Nitriles" Tetrahedron Lett.35. 8635-8638 (1994)
[Publications] 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)
[Publications] 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)
[Publications] K.Nozaki: "Acylcyanation of Terminal Acetylenes:Palladium Catalyzed Addition of Aryloyl Cyanides to Aryl acetylenes" J.Org.Chem.59. 2679-2681 (1994)
[Publications] 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)
[Publications] X.Zhang: "Enatioselective Hydrogenation of Acyclic Aromatic Ketones Catalyzed by BINAP-Ir(I)-Aminophosphine Systems" Tetrahedron Asymmetry. 5. 1179-1182 (1994)
[Publications] 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)
[Publications] X.Zhang: "Highly Enantioselective Hydrogenation of α、β-Unsaturated Carboxylic Acids Catalyzed by H8-BINAP-Ru(II)Complexes" Synlett. 501-503 (1994)
[Publications] K.Ono: "Palladium Catalyzed Arylation of N-Alkyl 0-Aryl Carbamates:Synthesis of Cinnamyl Alcohols via Heck Arylation" Tetrahedron Lett.35. 4133-4136 (1994)
[Publications] 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)
[Publications] 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)
[Publications] 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)
[Publications] 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).
[Publications] 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 Fiscal Year Annual Research Report

有機金属分子の融媒作用

Principal Investigator

山本 明夫 早稲田大学, 理工学研究科, 教授 (30016711)

Research Products

[Publications] Futoshi Kawataka: "Synthesis and Thermolysis Behavior of Monoethylpalladium Complexes,EtPd(X)(PMe3)2(X=Electronegative Ligands)" Organometallics. 13. 3517-3524 (1994)

[Publications] Thomas Rappert: "Synthesis of Cationic Imine- and Amine-Coordinated Hydridoruthenium Complexes Relevant to Reductive Amination" Chem.Lett.2211-2214 (1994)

[Publications] Thomas Rappert: "Synthesis and Properties of Cationic Hydrido(tertiary phosphine)ruthenium(II)Complex" Organometallics. 13. 4984-4993 (1994)

[Publications] Akio Yamamoto: "Palladium-Catalyzed Double and Single Carbonylation of Aryl Halides and Allylic Comounds" Bull.Chem.Soc.Jpn.68. 433-446 (1995)

[Publications] 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)

[Publications] K.Onitsuka: "Synthesis and Properties of Ferrocenylethynyl Transition Metal Complex of Platinum,Palladium and Nickel" Bull.Chem.Soc.Jpn.67. 2611-2613 (1994)

[Publications] K.Onitsuka: "Synthesis,and Molecular Structure and Reactions of a Novel μ-σ、π-Cyclopentadienediyl Platinum-Manganese Complex" Chem.Lett. 2067-2070 (1994)

[Publications] K.Onitsuka: "Synthesis and Structure of Novel Metallacycle Complexes of Ruthenium Derived from 1,1'-Dialkynylferrocene" Chem.Lett. 2276-2282 (1994)

[Publications] 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)

[Publications] 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)

[Publications] 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)

[Publications] 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)

[Publications] 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)

[Publications] 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)

[Publications] A.Fukuoka: "Synthesis and Structure of Novel Organo(siloxo)platimum Complexes.Facile Reduction by Dihydrogen." Chem.Lett.1641-1644 (1994)

[Publications] T.Sone: "Synthesis,Structure and Reactivities of cis-Dimethyl(ηl-allyl)gold(III)Complexes." Bull.Chem.Jpn. (in press).

[Publications] S.Komiya: "Organometallic Dinuclear Complexes of Transition Metals.Alkyl Transfer from Platinum,Palladium and Gold to Transition Metals" Trends in Organometallic Chemistry. (in press).

[Publications] 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)

[Publications] M.Suginome: "Novel Activation of Two Si-Si s-Bonds in a Molecule by tert-Alkyl Isocyanide-Palladium Complex" Organometallics. 13. 4148-4150 (1994)

[Publications] M.Hada: "Palladium-Catalyzed Intermolecular Cyanosilylation of Alkynes Leading to Stereoselective Syntheses of α,β-Unsaturated Nitriles" Tetrahedron Lett.35. 8635-8638 (1994)

[Publications] 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)

[Publications] 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)

[Publications] K.Nozaki: "Acylcyanation of Terminal Acetylenes:Palladium Catalyzed Addition of Aryloyl Cyanides to Aryl acetylenes" J.Org.Chem.59. 2679-2681 (1994)

[Publications] 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)

[Publications] X.Zhang: "Enatioselective Hydrogenation of Acyclic Aromatic Ketones Catalyzed by BINAP-Ir(I)-Aminophosphine Systems" Tetrahedron Asymmetry. 5. 1179-1182 (1994)

[Publications] 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)

[Publications] X.Zhang: "Highly Enantioselective Hydrogenation of α、β-Unsaturated Carboxylic Acids Catalyzed by H8-BINAP-Ru(II)Complexes" Synlett. 501-503 (1994)

[Publications] K.Ono: "Palladium Catalyzed Arylation of N-Alkyl 0-Aryl Carbamates:Synthesis of Cinnamyl Alcohols via Heck Arylation" Tetrahedron Lett.35. 4133-4136 (1994)

[Publications] 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)

[Publications] 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)

[Publications] 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)

[Publications] 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).

[Publications] 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).

山本明夫早稲田大学, 理工学研究科, 教授 (30016711)