2003 Fiscal Year Annual Research Report

ルイス酸・遷移金属触媒を用いる環境調和型分子変換プロセスの開拓

Research Project

Project/Area Number	14002001
Research Institution	Tohoku University
Principal Investigator	山本嘉則東北大学, 大学院・理学研究科, 教授 (60029519)
Co-Investigator(Kenkyū-buntansha)	門田功東北大学, 多元物質科学研究所, 助教授 (30250666) 中村達東北大学, 大学院・理学研究科, 助手 (00333899) 浅尾直樹東北大学, 大学院・理学研究科, 助教授 (60241519) 上條真東北大学, 多元物質科学研究所, 助手
Keywords	ルイス酸触媒 / 遷移金属触媒 / 不斉アリル化 / ビスπ-アリルパラジウム / シアノインドール / パラジウム-アクア錯体 / アルキシ / ポリ環状エーテル
Research Abstract	π電子配位性ルイス酸触媒の存在下、アルキニルベンゼンが芳香環化し、ナフタレン誘導体を与える反応を見いだした。また、二価のパラジウムが遷移金属触媒としてだけではなく、同時にルイス酸触媒としても働くことが明らかとなった。これに関しては、新たに「ルイス酸・遷移金属両機能性触媒反応の開発」として研究を進めることにした。光学活性π-アリルパラジウム触媒を用いたイミンの不斉アリル化について詳細な検討を行った。その結果、極少量の水を添加により、反応速度および不斉収率が大幅に向上することがわかった。パラジウムへの水の配位が重要な役割を果たしていると考えられる。この反応の一般性は高く、様々な置換基を有する基質でもほぼ同様の結果が得られた。また、イソシアニド、TMSアジド、アリルカーボネートの三成分をPd触媒のもとで、一気に連結してシアノインドールを構築できることを見い出した。π-アリルパラジウムアジドが中間体として介在する触媒反応であり、これはビス-π-アリルパラジウムの窒素アナログとも考えられる。光学浩性な配位子の存在下、パラジウム-酢酸触媒によるピペリジン、ピロリジン誘導体の不斉合成について詳細に検討した。その結果、80%以上の光学純度で生成物を得ることができた。また、触媒としてパラジウム-アクア錯体を用いることにより、内部アルキンに対するアミンの直接付加に成功した。ルイス酸による分子内アリル化反応とルテニウム触媒による閉環メタセシスを組み合わせることにより、ポリ環状エーテル合成のためのコンバージェントプロセスを開発することに成功した。この方法論を利用し、海産毒ガンビエロールの高効率全合成に成功した。

Research Products
(30 results)

All Other

All Publications (30 results)

[Publications] I.Kadota: "Total Synthesis of Gambierol"Journal of the American Chemical Society. 125(1). 46-47 (2003)
[Publications] R.Hamasaki: "Nonlinear Optical Studies of Fullerene-Arylethyne Hybrids"Journal of Materials Chemistry. 13(1). 21-26 (2003)
[Publications] M.Fujitsuka: "Solvent Polarity Dependence of Photoinduced Charge Separation and Recombination Processes of Ferrocene-C_<60> Dyads"Journal of Physical Chemistry A. 107(10). 1452-1458 (2003)
[Publications] I.Nakamura: "Palladium-Catalyzed Hydrocarbonation and Hydroamination of 3,3-Dihexylcyclopropene with Pronucleophiles"Journal of Organic Chemistry. 68(6). 2297-2299 (2003)
[Publications] N.Asao: "π-π Chelation Controlled Chemoselective Conjugate Addition of Lithium Dimethylcuprate"Tetrahedron Letters. 44(9). 1803-1805 (2003)
[Publications] A.Siriwardana: "Addition of Hydrogen Halides to Alkylidenecyclopropanes. A Highly Efficient and Stereoselective Method for the Preparation of Homoallylic Halides"Tetrahedron Letters. 44(5). 985-987 (2003)
[Publications] N.Tsuboya: "Nonlinear Optical Properties of Novel Fullerene-Ferrocene Hybrid Molecules"Journal of Materials Chemistry. 13(3). 511-513 (2003)
[Publications] N.Asao: "Me_2CuLi・TMSCl in CH_2Cl_2. The Most Powerful Methylating Agent for Sterically Congested α,β-Enoates"Tetrahedron Letters. 44(22). 4265-4266 (2003)
[Publications] T.Shimada: "Carbon-Carbon Bond Cleavage of Diynes through the Hydroamination with Transition Metal Catalysts"Journal of the American Chemical Society. 125(22). 6646-6647 (2003)
[Publications] S.Kamijo: "A Bimetallic Catalyst and Dual Role Catalyst : Synthesis of N-(Alkoxycarbonyl)indoles from 2-(Alkynyl)phenylisocyanates"Journal of Organic Chemistry. 68(12). 4764-4771 (2003)
[Publications] A.Siriwardana: "Addition of Water to Arylidenecyclopropanes : A Highly Efficient Method for the Preparation of gem-Aryl Disubstituted Homoallylic Alcohols"Tetrahedron Letters. 44(24). 4547-4550 (2003)
[Publications] S.Kamijo: "Synthesis of Triazoles from Nonactivated Terminal Alkynes via the Three-Component Coupling Reaction Using a Pd(0)-Cu(I) Bimetallic Catalyst"Journal of the American Chemical Society. 125(26). 7786-7787 (2003)
[Publications] N.Asao: "AuBr_3-Catalyzed Cyclization of o-(Alkynyl)nitrobenzenes. Efficient Synthesis of Isatogens and Anthranils"Tetrahedron Letters. 44(30). 5675-5677 (2003)
[Publications] B.-H.Oh: "Catalytic and Thermal Hydrocarbonation of Methyleneaziridines"ARKIVOC. (8). 67-78 (2003)
[Publications] N.Asao: "Lewis Acid-Catalyzed Benzannulation via Unprecedented [4+2] Cycloaddition of o-Alkynyl(oxo)benzenes and Enynals with Alkynes"Journal of the American Chemical Society. 125(36). 10921-10925 (2003)
[Publications] N.Asao: "Functionalized 1,2-Dihydronaphthalenes from the Cu(OTf)_2-Catalyzed [4+2] Cycloaddition of o-Alkynyl(oxo)benzenes with Alkenes"Angewandte Chemie, International Edition. 42(30). 3504-3506 (2003)
[Publications] I.Kadota: "Convergent Total Syntheses of Gambierol and 16-epi-Gambierol and Their Biological Activities"Journal of the American Chemical Society. 125(39). 11893-11899 (2003)
[Publications] Y.Yamamoto: "Boron-Gadolinium Binary System as a Magnetic Resonance Imaging Boron Carrier"Pure and Applied Chemistry. 75(9). 1343-1348 (2003)
[Publications] I.Kadota: "Convergent synthesis of the F-K ring segment of brevetoxin B"Tetrahedron Letters. 44(43). 7929-7932 (2003)
[Publications] R.A.Fernandes: "Chiral Bis-π-allylpalladium Complex Catalyzed Asymmetric Allylation of Imines : Enhancement of the Enantioselectivity and Chemical Yield in the Presence of Water"Journal of the American Chemical Society. 125(46). 14133-14139 (2003)
[Publications] I.Kadota: "A Simple and Practical Method for the Stereoselective Synthesis of (Z)-1-Iodo-1-alkenes from 1,1-Diiodo-1-alkenes"Tetrahedron Letters. 44(48). 8645-8647 (2003)
[Publications] S.Mondal: "Synthesis of Novel Antitumor Agent 1-Methoxy-5,10-dioxo-5,10-dihydro-1H-benzo[γ]isochromene Carboxylic Acid (3-dimethyl-aminopropyl)amide with a Dual Role Pd(II) Catalyst"Journal of Organic Chemistry. 68(24). 9496-9498 (2003)
[Publications] I.Kadota: "Convergent Synthesis of the A-F Ring Segment of Yessotoxin and Adriatoxin"Tetrahedron Letters. 44(50). 8935-8938 (2003)
[Publications] S.Kamijo: "Tetrazole Synthesis via the Palladium-Catalyzed Three Component Coupling Reaction"Molecular Diversity. 6(3-4). 181-192 (2003)
[Publications] B.-H.Oh: "Synthesis of 3-Methylenepyrrolidines by Palladium-Catalyzed [3+2]-Cycloaddition of Alkylidenecyclopropanes with Imines"Heterocycles. 61. 247-257 (2003)
[Publications] S.Kamijo: "Copper-Catalyzed Tandem Reaction between Imines and Alcohols Leading to Indoles"Tetrahedron Letters. 45(1). 35-38 (2004)
[Publications] S.Kamijo: "Four-Component Coupling Reactions of Silylacetylenes, Allyl Carbonates, and Trimethylsilyl Azide Catalyzed by a Pd(0)-Cu(I) Bimetallic Catalyst. Fully Substituted Triazole Synthesis from Seemingly Internal Alkynes"Tetrahedron Letters. 45(4). 689-691 (2004)
[Publications] R.A.Fernandes: "The First Catalytic Asymmetric Allylation of Imines with the Tetraallylsilane-TBAF-MeOH System, using the Chiral Bis-π-Allylpalladium Complex"Journal of Organic Chemistry. 69(3). 735-738 (2004)
[Publications] L.M.Lutete: "Palladium-Catalyzed Intramolecular Asymmetric Hydroamination of Alkynes"Journal of the American Chemical Society. 126(6). 1622-1623 (2004)
[Publications] G.B.Bajracharya: "Reduction of Carbonyl Function to a Methyl group"Synthesis. (2). 308-311 (2004)

2003 Fiscal Year Annual Research Report

ルイス酸・遷移金属触媒を用いる環境調和型分子変換プロセスの開拓

Principal Investigator

山本 嘉則 東北大学, 大学院・理学研究科, 教授 (60029519)

Research Products

[Publications] I.Kadota: "Total Synthesis of Gambierol"Journal of the American Chemical Society. 125(1). 46-47 (2003)

[Publications] R.Hamasaki: "Nonlinear Optical Studies of Fullerene-Arylethyne Hybrids"Journal of Materials Chemistry. 13(1). 21-26 (2003)

[Publications] M.Fujitsuka: "Solvent Polarity Dependence of Photoinduced Charge Separation and Recombination Processes of Ferrocene-C_<60> Dyads"Journal of Physical Chemistry A. 107(10). 1452-1458 (2003)

[Publications] I.Nakamura: "Palladium-Catalyzed Hydrocarbonation and Hydroamination of 3,3-Dihexylcyclopropene with Pronucleophiles"Journal of Organic Chemistry. 68(6). 2297-2299 (2003)

[Publications] N.Asao: "π-π Chelation Controlled Chemoselective Conjugate Addition of Lithium Dimethylcuprate"Tetrahedron Letters. 44(9). 1803-1805 (2003)

[Publications] A.Siriwardana: "Addition of Hydrogen Halides to Alkylidenecyclopropanes. A Highly Efficient and Stereoselective Method for the Preparation of Homoallylic Halides"Tetrahedron Letters. 44(5). 985-987 (2003)

[Publications] N.Tsuboya: "Nonlinear Optical Properties of Novel Fullerene-Ferrocene Hybrid Molecules"Journal of Materials Chemistry. 13(3). 511-513 (2003)

[Publications] N.Asao: "Me_2CuLi・TMSCl in CH_2Cl_2. The Most Powerful Methylating Agent for Sterically Congested α,β-Enoates"Tetrahedron Letters. 44(22). 4265-4266 (2003)

[Publications] T.Shimada: "Carbon-Carbon Bond Cleavage of Diynes through the Hydroamination with Transition Metal Catalysts"Journal of the American Chemical Society. 125(22). 6646-6647 (2003)

[Publications] S.Kamijo: "A Bimetallic Catalyst and Dual Role Catalyst : Synthesis of N-(Alkoxycarbonyl)indoles from 2-(Alkynyl)phenylisocyanates"Journal of Organic Chemistry. 68(12). 4764-4771 (2003)

[Publications] A.Siriwardana: "Addition of Water to Arylidenecyclopropanes : A Highly Efficient Method for the Preparation of gem-Aryl Disubstituted Homoallylic Alcohols"Tetrahedron Letters. 44(24). 4547-4550 (2003)

[Publications] S.Kamijo: "Synthesis of Triazoles from Nonactivated Terminal Alkynes via the Three-Component Coupling Reaction Using a Pd(0)-Cu(I) Bimetallic Catalyst"Journal of the American Chemical Society. 125(26). 7786-7787 (2003)

[Publications] N.Asao: "AuBr_3-Catalyzed Cyclization of o-(Alkynyl)nitrobenzenes. Efficient Synthesis of Isatogens and Anthranils"Tetrahedron Letters. 44(30). 5675-5677 (2003)

[Publications] B.-H.Oh: "Catalytic and Thermal Hydrocarbonation of Methyleneaziridines"ARKIVOC. (8). 67-78 (2003)

[Publications] N.Asao: "Lewis Acid-Catalyzed Benzannulation via Unprecedented [4+2] Cycloaddition of o-Alkynyl(oxo)benzenes and Enynals with Alkynes"Journal of the American Chemical Society. 125(36). 10921-10925 (2003)

[Publications] N.Asao: "Functionalized 1,2-Dihydronaphthalenes from the Cu(OTf)_2-Catalyzed [4+2] Cycloaddition of o-Alkynyl(oxo)benzenes with Alkenes"Angewandte Chemie, International Edition. 42(30). 3504-3506 (2003)

[Publications] I.Kadota: "Convergent Total Syntheses of Gambierol and 16-epi-Gambierol and Their Biological Activities"Journal of the American Chemical Society. 125(39). 11893-11899 (2003)

[Publications] Y.Yamamoto: "Boron-Gadolinium Binary System as a Magnetic Resonance Imaging Boron Carrier"Pure and Applied Chemistry. 75(9). 1343-1348 (2003)

[Publications] I.Kadota: "Convergent synthesis of the F-K ring segment of brevetoxin B"Tetrahedron Letters. 44(43). 7929-7932 (2003)

[Publications] R.A.Fernandes: "Chiral Bis-π-allylpalladium Complex Catalyzed Asymmetric Allylation of Imines : Enhancement of the Enantioselectivity and Chemical Yield in the Presence of Water"Journal of the American Chemical Society. 125(46). 14133-14139 (2003)

[Publications] I.Kadota: "A Simple and Practical Method for the Stereoselective Synthesis of (Z)-1-Iodo-1-alkenes from 1,1-Diiodo-1-alkenes"Tetrahedron Letters. 44(48). 8645-8647 (2003)

[Publications] S.Mondal: "Synthesis of Novel Antitumor Agent 1-Methoxy-5,10-dioxo-5,10-dihydro-1H-benzo[γ]isochromene Carboxylic Acid (3-dimethyl-aminopropyl)amide with a Dual Role Pd(II) Catalyst"Journal of Organic Chemistry. 68(24). 9496-9498 (2003)

[Publications] I.Kadota: "Convergent Synthesis of the A-F Ring Segment of Yessotoxin and Adriatoxin"Tetrahedron Letters. 44(50). 8935-8938 (2003)

[Publications] S.Kamijo: "Tetrazole Synthesis via the Palladium-Catalyzed Three Component Coupling Reaction"Molecular Diversity. 6(3-4). 181-192 (2003)

[Publications] B.-H.Oh: "Synthesis of 3-Methylenepyrrolidines by Palladium-Catalyzed [3+2]-Cycloaddition of Alkylidenecyclopropanes with Imines"Heterocycles. 61. 247-257 (2003)

[Publications] S.Kamijo: "Copper-Catalyzed Tandem Reaction between Imines and Alcohols Leading to Indoles"Tetrahedron Letters. 45(1). 35-38 (2004)

[Publications] S.Kamijo: "Four-Component Coupling Reactions of Silylacetylenes, Allyl Carbonates, and Trimethylsilyl Azide Catalyzed by a Pd(0)-Cu(I) Bimetallic Catalyst. Fully Substituted Triazole Synthesis from Seemingly Internal Alkynes"Tetrahedron Letters. 45(4). 689-691 (2004)

[Publications] R.A.Fernandes: "The First Catalytic Asymmetric Allylation of Imines with the Tetraallylsilane-TBAF-MeOH System, using the Chiral Bis-π-Allylpalladium Complex"Journal of Organic Chemistry. 69(3). 735-738 (2004)

[Publications] L.M.Lutete: "Palladium-Catalyzed Intramolecular Asymmetric Hydroamination of Alkynes"Journal of the American Chemical Society. 126(6). 1622-1623 (2004)

[Publications] G.B.Bajracharya: "Reduction of Carbonyl Function to a Methyl group"Synthesis. (2). 308-311 (2004)

山本嘉則東北大学, 大学院・理学研究科, 教授 (60029519)