2002 年度実績報告書

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

研究課題

研究課題/領域番号	14002001
研究機関	東北大学
研究代表者	山本嘉則東北大学, 大学院・理学研究科, 教授 (60029519)
研究分担者	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
キーワード	ルイス酸触媒 / 遷移金属触媒 / キレーション / 不斉アリル化 / ビスπ-アリルパラジウム / メチレンシクロプロパン / 触媒的アルキル化 / 環状エーテル
研究概要	分子内にアルキンを有するカルボニル化合物に対する求核付加反応について検討を行った。その結果、ある種のルイス酸の存在下での反応では、通常の立体効果では説明できない選択性が親察された。これは、ルイス酸がアルキンとカルボニル酸素との間にキレートを形成した結果であると考えられる。また、求核体としてアルコールを用いた場合には、酢酸パラジウムがルイス酸としてだけではなく、同時に遷移金属触媒としても働くことを見い出した。ピネン誘導体から調製した光学活性π-アリルパラジウム触媒を用い、イミンの不斉アリル化について検討した。反応条件を詳細に検討した結果、90%の光学純度で目的のアリル化体を得ることに成功した。環状イミンの不斉アリル化についても検討したが、今のところよい結果は得られていない。この反応の不斉誘導は、イミンの幾何異性が重要であることが明らかになった。メチレンシクロプロパン化合物をマスクされたアルキル化剤として利用した、C-H結合活性化を伴うアルキル化反応を研究し、フラン、ピロール、チオフェンなどの種々の複素芳香環化合物の触媒的アルキル化反応を開発した。この研究において、5員環複素芳香環のα位のC-H結合が選択的に活性化されることが見出された。また5員環複素芳香族化合物のパラジウム触媒反応における反応性についての知見が得られた。また、メチレンシクロプロパン化合物を利用したケトン化合物のαアルキル化反応を開発した。パラジウム-酢酸触媒を用いるアミンとアルキンとの分子内反応について検討し、ピペリジン、ピロリジン誘導体を高収率で得ることに成功した。また、不斉配位子を有する触媒を用いることにより、80%の光学純度で生成物を得ることに成功した。さらにアルコールの分子内反応を行うことにより、環状エーテルの触媒的合成に成功した。

研究成果
(42件)

すべてその他

すべて文献書誌 (42件)

[文献書誌] N.Asao: "Pd(II) Acts Simultaneously as a Lewis Acid and as a Transition-Metal Catalysts : Synthesis of Cyclic Alkenyl Ethers from Acetylenic Aldehydes"Journal of the American Chemical Society. 124. 764-765 (2002)
[文献書誌] D.H.Camacho: "Synthesis of (E)-1,2-Divinyl-1,2-diethynylethene (DVDEE) via the Palladium-Catalyzed Reaction of Conjugated Diynes. A New Building Block for Molecular Scaffolding"Journal of the American Chemical Society. 124. 924-925 (2002)
[文献書誌] M.Bao: "Nucleophilic Allylation-Heterocyclization via Bis-π-allylpalladium Complexes : Synthesis of Five and Six-Membered Heterocycles"Chemistry Letter. 158-159 (2002)
[文献書誌] D.H.Camacho: "'Anti-Wacker'-type Hydroalkoxylation of Diynes Catalyzed by Palladium(0)"Tetrahedron Letters. 43. 1085-1088 (2002)
[文献書誌] I.Kadota: "Convergent Synthesis of Polycyclic Ethers via the Intramolecular Allylation of α-Acetoxy Ethers and Subsequent Ring-Closing Metathesis"Journal of the American Chemical Society. 124. 3562-3566 (2002)
[文献書誌] I.Kadota: "Syntheses of the AB and EFGH Ring Segments of Gambierol"Tetrahedron. 58. 1799-1816 (2002)
[文献書誌] J.-G.Shim: "Catalytic and Highly Regiospecific Carbon-Carbon Bond Formation at α-Position of Michael Acceptor by Palladium Complex"Chemical Communication. 852-853 (2002)
[文献書誌] D.H.Camacho: "Palladium-Catalyzed Addition of Ketones to Alkylidenecyclopropanes"Tetrahedron Letters. 43. 2903-2907 (2002)
[文献書誌] T.Kawasaki: "Synthesis of Phthalides and 3.4-Dihydroisocoumarines Using the Palladium-Catalyzed Intramolecular Benzannulation Strategy"Journal of Organic Chemistry. 67. 2653-2658 (2002)
[文献書誌] I.Kadota: "Concise Synthesis of Cyclic Ethers via the Palladium-Catalyzed Coupling of Ketone Acetal Triflates and Organozinc Reagents. Application to the Interative Synthesis of Polycyclic Ethers"Journal of Organic Chemistry. 67. 3494-3498 (2002)
[文献書誌] S.Kamijo: "Cyanamide Synthesis by the Palladium-Catalyzed Cleavage of a Si-N Bond"Angewante Chemie. 41. 1780-1782 (2002)
[文献書誌] I.Nakamura: "Addition of Heteroaromatics to Alkylidenecyclopropanes Catalyzed by Palladium"Journal of Organic Chemistry. 67. 3445-3449 (2002)
[文献書誌] T.Kawasaki: "Nichel(0)-Catalyzed Dimerization of Ethyl Cyclopropylideneacetates"Journal of Organic Chemistry. 67. 4911-4915 (2002)
[文献書誌] T.Kawasaki: "Synthesis of 6H-Dibenzo[b,d]pyran-6-ones from Aryl 3-Bromopropenoates via a Sequential One-Pot Procedure Using the Sonogashira Coupling-Benzannulation Reaction"Journal of Organic Chemistry. 67. 5138-5141 (2002)
[文献書誌] N.Tsuboya: "Nonlinear Optical Properties of Novel Carborane-ferrocene Conjugated Dyads. Electron-withdrawing Characteristics of Carboranes"Journal of Material Chemistry. 12. 2701-2705 (2002)
[文献書誌] S.Kamijo: "A New Pd^0-Cu^I Bimetallic Catalyst for the Synthesis of Indoles from Isocyanates and Allyl Carbonates"Angewante Chemie. 41. 3230-3233 (2002)
[文献書誌] S.Kamijo: "Synthesis of Allyl Cyanamides and N-Cyanoindoles via the Palladium-Catalyzed Three Component Coupling Reaction"Journal of the American Chemical Society. 124. 11940-11945 (2002)
[文献書誌] S.Kamijo: "Palladium-Catalyzed Selective Synthesis of 2-Allyltetrazoles"Journal of Organic Chemistry. 67. 7413-7417 (2002)
[文献書誌] N.Mimura: "Relative Stabilities of Some Synthetically Useful 2,3-cis-Disubstituted Aziridines and Their 2,3-Trans Isomers"Journal of Organic Chemistry. 67. 5796-5801 (2002)
[文献書誌] K.Aoyagi: "Palladium-Catalyzed Aminoallylation of Activated Olefins with Allylic Halides and Phthalimide"Journal of Organic Chemistry. 67. 5977-5980 (2002)
[文献書誌] H.Nakamura: "Tandem Nucleophilic Allylation-alkoxyallylation of Alkynylaldehydes via Amphiphilic Bis-π-allylpalladium Complexes"Tetrahedron Letters. 43. 7631-7633 (2002)
[文献書誌] N.Asao: "Lewis Acid Catalyzed Stereoselective Hydrosilylation of Ketones under the Control of σ-π Chelation"Tetrahedron. 58. 8195-8203 (2002)
[文献書誌] L.M.Lutete: "Hydroamination of Alkynes Catalyzed by Palladium / Benzoic Acid"Hetrocycles. 58. 347-357 (2002)
[文献書誌] N.Asao: "AuCl_3-Catalyzed Benzannulation : Synthesis of Naphthyl Ketone Derivatives from o-Alkynylbenzaldehydes with Alkynes"Journal of the American Chemical Chemistry. 124. 12650-12651 (2002)
[文献書誌] T.Shimada: "Palladium-Catalyzed Intermolecular Hydroamination of Alkynes. A Dramatic Rate-Enhancement Effect of o-Aminophenol"Journal of the American Chemical Chemistry. 124. 12670-12671 (2002)
[文献書誌] B.H.Oh: "Palladium-catalyzed Hydrocarbonation of Methyleneaziridines with Carbon Pronucleophiles"Tetrahedron Letters. 43. 9625-9628 (2002)
[文献書誌] S.Kamijo: "Regiospecific Synthesis of 2-Allyl-1,2,3-triazoles by Palladium-catalyzed 1,3-Dipolar Cycloaddition"Tetrahedron Letters. 43. 9707-9710 (2002)
[文献書誌] I.Nakamura: "Indenol Ether Formation from Aryl Alkynes Bearing ortho-Acetals : An Unprecedented Rearrangement in Palladium-Catalyzed Carboalkoxylation"Angewante Chemie. 41. 4328-4331 (2002)
[文献書誌] R.Hamasaki: "Nonlinear Optical Studies of Fullerene-arylethyne Hybrids"Journal of Material Chemistry. 13. 21-26 (2002)
[文献書誌] A.I.Siriwardana: "Addition of Hydrogen Halides to Alkylidenecyclopropanes : A Highly Efficient and Stereoselective Method for the Preparation of Homoallylic Halides"Tetrahedron Letters. 44. 985-987 (2002)
[文献書誌] T.Shimada: "Palladium-Catalyzed Intermolecular Hydroamination of Alkynes. A Dramatic Rate-Enhancement Effect of o-Aminophenol"Journal of the American Chemical Chemistry. 124. 12670-12671 (2002)
[文献書誌] B.H.Oh: "Palladium-catalyzed Hydrocarbonation of Methyleneaziridines with Carbon Pronucleophiles"Tetrahedron Letters. 43. 9625-9628 (2002)
[文献書誌] S.Kamijo: "Regiospecific Synthesis of 2-Allyl-1,2,3-triazoles by Palladium-catalyzed 1,3-Dipolar Cycloaddition"Tetrahedron Letters. 43. 9707-9710 (2002)
[文献書誌] I.Nakamura: "Indenol Ether Formation from Aryl Alkynes Bearing ortho-Acetals : An Unprecedented Rearrangement in Palladium-Catalyzed Carboalkoxylation"Angewante Chemie. 41. 4328-4331 (2002)
[文献書誌] R.Hamasaki: "Nonlinear Optical Studies of Fullerene-arylethyne Hybrids"Journal of Material Chemistry. 13. 21-26 (2003)
[文献書誌] I.Kadota: "Total Synthesis of Gambierol"Journal of the American Chemical Chemistry. 125. 46-47 (2003)
[文献書誌] Y.Chounan: "Copper-Mediated Synthesis of Natural and Unnatural Products"N.Krause, Wiley-VCH. 377 (2002)
[文献書誌] Y.Yamamoto: "New Transformations with Lewis Acid and Transition Metal Catalysts. Application to the Synthesis of Polycyclic Ethers, in "My Favorite Organic Synthesis""有機合成化学協会、化学同人. 260 (2002)
[文献書誌] V.Gevorgyan: "Carbopalladation of Alkynes Followed by Trapping with Electrophiles, in "Handbook of Organopalladium Chemistry for Organic Synthesis Vol.1""E.Negishi, Wiley-Interscience. 1662 (2002)
[文献書誌] S.Saito: "Palladium-Catalyzed Benzannulation Reactions of Conjugated Enynes and Diynes in "Handbook of Organopalladium Chemistry for Organic Synthesis Vol.1""E.Negishi, Wiley-Interscience. 1662 (2002)
[文献書誌] H.Nakamura: "Palladium-Catalyzed Reactions of Soft Carbon Nucleophiles with Dienes, in "Handbook of Organopalladium Chemistry for Organic Synthesis Vol.2""E.Negishi, Wiley-Interscience. 1617 (2002)
[文献書誌] H.Nakamura: "Cope, Claisen, and Other [3,3] Rearrangements, in "Handbook of Organopalladium Chemistry for Organic Synthesis Vol.2""E.Negishi, Wiley-Interscience. 1617 (2002)

2002 年度 実績報告書

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

研究代表者

山本 嘉則 東北大学, 大学院・理学研究科, 教授 (60029519)

研究成果

[文献書誌] N.Asao: "Pd(II) Acts Simultaneously as a Lewis Acid and as a Transition-Metal Catalysts : Synthesis of Cyclic Alkenyl Ethers from Acetylenic Aldehydes"Journal of the American Chemical Society. 124. 764-765 (2002)

[文献書誌] D.H.Camacho: "Synthesis of (E)-1,2-Divinyl-1,2-diethynylethene (DVDEE) via the Palladium-Catalyzed Reaction of Conjugated Diynes. A New Building Block for Molecular Scaffolding"Journal of the American Chemical Society. 124. 924-925 (2002)

[文献書誌] M.Bao: "Nucleophilic Allylation-Heterocyclization via Bis-π-allylpalladium Complexes : Synthesis of Five and Six-Membered Heterocycles"Chemistry Letter. 158-159 (2002)

[文献書誌] D.H.Camacho: "'Anti-Wacker'-type Hydroalkoxylation of Diynes Catalyzed by Palladium(0)"Tetrahedron Letters. 43. 1085-1088 (2002)

[文献書誌] I.Kadota: "Convergent Synthesis of Polycyclic Ethers via the Intramolecular Allylation of α-Acetoxy Ethers and Subsequent Ring-Closing Metathesis"Journal of the American Chemical Society. 124. 3562-3566 (2002)

[文献書誌] I.Kadota: "Syntheses of the AB and EFGH Ring Segments of Gambierol"Tetrahedron. 58. 1799-1816 (2002)

[文献書誌] J.-G.Shim: "Catalytic and Highly Regiospecific Carbon-Carbon Bond Formation at α-Position of Michael Acceptor by Palladium Complex"Chemical Communication. 852-853 (2002)

[文献書誌] D.H.Camacho: "Palladium-Catalyzed Addition of Ketones to Alkylidenecyclopropanes"Tetrahedron Letters. 43. 2903-2907 (2002)

[文献書誌] T.Kawasaki: "Synthesis of Phthalides and 3.4-Dihydroisocoumarines Using the Palladium-Catalyzed Intramolecular Benzannulation Strategy"Journal of Organic Chemistry. 67. 2653-2658 (2002)

[文献書誌] I.Kadota: "Concise Synthesis of Cyclic Ethers via the Palladium-Catalyzed Coupling of Ketone Acetal Triflates and Organozinc Reagents. Application to the Interative Synthesis of Polycyclic Ethers"Journal of Organic Chemistry. 67. 3494-3498 (2002)

[文献書誌] S.Kamijo: "Cyanamide Synthesis by the Palladium-Catalyzed Cleavage of a Si-N Bond"Angewante Chemie. 41. 1780-1782 (2002)

[文献書誌] I.Nakamura: "Addition of Heteroaromatics to Alkylidenecyclopropanes Catalyzed by Palladium"Journal of Organic Chemistry. 67. 3445-3449 (2002)

[文献書誌] T.Kawasaki: "Nichel(0)-Catalyzed Dimerization of Ethyl Cyclopropylideneacetates"Journal of Organic Chemistry. 67. 4911-4915 (2002)

[文献書誌] T.Kawasaki: "Synthesis of 6H-Dibenzo[b,d]pyran-6-ones from Aryl 3-Bromopropenoates via a Sequential One-Pot Procedure Using the Sonogashira Coupling-Benzannulation Reaction"Journal of Organic Chemistry. 67. 5138-5141 (2002)

[文献書誌] N.Tsuboya: "Nonlinear Optical Properties of Novel Carborane-ferrocene Conjugated Dyads. Electron-withdrawing Characteristics of Carboranes"Journal of Material Chemistry. 12. 2701-2705 (2002)

[文献書誌] S.Kamijo: "A New Pd^0-Cu^I Bimetallic Catalyst for the Synthesis of Indoles from Isocyanates and Allyl Carbonates"Angewante Chemie. 41. 3230-3233 (2002)

[文献書誌] S.Kamijo: "Synthesis of Allyl Cyanamides and N-Cyanoindoles via the Palladium-Catalyzed Three Component Coupling Reaction"Journal of the American Chemical Society. 124. 11940-11945 (2002)

[文献書誌] S.Kamijo: "Palladium-Catalyzed Selective Synthesis of 2-Allyltetrazoles"Journal of Organic Chemistry. 67. 7413-7417 (2002)

[文献書誌] N.Mimura: "Relative Stabilities of Some Synthetically Useful 2,3-cis-Disubstituted Aziridines and Their 2,3-Trans Isomers"Journal of Organic Chemistry. 67. 5796-5801 (2002)

[文献書誌] K.Aoyagi: "Palladium-Catalyzed Aminoallylation of Activated Olefins with Allylic Halides and Phthalimide"Journal of Organic Chemistry. 67. 5977-5980 (2002)

[文献書誌] H.Nakamura: "Tandem Nucleophilic Allylation-alkoxyallylation of Alkynylaldehydes via Amphiphilic Bis-π-allylpalladium Complexes"Tetrahedron Letters. 43. 7631-7633 (2002)

[文献書誌] N.Asao: "Lewis Acid Catalyzed Stereoselective Hydrosilylation of Ketones under the Control of σ-π Chelation"Tetrahedron. 58. 8195-8203 (2002)

[文献書誌] L.M.Lutete: "Hydroamination of Alkynes Catalyzed by Palladium / Benzoic Acid"Hetrocycles. 58. 347-357 (2002)

[文献書誌] N.Asao: "AuCl_3-Catalyzed Benzannulation : Synthesis of Naphthyl Ketone Derivatives from o-Alkynylbenzaldehydes with Alkynes"Journal of the American Chemical Chemistry. 124. 12650-12651 (2002)

[文献書誌] T.Shimada: "Palladium-Catalyzed Intermolecular Hydroamination of Alkynes. A Dramatic Rate-Enhancement Effect of o-Aminophenol"Journal of the American Chemical Chemistry. 124. 12670-12671 (2002)

[文献書誌] B.H.Oh: "Palladium-catalyzed Hydrocarbonation of Methyleneaziridines with Carbon Pronucleophiles"Tetrahedron Letters. 43. 9625-9628 (2002)

[文献書誌] S.Kamijo: "Regiospecific Synthesis of 2-Allyl-1,2,3-triazoles by Palladium-catalyzed 1,3-Dipolar Cycloaddition"Tetrahedron Letters. 43. 9707-9710 (2002)

[文献書誌] I.Nakamura: "Indenol Ether Formation from Aryl Alkynes Bearing ortho-Acetals : An Unprecedented Rearrangement in Palladium-Catalyzed Carboalkoxylation"Angewante Chemie. 41. 4328-4331 (2002)

[文献書誌] R.Hamasaki: "Nonlinear Optical Studies of Fullerene-arylethyne Hybrids"Journal of Material Chemistry. 13. 21-26 (2002)

[文献書誌] A.I.Siriwardana: "Addition of Hydrogen Halides to Alkylidenecyclopropanes : A Highly Efficient and Stereoselective Method for the Preparation of Homoallylic Halides"Tetrahedron Letters. 44. 985-987 (2002)

[文献書誌] T.Shimada: "Palladium-Catalyzed Intermolecular Hydroamination of Alkynes. A Dramatic Rate-Enhancement Effect of o-Aminophenol"Journal of the American Chemical Chemistry. 124. 12670-12671 (2002)

[文献書誌] B.H.Oh: "Palladium-catalyzed Hydrocarbonation of Methyleneaziridines with Carbon Pronucleophiles"Tetrahedron Letters. 43. 9625-9628 (2002)

[文献書誌] S.Kamijo: "Regiospecific Synthesis of 2-Allyl-1,2,3-triazoles by Palladium-catalyzed 1,3-Dipolar Cycloaddition"Tetrahedron Letters. 43. 9707-9710 (2002)

[文献書誌] I.Nakamura: "Indenol Ether Formation from Aryl Alkynes Bearing ortho-Acetals : An Unprecedented Rearrangement in Palladium-Catalyzed Carboalkoxylation"Angewante Chemie. 41. 4328-4331 (2002)

[文献書誌] R.Hamasaki: "Nonlinear Optical Studies of Fullerene-arylethyne Hybrids"Journal of Material Chemistry. 13. 21-26 (2003)

[文献書誌] I.Kadota: "Total Synthesis of Gambierol"Journal of the American Chemical Chemistry. 125. 46-47 (2003)

[文献書誌] Y.Chounan: "Copper-Mediated Synthesis of Natural and Unnatural Products"N.Krause, Wiley-VCH. 377 (2002)

[文献書誌] Y.Yamamoto: "New Transformations with Lewis Acid and Transition Metal Catalysts. Application to the Synthesis of Polycyclic Ethers, in "My Favorite Organic Synthesis""有機合成化学協会、化学同人. 260 (2002)

[文献書誌] V.Gevorgyan: "Carbopalladation of Alkynes Followed by Trapping with Electrophiles, in "Handbook of Organopalladium Chemistry for Organic Synthesis Vol.1""E.Negishi, Wiley-Interscience. 1662 (2002)

[文献書誌] S.Saito: "Palladium-Catalyzed Benzannulation Reactions of Conjugated Enynes and Diynes in "Handbook of Organopalladium Chemistry for Organic Synthesis Vol.1""E.Negishi, Wiley-Interscience. 1662 (2002)

[文献書誌] H.Nakamura: "Palladium-Catalyzed Reactions of Soft Carbon Nucleophiles with Dienes, in "Handbook of Organopalladium Chemistry for Organic Synthesis Vol.2""E.Negishi, Wiley-Interscience. 1617 (2002)

[文献書誌] H.Nakamura: "Cope, Claisen, and Other [3,3] Rearrangements, in "Handbook of Organopalladium Chemistry for Organic Synthesis Vol.2""E.Negishi, Wiley-Interscience. 1617 (2002)

2002 年度実績報告書

山本嘉則東北大学, 大学院・理学研究科, 教授 (60029519)