2002 年度実績報告書

π電子配位性分子触媒を用いた分子変換反応の開発

研究課題

研究課題/領域番号	14103007
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	上條真東北大学, 多元物質科学研究所, 助手 (00359548) 中村達東北大学, 大学院・理学研究科, 助手 (00333899)
キーワード	ルイス酸 / アセチレン結合 / σ-π型キレーション / π-電子 / π-配位 / 遷移金属錯体触媒 / メチレンシクロプロパン / C-H結合活性化
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ヒドロシリル化反応について検討を行った。その結果、B(C_6F_5)_3を触媒として用いると、極めて高い1,3-不斉誘導が発現することを見出した。これは、ルイス酸がアルキンとカルボニル酸素との間でσ-π型キレートを形成した結果であると考えられる。また、酢酸パラジウム触媒存在下、求核体としてアルコールを用いた場合には、環化反応が進行し、環状アルケニルエーテルが高収率で得られた。この反応において、酢酸パラジウムは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を見い出した。パラジウム触媒存在下でメテレンシクロプロパン化合物はマスクされたアルキル化剤として働くことを利用して、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、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

(21件)

すべてその他

すべて文献書誌 (21件)

[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 Society. 124・43. 12650-12651 (2002)
[文献書誌] N.Asao: "Pd(II)Acts Simultaneously as a Lewis Acid and as a Transition-Metal Catalyst : Synthesis of Cyclic Alkenyl Ethers from Acetylenic Aldehydes"Journal of the American Chemical Society. 124・5. 764-765 (2002)
[文献書誌] N.Asao: "Lewis acid catalyzed stereoselective hydrosilylation of ketones under the control of σ-π chelation"Tetrahedron. 58・41. 8195-8203 (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"J. AM. CHEM. SOC.. 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 Letters. 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 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] Y.Chounan: "Copper-Mediated Synthesis of Natural and Unnatural Products"N.Krause, Wiley-VCH. 377 (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)

2002 年度 実績報告書

π電子配位性分子触媒を用いた分子変換反応の開発

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: "AuCl_3-Catalyzed Benzannulation : Synthesis of Naphthyl Ketone Derivatives from o-Alkynylbenzaldehydes with Alkynes"Journal of the American Chemical Society. 124・43. 12650-12651 (2002)

[文献書誌] N.Asao: "Pd(II)Acts Simultaneously as a Lewis Acid and as a Transition-Metal Catalyst : Synthesis of Cyclic Alkenyl Ethers from Acetylenic Aldehydes"Journal of the American Chemical Society. 124・5. 764-765 (2002)

[文献書誌] N.Asao: "Lewis acid catalyzed stereoselective hydrosilylation of ketones under the control of σ-π chelation"Tetrahedron. 58・41. 8195-8203 (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"J. AM. CHEM. SOC.. 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 Letters. 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 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] Y.Chounan: "Copper-Mediated Synthesis of Natural and Unnatural Products"N.Krause, Wiley-VCH. 377 (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)

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)