2002 Fiscal Year Annual Research Report

π電子配位性分子触媒を用いた分子変換反応の開発

Research Project

Project/Area Number	14103007
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)	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)
Keywords	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
Research Abstract	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。

Research Products

(21 results)

All Other

All Publications (21 results)

[Publications] 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)
[Publications] 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)
[Publications] N.Asao: "Lewis acid catalyzed stereoselective hydrosilylation of ketones under the control of σ-π chelation"Tetrahedron. 58・41. 8195-8203 (2002)
[Publications] 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)
[Publications] M.Bao: "Nucleophilic Allylation-Heterocyclization via Bis-π-allylpalladium Complexes : Synthesis of Five and Six-Membered Heterocycles"Chemistry Letters. 158-159 (2002)
[Publications] D.H.Camacho: "'Anti-Wacker'-type Hydroalkoxylation of Diynes Catalyzed by Palladium(0)"Tetrahedron Letters. 43. 1085-1088 (2002)
[Publications] 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)
[Publications] I.Kadota: "Syntheses of the AB and EFGH Ring Segments of Gambierol"Tetrahedron. 58. 1799-1816 (2002)
[Publications] 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)
[Publications] D.H.Camacho: "Palladium-Catalyzed Addition of Ketones to Alkylidenecyclopropanes"Tetrahedron Letters. 43. 2903-2907 (2002)
[Publications] T.Kawasaki: "Synthesis of Phthalides and 3.4-Dihydroisocoumarines Using the Palladium-Catalyzed Intramolecular Benzannulation Strategy"Journal of Organic Chemistry. 67. 2653-2658 (2002)
[Publications] 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)
[Publications] S.Kamijo: "Cyanamide Synthesis by the Palladium-Catalyzed Cleavage of a Si-N Bond"Angewante Chemie. 41. 1780-1782 (2002)
[Publications] I.Nakamura: "Addition of Heteroaromatics to Alkylidenecyclopropanes Catalyzed by Palladium"Journal of Organic Chemistry. 67. 3445-3449 (2002)
[Publications] T.Kawasaki: "Nichel(0)-Catalyzed Dimerization of Ethyl Cyclopropylideneacetates"Journal of Organic Chemistry. 67. 4911-4915 (2002)
[Publications] 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)
[Publications] N.Tsuboya: "Nonlinear Optical Properties of Novel Carborane-ferrocene Conjugated Dyads. Electron-withdrawing Characteristics of Carboranes"Journal of Material Chemistry. 12. 2701-2705 (2002)
[Publications] 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)
[Publications] Y.Chounan: "Copper-Mediated Synthesis of Natural and Unnatural Products"N.Krause, Wiley-VCH. 377 (2002)
[Publications] 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)
[Publications] 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 Fiscal Year Annual Research Report

π電子配位性分子触媒を用いた分子変換反応の開発

Principal Investigator

山本 嘉則 東北大学, 大学院・理学研究科, 教授 (60029519)

Research Products

[Publications] 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)

[Publications] 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)

[Publications] N.Asao: "Lewis acid catalyzed stereoselective hydrosilylation of ketones under the control of σ-π chelation"Tetrahedron. 58・41. 8195-8203 (2002)

[Publications] 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)

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

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

[Publications] 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)

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

[Publications] 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)

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

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

[Publications] 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)

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

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

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

[Publications] 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)

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

[Publications] 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)

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

[Publications] 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)

[Publications] 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)

山本嘉則東北大学, 大学院・理学研究科, 教授 (60029519)