2003 Fiscal Year Annual Research Report

多元素環状化合物の創製

Research Project

Project/Area Number	12056101
Research Institution	The University of Tokyo
Principal Investigator	奈良坂紘一東京大学, 大学院・理学系研究科, 教授 (50016151)
Co-Investigator(Kenkyū-buntansha)	岩澤伸治東京工業大学, 大学院・理工学研究科, 教授 (40168563) 村上正浩京都大学, 大学院・工学研究科, 教授 (20174279) 橋本俊一北海道大学, 大学院・薬学研究科, 教授 (80107391)
Keywords	多元素環状化合物 / 合成 / オキシム / Bラクタム / 触媒反応 / 複素環化合物 / カルボニルイリド
Research Abstract	本特定領域研究は,従来複素環化合物と呼ばれていたN,S,Oを含む環状化合物に加え,P,Siから各種金属元素に至る多種の完素を含んだ環状化合物群,すなわち多元素環状化合物の,革新的な合成法や多段階合成戦略の開発を検討するとともに,これら化合物の反応性を総合的な見地から解明することを目的とする。本年度は、平成15年6月10・11日に北海道大学学術交流会館にて第三回公開シンポジウムを、また平成16年1月8・9日に東京大学弥生講堂にて第四回公開シンポジウムを開催し、それぞれ36名、35名の班員が成果報告を行った。いずれのシンポジウムも多数の大学ならびに企業の研究者に加え、近隣の大学の学生が参加し、活発な質疑討論が行われた。また現在、班員全員に3年間にわたる本特定領域研究の成果報告書の作成を依頼し,近日中にこれをとりまとめの冊子として班員に配布する予定である。併せて本特定領域研究で得られた新たな知見の中から特に優れた成果を選び、それらの研究背景をも含めて解説した教科書的な書籍を作成するための準備を行っている。本年度は本特定領域研究の最終年度にあたり,班員が各自の研究課脚に関しとりまとめを行うべく研究を遂行した。以下にその中から代表的な成果を示す。奈良坂はオキシム化合物を利用して,一電子還元を利用するラジカル環化反応の触媒化やパラジウム触媒を用いる新形式の含窒素複素環化合物の合成法の開発に成功した。橋本はスクアレン合成酵素阻害剤であるザラゴジン酸の立体選択的な第二世代合成法の確立に成功した。村上はカチオン性ルテニウム・ビニリデン錯体を触媒として利用する、ピリジンの2位のアルケニル化反応の開発に成功した。岩澤はタングステン錯体を利用する金属含有1,3-双極子の創製に関する研究を展開し,活性中間体の同定ならびに反応機構に関し興味深い知見を得た。

Research Products
(18 results)

All Other

All Publications (18 results)

[Publications] M.Nakamura, M.Yamane, H.Sakurai, K.Narasaka: "Preparation of Furans by Palladium-Catalyzed Reaction of Acylchromates and Propargylic Tosylates"Heterocycles. 59. 333-345 (2003)
[Publications] S.Zaman, M.Kitamura, K.Narasaka: "Synthesis of Polycyclic Imines by Palladium-Catalyzed Domino Cyclization of Di- and Trienyl Ketone O-Pentafluorobenzoyloximes"Bull.Chem.Soc.Jpn.. 76巻. 1055-1062 (2003)
[Publications] M.Kitamura, S.Chiba, K.Narasaka: "Synthesis of Primary Amines and N-Methylamines by the Electrophilic Amination of Grignard Reagents with 2-Imidazolidinone O-Sulfonyloxime"Bull.Chem.Soc.Jpn.. 76巻. 1063-1070 (2003)
[Publications] M.Yoshida, M.Kitamura, K.Narasaka: "Synthesis of Dihydropyrrole and Pyrrole Derivatives by Radical Cyclization of γ,δ-Unsaturated Ketone O-Acetyloximes."Bull.Chem.Soc.Jpn.. 76巻. 2003-2008 (2003)
[Publications] H.Yanagisawa, K.Miura, M.Kitamura, K.Narasaka: "Intramolecular Substitution Reaction of Lithium Alkylidene Carbeniods. Regioselective Synthesis of Indenes"Bull.Chem.Soc.Jpn.. 76. 2009-2026 (2003)
[Publications] M.Kitamura, M.Yoshida, T.Kikuchi, K.Narasaka: "Synthesis of Quinolines and 2H-Dihydropyrroles by Nucleophilic Substraction at the Nitrogen Atom of Oxime Derivatives"Synthesis. 2003. 2415-2426 (2003)
[Publications] M.Murakami, S.Hori: "Ruthenium-Mediated Regio- and Stereoselective Alkenylation of Pyridine"J.Am.Chem.Soc.. 125. 4720-4721 (2003)
[Publications] S.Suginome, A.Yamamoto, M.Murakami: "Palladium- and Nickel-Catalyzed Intramolecular Cyanoboration of Alkynes"J.Am.Chem.Soc.. 125. 6358-6359 (2003)
[Publications] S.Suginome, T.Ohmura, Y.Miyake, S.Mitani, Y.Ito, M.Murakami: "Enantioface-Selective Palladium-Catallyzed Silaboration of Allenes via Double Asymmetric Induction"J.Am.Chem.Soc.. 125. 11174-11175 (2003)
[Publications] M.Murakami, M.Hasegawa, H.Igawa: "Theoretical and Experimental Studies on the Thermal Ring Opening Reaction of Cyclobutene Having a Stannyl Substituent at the 3-Position"J.Org.Chem.. 69. 587-590 (2004)
[Publications] T.Miura, K.Kiyota, H.Kusama, K.Lee, H.Kim, S.Kim, P.H.Lee, N.Iwasawa: "W(CO)_5(L)-Catalyzed Endo-Selective Cyclization of Allenyl Silyl Enol Ethers : An Efficient Method for the Cyclopentene Annulation onto α,β-Unsaturated Ketones,"Org.Lett.. 5. 1725-1728 (2003)
[Publications] K.Lee, H.Kim, T.Miura, K.Kiyota, H.Kusama, S.Kim, N.Iwasawa, P.H.Lee: "Indium-Mediated β-Allylation, β-Propargylation, and β-Allenylation onto α,β-Unsaturated Ketones : Reactions of in-Situ-Generated 3- tert-Butyldimethylsillyloxyalk-2-enylsulfonium Salts with in-Situ-Generated Organoindium Reagents,"J.Am.Chem.Soc.. 125. 9682-9688 (2003)
[Publications] J.Takaya, H.Kusama, N.Iwasawa: "Isolation and Reaction of (Indolin-3-ylidene)pentacarbonyltungsten Generated from Tungsten-Containing Azomethine Ylide"Chem.Lett.. 33. 16-17 (2004)
[Publications] H.Kusama, H.Funami, J.Takaya, N.Iwasawa: "Platinum(II)-Catalyzed Reaction of 2-Alkynylbenzoates or Benzothioates with Vinyl Ethers : A Concise Method for Synthesis of 1-Acyl-4-alkoxy- or 1 -Acyl-4-alkylsulfanyl-naphthalene Derivatives"Org.Lett.. 6. 605-608 (2004)
[Publications] M.Nakajima, T.Yokota, M.Saito, S.Hashimoto: "Enantioselective Aldol Reactions of Trichlorosilyl Enol Ethers Catalyzed by Chiral N, N'-dioxides and Monodentate N-oxides"Tetrahedron Lett.. 45. 61-64 (2003)
[Publications] S.Nakamura, Y.Hirata, T.Kurosaki, M.Anada, O.Kataoka, S.Kitagaki, S.Hashimoto: "Total Synthesis of the Squalene Synthase Inhibitor Zaragozic Acid C by a Carbonyl Ylide Cycloaddition Strategy"Angew.Chem., Int.Ed.. 42. 5351-5355 (2003)
[Publications] M.Nakajima, S.Yamamoto, Y.Yamaguchi, S.Nakamura, S.Hashimoto: "Enantioselective Michael Additions of β-Keto Esters to α,β-Unsaturated Carbonyl Compounds Catalyzed by a Chiral Biquinoline N, N'-dioxide-Scandium Trifluoromethanesulfonate Complex,"Tetrahedron. 59. 7307-73** (2003)
[Publications] H.Tsutsui, Y.Yamaguchi, S.Kitagaki, S.Nakamura, M.Anada, S.Hashimoto: "Dirhodium(II) Tetrakis[N-tetrafluorophthaloyl-(S)- tert-leucinate] : an Exceptionally Effective Rh(II) Catalyst for Enantiotopically Selective Aromatic C-H Insertions of Diazo Ketoesters,"Tetrahedron Asym.. 14. 817-821 (2003)

2003 Fiscal Year Annual Research Report

多元素環状化合物の創製

Principal Investigator

奈良坂 紘一 東京大学, 大学院・理学系研究科, 教授 (50016151)

Research Products

[Publications] M.Nakamura, M.Yamane, H.Sakurai, K.Narasaka: "Preparation of Furans by Palladium-Catalyzed Reaction of Acylchromates and Propargylic Tosylates"Heterocycles. 59. 333-345 (2003)

[Publications] S.Zaman, M.Kitamura, K.Narasaka: "Synthesis of Polycyclic Imines by Palladium-Catalyzed Domino Cyclization of Di- and Trienyl Ketone O-Pentafluorobenzoyloximes"Bull.Chem.Soc.Jpn.. 76巻. 1055-1062 (2003)

[Publications] M.Kitamura, S.Chiba, K.Narasaka: "Synthesis of Primary Amines and N-Methylamines by the Electrophilic Amination of Grignard Reagents with 2-Imidazolidinone O-Sulfonyloxime"Bull.Chem.Soc.Jpn.. 76巻. 1063-1070 (2003)

[Publications] M.Yoshida, M.Kitamura, K.Narasaka: "Synthesis of Dihydropyrrole and Pyrrole Derivatives by Radical Cyclization of γ,δ-Unsaturated Ketone O-Acetyloximes."Bull.Chem.Soc.Jpn.. 76巻. 2003-2008 (2003)

[Publications] H.Yanagisawa, K.Miura, M.Kitamura, K.Narasaka: "Intramolecular Substitution Reaction of Lithium Alkylidene Carbeniods. Regioselective Synthesis of Indenes"Bull.Chem.Soc.Jpn.. 76. 2009-2026 (2003)

[Publications] M.Kitamura, M.Yoshida, T.Kikuchi, K.Narasaka: "Synthesis of Quinolines and 2H-Dihydropyrroles by Nucleophilic Substraction at the Nitrogen Atom of Oxime Derivatives"Synthesis. 2003. 2415-2426 (2003)

[Publications] M.Murakami, S.Hori: "Ruthenium-Mediated Regio- and Stereoselective Alkenylation of Pyridine"J.Am.Chem.Soc.. 125. 4720-4721 (2003)

[Publications] S.Suginome, A.Yamamoto, M.Murakami: "Palladium- and Nickel-Catalyzed Intramolecular Cyanoboration of Alkynes"J.Am.Chem.Soc.. 125. 6358-6359 (2003)

[Publications] S.Suginome, T.Ohmura, Y.Miyake, S.Mitani, Y.Ito, M.Murakami: "Enantioface-Selective Palladium-Catallyzed Silaboration of Allenes via Double Asymmetric Induction"J.Am.Chem.Soc.. 125. 11174-11175 (2003)

[Publications] M.Murakami, M.Hasegawa, H.Igawa: "Theoretical and Experimental Studies on the Thermal Ring Opening Reaction of Cyclobutene Having a Stannyl Substituent at the 3-Position"J.Org.Chem.. 69. 587-590 (2004)

[Publications] T.Miura, K.Kiyota, H.Kusama, K.Lee, H.Kim, S.Kim, P.H.Lee, N.Iwasawa: "W(CO)_5(L)-Catalyzed Endo-Selective Cyclization of Allenyl Silyl Enol Ethers : An Efficient Method for the Cyclopentene Annulation onto α,β-Unsaturated Ketones,"Org.Lett.. 5. 1725-1728 (2003)

[Publications] J.Takaya, H.Kusama, N.Iwasawa: "Isolation and Reaction of (Indolin-3-ylidene)pentacarbonyltungsten Generated from Tungsten-Containing Azomethine Ylide"Chem.Lett.. 33. 16-17 (2004)

[Publications] H.Kusama, H.Funami, J.Takaya, N.Iwasawa: "Platinum(II)-Catalyzed Reaction of 2-Alkynylbenzoates or Benzothioates with Vinyl Ethers : A Concise Method for Synthesis of 1-Acyl-4-alkoxy- or 1 -Acyl-4-alkylsulfanyl-naphthalene Derivatives"Org.Lett.. 6. 605-608 (2004)

[Publications] M.Nakajima, T.Yokota, M.Saito, S.Hashimoto: "Enantioselective Aldol Reactions of Trichlorosilyl Enol Ethers Catalyzed by Chiral N, N'-dioxides and Monodentate N-oxides"Tetrahedron Lett.. 45. 61-64 (2003)

[Publications] S.Nakamura, Y.Hirata, T.Kurosaki, M.Anada, O.Kataoka, S.Kitagaki, S.Hashimoto: "Total Synthesis of the Squalene Synthase Inhibitor Zaragozic Acid C by a Carbonyl Ylide Cycloaddition Strategy"Angew.Chem., Int.Ed.. 42. 5351-5355 (2003)

[Publications] M.Nakajima, S.Yamamoto, Y.Yamaguchi, S.Nakamura, S.Hashimoto: "Enantioselective Michael Additions of β-Keto Esters to α,β-Unsaturated Carbonyl Compounds Catalyzed by a Chiral Biquinoline N, N'-dioxide-Scandium Trifluoromethanesulfonate Complex,"Tetrahedron. 59. 7307-73** (2003)

奈良坂紘一東京大学, 大学院・理学系研究科, 教授 (50016151)