2002 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よばれていた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元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。本年度は実質的な研究の2年目にあたり,公募研究への新規参加者の数も多かったため,まず年度初めに班員全員に研究計画の提出を求め,これをまとめて冊子としたものを作成し,班員に配布した。併せてこれを参考に班員間での意見交換ならびに共同研究を積極的に推進することを依頼した。次いで平成14年9月25,26日に大阪大学豊中キャンパスにて第二回公開シンポジウムを開催し,38名の班員の成果報告・討論を行った。本シンポジウムは日本化学会秋期年会の一環として行われ,班員のみならず多数の日本化学会参加者が成果報告を聴講した。また年度末には班員に本年度の成果報告書の作成を依頼し,近日中にこれを冊子としてまとめ班員に配布する予定である。本年度の研究は概ね順調に進展し興味深い成果が挙がっている。例えば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触媒的な合成法の開発に成功した。橋本はピンナトキシンAの全合成に向けその基本骨格となるBCDEFG環の最後のG環部を分子内Diels-Alder反応を利用して立体選択的に構築することに成功した。村上はロジウム錯体を利用し炭素-炭素結合の切断を伴う反応性メタラサイクルの創製を実現し,これを利用して各種複素環化合物の合成を行った。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,多環性インドール化合物合成に全く新しい手法を提供した。

Research Products
(18 results)

All Other

All Publications (18 results)

[Publications] Koganemaru Y, Kitamura M, Narasaka K: "Synthesis of dihydropyrrole derivatives by copper-catalyzed cyclization of γ,δ-unsaturated ketone O-methoxycarbonyloximes"Chem. Lett.. 8号. 784-785 (2002)
[Publications] Tsutsui H, Kitamura M, Narasaka K: "Synthesis of pyrrole derivatives by palladium-catalyzed cyclization of γ,δ-unsaturated ketone O-pentafluorobenzoyloximes"Bull. Chem. Soc. Jpn.. 75巻7号. 1451-1460 (2002)
[Publications] Kitamura M, Chiba S, Saku O, Narasaka K: "Palladium-catalyzed synthesis of 1-azaazulenes from cycloheptatrienylmethyl ketone O-pentafluorobenzoyl oximes"Chem. Lett.. 6号. 606-607 (2002)
[Publications] Narasaka K: "Metal-assisted amination with oxime derivatives"Pure Appl. Chem.. 74巻1号. 143-149 (2002)
[Publications] Yoshida M, Kitamura M, Narasaka K: "Synthesis of 3,4-dihydro-2H-pyrroles from gamma, delta-unsaturated ketone O-acetyloximes"Chem. Lett.. 2号. 144-145 (2002)
[Publications] Yanagisawa H, Miura K, Kitamura M, Narasaka K, Ando K: "Intramolecular substitution reaction of alkylidene-lithium carbenoids : Regioselective synthesis of indenes"Helv. Chim. Acta.. 85巻10号. 3130-3135 (2002)
[Publications] H.Saito, H.Oishi, S.Kitagaki, S.Nakamura, M.Anada, S.Hashimoto: "Enantio-and Diastereoselective Synthesis of cis-2-Aryl-3-methoxycarbonyl-2,3-dihydrobenzofurans via the Rh-(II)-Catalyzed C-H Insertion Process"Org. Lett.. 4号. 3887-3890 (2002)
[Publications] M.Yamawaki, H.Tsutsui, S.Kitagaki, M.Anada, S.Hashimoto: "Dirhodium(II) Tetrakis[N-tetrachlorophthaloyl-(S)-tert-leucinate] : a New Chiral Rh(II) Catalyst for Enantioselective Amidation of C-H Bonds"Tetrahedron Lett.. 43巻. 9561-9564 (2002)
[Publications] S.Nakamura, J.Inagaki, M.Kudo, T.Sugimoto, K.Obara, M.Nakajima, S.Hashimoto: "Studies Directed toward the Total Synthesis of Pinnatoxin A : Synthesis of the 6,5,6-Dispiroketal (BCD Ring) System by Double Hemiketal Formation/Hetero-Michael Addition Strategy"Tetrahedron. 58巻. 10353-10374 (2002)
[Publications] S.Nakamura, J.Inagaki, T.Sugimoto, Y.Ura, S.Hashimoto: "A Highly Stereoselective Synthesis of the C10-C31 (BCDEF Ring) Portion of Pinnatoxin A"Tetrahedron. 58巻. 10375-10386 (2002)
[Publications] M.Murakami, T.Itahashi, Y.Ito: "Catalyzed Intramolecular Olefin Insertion into a CarbonCarbon Single Bond"J. Am. Chem. Soc.. 124号. 13976-13977 (2002)
[Publications] M.Murakami, H.Igawa, Y.Ito: "Rhodium-catalysed Addition of Arylboronic Acids to Oxabenzonorbornadienes"Chem. Commun.. 390-391 (2002)
[Publications] M.Murakami, M.Ubukata, Y.Ito: "Ruthenium-Mediated Domino Sequence FormingSix-Membered Ring Diene from Ene-Yne and Alkene"Chem. Lett. 294-295 (2002)
[Publications] M.Murakami, H.Igawa: "A Study on the Stereochemical Course of b-Oxygen Elimination with a Rhodium(I) complex"Helv. Chim. Acta. 85巻. 4182-4188 (2002)
[Publications] H.Kusama, Y.Shiozawa, M.Shido, N.Iwasasa: "Tandem Cyclizations of Benzopyranylidenetungsten(0) Complexes with Electron-Rich Dienes for the Stereoselective Synthesis of Polycyclic Carbon Skeletons"Chem. Lett.. 124-125 (2002)
[Publications] H.Kusama, H.Yamabe, N.Iwasawa: "W(CO)_5-Amine Catalyzed Exo-and Endo-Selective Cyclizations of w-Alkynyl Silyl Enol Ethers : A Highly Useful Method for the Construction of Polycyclic Compounds"Org. Lett.. 4巻. 2569-2571 (2002)
[Publications] H.Kusama, J.Takaya, N.Iwasawa: "A Facile Method for the Synthesis of Polycyclic Indole Derivatives : The Generation and Reaction of Tungsten-Containing Azomethine Ylides"J. Am. Chem. Soc.. 124. 11592-11593 (2002)
[Publications] N.Iwasawa, T.Miura, K.Kiyota, H.Kusama, K.Lee, P.H.Lee: "An Efficient Method for the Cyclopentene Annulation onto a, b-Unsaturated Ketones : W(CO)_5(L)Catalyzed 5-Endo-Dig Cyclization of 6-Siloxy-5-en-1-ynes"Org. Lett.. 4巻. 4463-4466 (2002)

2002 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] Koganemaru Y, Kitamura M, Narasaka K: "Synthesis of dihydropyrrole derivatives by copper-catalyzed cyclization of γ,δ-unsaturated ketone O-methoxycarbonyloximes"Chem. Lett.. 8号. 784-785 (2002)

[Publications] Tsutsui H, Kitamura M, Narasaka K: "Synthesis of pyrrole derivatives by palladium-catalyzed cyclization of γ,δ-unsaturated ketone O-pentafluorobenzoyloximes"Bull. Chem. Soc. Jpn.. 75巻7号. 1451-1460 (2002)

[Publications] Kitamura M, Chiba S, Saku O, Narasaka K: "Palladium-catalyzed synthesis of 1-azaazulenes from cycloheptatrienylmethyl ketone O-pentafluorobenzoyl oximes"Chem. Lett.. 6号. 606-607 (2002)

[Publications] Narasaka K: "Metal-assisted amination with oxime derivatives"Pure Appl. Chem.. 74巻1号. 143-149 (2002)

[Publications] Yoshida M, Kitamura M, Narasaka K: "Synthesis of 3,4-dihydro-2H-pyrroles from gamma, delta-unsaturated ketone O-acetyloximes"Chem. Lett.. 2号. 144-145 (2002)

[Publications] Yanagisawa H, Miura K, Kitamura M, Narasaka K, Ando K: "Intramolecular substitution reaction of alkylidene-lithium carbenoids : Regioselective synthesis of indenes"Helv. Chim. Acta.. 85巻10号. 3130-3135 (2002)

[Publications] H.Saito, H.Oishi, S.Kitagaki, S.Nakamura, M.Anada, S.Hashimoto: "Enantio-and Diastereoselective Synthesis of cis-2-Aryl-3-methoxycarbonyl-2,3-dihydrobenzofurans via the Rh-(II)-Catalyzed C-H Insertion Process"Org. Lett.. 4号. 3887-3890 (2002)

[Publications] M.Yamawaki, H.Tsutsui, S.Kitagaki, M.Anada, S.Hashimoto: "Dirhodium(II) Tetrakis[N-tetrachlorophthaloyl-(S)-tert-leucinate] : a New Chiral Rh(II) Catalyst for Enantioselective Amidation of C-H Bonds"Tetrahedron Lett.. 43巻. 9561-9564 (2002)

[Publications] S.Nakamura, J.Inagaki, T.Sugimoto, Y.Ura, S.Hashimoto: "A Highly Stereoselective Synthesis of the C10-C31 (BCDEF Ring) Portion of Pinnatoxin A"Tetrahedron. 58巻. 10375-10386 (2002)

[Publications] M.Murakami, T.Itahashi, Y.Ito: "Catalyzed Intramolecular Olefin Insertion into a CarbonCarbon Single Bond"J. Am. Chem. Soc.. 124号. 13976-13977 (2002)

[Publications] M.Murakami, H.Igawa, Y.Ito: "Rhodium-catalysed Addition of Arylboronic Acids to Oxabenzonorbornadienes"Chem. Commun.. 390-391 (2002)

[Publications] M.Murakami, M.Ubukata, Y.Ito: "Ruthenium-Mediated Domino Sequence FormingSix-Membered Ring Diene from Ene-Yne and Alkene"Chem. Lett. 294-295 (2002)

[Publications] M.Murakami, H.Igawa: "A Study on the Stereochemical Course of b-Oxygen Elimination with a Rhodium(I) complex"Helv. Chim. Acta. 85巻. 4182-4188 (2002)

[Publications] H.Kusama, Y.Shiozawa, M.Shido, N.Iwasasa: "Tandem Cyclizations of Benzopyranylidenetungsten(0) Complexes with Electron-Rich Dienes for the Stereoselective Synthesis of Polycyclic Carbon Skeletons"Chem. Lett.. 124-125 (2002)

[Publications] H.Kusama, H.Yamabe, N.Iwasawa: "W(CO)_5-Amine Catalyzed Exo-and Endo-Selective Cyclizations of w-Alkynyl Silyl Enol Ethers : A Highly Useful Method for the Construction of Polycyclic Compounds"Org. Lett.. 4巻. 2569-2571 (2002)

[Publications] H.Kusama, J.Takaya, N.Iwasawa: "A Facile Method for the Synthesis of Polycyclic Indole Derivatives : The Generation and Reaction of Tungsten-Containing Azomethine Ylides"J. Am. Chem. Soc.. 124. 11592-11593 (2002)

[Publications] N.Iwasawa, T.Miura, K.Kiyota, H.Kusama, K.Lee, P.H.Lee: "An Efficient Method for the Cyclopentene Annulation onto a, b-Unsaturated Ketones : W(CO)_5(L)Catalyzed 5-Endo-Dig Cyclization of 6-Siloxy-5-en-1-ynes"Org. Lett.. 4巻. 4463-4466 (2002)

奈良坂紘一東京大学, 大学院・理学系研究科, 教授 (50016151)