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1993 Fiscal Year Annual Research Report

新しい選択的有機化学プロセスの開発と生理活性分子の高効率合成への応用に関する研究

Research Project

Project/Area Number 03403017
Research InstitutionHokkaido University

Principal Investigator

杉野目 浩  北海道大学, 工学部, 教授 (00000779)

Co-Investigator(Kenkyū-buntansha) 仙北 久典  北海道大学, 工学部, 助手 (50241360)
折登 一彦  北海道大学, 工学部, 助教授 (20109482)
徳田 昌生  北海道大学, 工学部, 助教授 (80001296)
Keywords光化学反応 / ラジカル反応 / ストロイド / リグナン / キノン / アルコキシルラジカル / セスキテルペン合成 / 電極反応
Research Abstract

交付申請書類記載の各項目順に成果を記す。
1キノンの光付加反応-光で生成した2-メルカプトナフトキノンとオレフィンの[3+2]光付加、[3+2]光付加反応をキーステップとする天然物イソタンシノンの骨格合成、2-アリールアミノ-、2-アルキルアミノナフトキノンの光アルキルならびに光アシル化反応、2-ヒドロキシナフトキノンとナフトール類の光付加など有機合成化学に有用な新プロセスを開発し、さらに天然物合成に応用した。
2[2+2]光シクロ付加-β-開裂反応をキーステップとする有機合成法の開発-新たにこの2段階プロセスによる官能基を有するビシクロ[5.4.0]ウンデカン骨格合成法を開発し、該法により、セスキテルペンであるヒマチャレンの全合成を達成した。
3ステロイドエノンオキシムの光転位-新たに多数のコレスタン系α,β-不飽和オキシムを合成し、第1,2年度に見い出した光異性化、立体特異的光付加の一般性を吟味し、新知見を得た。
4アルコキシルラジカルの選択的フラグメンテーションを利用するリグナンの全合成一新たに天然リグナンである(±)-ヤンガンビンの全合成を達成した。
5反応性電極を用いる新規有機合成-電解調整亜鉛が有機合成に極めて有用であることを見い出し、この活性亜鉛を用いてアルデヒド、ケトン類の有効なイソプレニル化法を開発し、(±)-イプセノールを合成してその有効性を示した。
6その他-第1,2年度の研究成果を含め全般につき、とりまとめを行なった。

  • Research Products

    (33 results)

All Other

All Publications (33 results)

  • [Publications] H.Suginome: "Photoinduced Molecular Transformations.Part 137.A New General Synthesis of 3-Substituted (1H)-3,4-Dihydrobenzo[2]pyran-1-ones, (3,4-Dihydrocoumarins).." J.Chem.Soc.Perkin Trans.1. 111-115 (1993)

  • [Publications] H.Suginome: "Photoinduced Molecular Transformations.Part 138.A New Route to Dibenzo[a,d]cycloalkanes and Their Naphtho-analogues via Ring Expansion of..." J.Chem.Soc.Perkin Trans.1. 825-829 (1993)

  • [Publications] H.Suginome: "One Step Synthesis of 2,3-Dihydronaphtho[2,3-b]thiophene-4, 9-diones by a New Regioselective [2+3] Photoaddition of Photogenerated 2-Mercapto...." J.Chem.Soc.Chem.Commun.807-809 (1993)

  • [Publications] H.Suginome: "Photoinduced Molecular Transformations.140.New One-step General Synthesis of Naphtho[2,3-b]furan-4,9-diones and Their 2,3-Dihydro Derivatives by the...." J.Org.Chem.58. 4614-4618 (1993)

  • [Publications] H.Suginome: "Photoinduced Molecular Transformations.141.New One-Step General Synthesis of 4,7-Benzofurandiones by the Regioselective (3+2) Photoaddition of 2-...." J.Chem.Soc.Perkin Trans.1. 1449-1452 (1993)

  • [Publications] H.Suginome: "Photoinduced Molecular Transformations.Part 142.New One-step Syntheses of 1H-Benz[f]indole-4,9-diones and 1H-Indole-4,7-diones by a New...." Helv.Chim.Acta.76. 2942-2950 (1993)

  • [Publications] H.Suginome: "Photoinduced Molecular Transformations.Part 143.(2+2)Photoaddition of 3-Hydroxy-1-benzopyran-2-one, 3-Benzyloxycarbonyloxy-1-benzopyran-2-...." J.Chem.Soc.Perkin Trans.1. 2837-2842 (1993)

  • [Publications] H.Suginome: "Photoinduced Molecular Transformations.Part 144.One-Carbon Intercalation of γ- and δ-Lactones involving the β-Scission of Alkoxyl Radicals as the Key Step:.." J.Chem.Soc.Perkin Trans.1. 3007-3010 (1993)

  • [Publications] M.Tokuda: "New Total Synthesis of(-)-N-Methylanisomycin by Anodic Cyclization of δ-Alkenylamine" Tetrahedron. 49. 2413-2426 (1993)

  • [Publications] M.Tokuda: "Convenient lsoprenylation of Aldebydes and Ketones: Synthesis of(±)-lpsenol" Synthesis. 1086-1088 (1993)

  • [Publications] M.Tokuda: "New Preparation of Reactive Zinc Metal by Electrolysis and Its Use for a Facile Isopreneylation of Aldehydes and Ketones" Tetrahedron Lett.7607-7610 (1993)

  • [Publications] H.Suginome: "Photoinduced Molecular Transformations.Part 145.Regioselective[3+2]Photoadditions of 2-Hydroxy-1,4-phenanthrenedione with Electron-rich ...." J.Chem.Soc.Perkin Trans.1. (発表予定).

  • [Publications] H.Suginome: "Photoinduced Molecular Transformations.Part 146.Photoacylation and Photoalkylation of 2-Arylamino- and 2-Alkylamino-1,4-naphthoquinones" J.Chem.Soc.Perkin Trans.1. (発表予定).

  • [Publications] H.Suginome: "Photoinduced Molecular Transformations.Part 147.(2+2)Photoaddition of Protected 4-Hydroxy-1(2H)-isoquinolinone with an Electron-deficient Alkene..." Heterocycles. 37. 283-288 (1994)

  • [Publications] K.Orito: "A New Synthesis of Functionalized Bicyclo[5.4.0]undecane Skeleton based on a sequence involving[2+2]Photoaddition and Regioselective β-Scission of ...." J.Chem.Soc.Chem.Commun.(発表予定).

  • [Publications] H.Suginome: "Photoinduced Molecular Transformations.Part 149.Photochemistry of the Oximes of Some Steroidal α,β-Unsaturated Cyclic Ketones and Their Deuterio..." J.Chem.Soc.Perkin Trans.1. (発表予定).

  • [Publications] H.Suginome: "Photoinduced Molecular Transformations.Part 150.New Photoadditions of 2-Hydroxy-1,4-naphthoquinones with Naphthols and their Derivatives" J.Chem.Soc.Perkin Trans.1. (発表予定).

  • [Publications] H.Suginome: "Photoinduced Molecular Transformations.Part 151.A New Total Synthesis of(±)-α-Himachalene based on a Sequence involving[2+2]Photoaddition and..." J.Chem.Soc.Perkin Trans.1. (発表予定).

  • [Publications] H.Suginome: "Photoinduced Molecular Transformations.Part 152.Photorearrangements of the Oximes of the Cholestane Series with a Double Bond at Their Bridgehead Position" J.Chem.Soc.Perkin Trans.1. (発表予定).

  • [Publications] H.Suginome: "Photoinduced Molecular Transformations.Part 153.Ring Expansion based on(2+2)Photoaddition followed by β-Scission of Alkoxyl Radicals generated from..." J.Chem.Soc.Perkin Trans.1. (発表予定).

  • [Publications] M.Tokuda: "New Stereoselective Synthesis of trans-2,5-Disubstituted Pyrrolidines by Cyclization of Aminyl Radicals generated from 2- and/or 5-substituted ...." J.Chem.Soc.Perkin Trans.1. (発表予定).

  • [Publications] K.Orito: "New Synthesis of Phthalideisoquinoline Alkaloids via a Stereoselective Hydride Reduction of 1-(2'-Bromobenzoyl)-3,4-dihydroisoquinoline Methiodide, ...." Synlett. (発表予定).

  • [Publications] H.Suginome: "Photoinduced Molecular Transformations.Part 154.One-Step Synthesis of 1H-Benz[g]indole-4,5-diones by a Regioselective[3+2]Photoaddition of 4-Amino..." J.Chem.Soc.Perkin Trans.1. (発表予定).

  • [Publications] K.Orito: "Photoinduced Molecular Transformations.Part 155.A New Stereo- and Regioselective Synthesis of 2,6-Diaryl-3,7-dioxabicyclo[3.3.0]octane Lignans..." J.Org.Chem.(発表予定).

  • [Publications] K.Orito: "Photoinduced Molecular Transformations.Part 156.Total Synthesis of(±)-Methyl Piperitol and(±)-Yanganbin based on a Selective β-Scission of ..." J.Org.Chem.(発表予定).

  • [Publications] H.Suginome: "New Synthesis of Mecrolides by Three or Four-Atoms Ring Expansion of Cyclic Ketones through a Consecutive Intramolecular Homolytic Addition-β-Scission..." J.Chem.Soc.Chem.Commun.(発表予定).

  • [Publications] H.Suginome: "Photoinduced Molecualr Transformations.Part 158.A New Total Synthesis of(±)-Caryophyllene and (±)-Isocaryophyllene based on Three-carbon Ring..." J.Chem.Soc.Perkin Trans.1. (発表予定).

  • [Publications] H.SUGINOME: "Hypohalite Photochemistry. in“Handbook of Organic Photochemistry and Photobiology"" CRC Press,London,U.K.(発表予定),

  • [Publications] H.SUGINOME: "Remote Functionalization by Nitrites - the Barton Reaction. in“Handbook of Organic Photochemistry and Photobiology"" CRC Press,London,U.K.(発表予定),

  • [Publications] H.SUGINOME: "Z-E Isomerization of Imines, Oximes and Azo-Compounds, in“Handbook of Organic Photochemistry and Photobiology"" CRC Press,London,U.K.(発表予定),

  • [Publications] H.SUGINOME: "“A Dictionary of Scientists"" Harpu Collins,Glasgow,U.K.(発表予定),

  • [Publications] H.SUGINOME: "“Photochemical Key Steps in Organic Synthesis"" VCH Verlag,Weinheim,Germany(発表予定),

  • [Publications] H.SUGINOME: "Mercury(II) Oxide/Iodine(or Bromine)in“Encyclopedia of Reagents for Organic Synthesis"" Wiley,New York,U.S.A.(発表予定),

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Published: 1995-02-08   Modified: 2016-04-21  

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