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1990 Fiscal Year Annual Research Report

新しい選択的ラジカルプロセスによる有機合成法の開発に関する研究

Research Project

Project/Area Number 01470085
Research InstitutionHokkaido University

Principal Investigator

杉野目 浩  北海道大学, 工学部, 教授 (00000779)

Co-Investigator(Kenkyū-buntansha) 小林 和裕  北海道大学, 工学部, 助手 (90161976)
折登 一彦  北海道大学, 工学部, 助手 (20109482)
徳田 昌生  北海道大学, 工学部, 助教授 (80001296)
Keywordsマクロリド合成 / ステロイド / リグナン合成 / 電極反応 / 光化学反応 / アルコキシルラジカル / 含複素環キノン / 有機分子変換
Research Abstract

交付申請書記載の各項目順に成果を記す。
1・生物活性を有する18ーならびに19ーノルステロイドの高効率合成
昨年度にひきつゞき、ステロイド系ラクト-ルから発生せしめたアルコキシルラジカルの位置選択的ベ-タ開裂反応をキ-ステップとして種々の18ーノルアンドロスタン系ステロイドを合成した。
2・〔2+3〕光付加反応によるフロナフトキノンおよびベンズインド-ルキノン類の合成
2ーヒドロキシナフトキノンとオレフインならびに2ーアミノナフトキノンとオレフインの新しい〔2+3〕光付加反応を見出し、これらの付加反応をキ-ステップとして天然フロナフトキノンであるマチュリノンを含む多数のフロナフトキノンを合成した。また、天然ベンズインド-ルキノンであるキナマイシンの骨格を含む多数のベンズインド-ルキノンを合成した。
3・アルコキシルラジカルの位置選択的ベ-タ開裂反応を利用するリグナン類の合成
アルコキシルラジカルの位置選択的ベ-タ開裂反応をキ-ステップとするリグナン合成の新しい一般法を確立し、同法により(±)セサシンの新合成を行った。
4・電極反応による含窒素複素環の合成
電極酸化応で生成する窒素原子ラジカルの分子内二重結合への付加を利用して種々のピロリジン環を合成する新方法を確立した。
5・マクロリドの新合成法の開発
アルコキシルラジカルの遠隔ラジカル付加ー位置選択的ベ-タ開裂反応を利用して天然マクロリドである(±)ルシフエイオリドを含む多数の11ー16員環マクロリドを合成した。

  • Research Products

    (28 results)

All Other

All Publications (28 results)

  • [Publications] H.Suginome: "Photoinduced Molecular Transformations.105.Intramolecular Addition vs.βーScission of Oxyl Radical generated from AーHomoー5αーcholestー1ーenー4αー and 4βーols Hypoiodites and 4ーMethyl Hypoiodites" J.Chem.Soc.Perkin Trans.1. 1033-1039 (1990)

  • [Publications] H.Suginome: "Photoinduced Molecular Transformations.106.The Formation of Cyclic Anhydrides via Regioselective βーScission of Alkoxyl Radicals generated from 5ー and 6ーMembered αーHydroxy Cyclic ketones" J.Chem.Soc.Perkin Trans.1. 1239-1245 (1990)

  • [Publications] M.Tokuda: "Regioselectivity in Electrochemical Allylation of Carbonyl Compounds.A Synthesis of Egomaketone by a Regioselective Allylation" J.Org.Chem.54. 5608-5613 (1989)

  • [Publications] K.Orito: "ALongーrange Intramolecular Functionalization by Alkoxy Radicals:a Longーrange Intramolecular Hydroxylation of Cー25 of Cholestane Side Chain" J.Chem.Soc.Chem.Commun.1829-1831 (1989)

  • [Publications] H.Suginome: "Photoinduced Molecular Transformations.Part 107.A Versatile Substitution of a Carbonyl Group of Steroidal Ketones by a Hetero Atom.The Synthesis of Azaー,Oxa,Thia,Selenaー,and Teluriosteroids" J.Org.Chem.55. 2170-2176 (1990)

  • [Publications] H.Suginome: "Photoinduced Molecular Transformations.Part 109.A Conformational Dependence of the Stereochemistry of Photochemical 1,3ーAcyl Shifts of β,γーUnsaturated Cyclic Ketones,BーHomocholestー5ーenー7aーone and AーHomoー5αーcholestー1ーenー4ーone" J.Chem.Soc.,Perkin Trans.1. 1247-1257 (1990)

  • [Publications] K.Orito: "A Longーrange Intramolecular Functionalization by Alkoxyl Redicals:a Longーrange Intramolecular Oxygnation of C(15) of the Androstane Skeleton" J.Chem.Soc.,Chem.Commun.1074-1076 (1990)

  • [Publications] K.Orito: "A WagnerーMeerwein Rearrangement of the Cholestane Skeleton induced by a Longーrange Intramolecular Hybrogen Abstraction by Alkoxyl Radical to a CarbonーCarbon Double Bond" J.Chem.Soc.,Chem.Commun.1076-1078 (1990)

  • [Publications] K.Orito: "LongーRange Intramolecular Functionalization by Alkoxyl Radicals;LongーRange Intramolecular double Functionalization of Ring C of Cholestane and Androstane skeletons" Tetrahedron lett.5921-5924 (1990)

  • [Publications] H.Suginome: "Intramolecular β,γーAddition of Allylic Alkoxyl Radicals.A New General Synthesis of αーIodoepoxides by Photolysis of Allylic Alkohol Hypoiodites in the Presence of Mercury(II) Oxide,Iodine and Pyridine in Benzene" J.Chem.Soc.,Chem.Commun.1629-1631 (1990)

  • [Publications] M.Tokuda: "NewFacile Synthesis of Substituted 2ーBenzylideneーpyrrolidines by the Anionic Cyclization of σーAlkynylamines" Tetrahedron Lett.31. 5353-5356 (1990)

  • [Publications] H.Suginome: "Photoinduced Molecular Transformations.Part 119.Photochemical Nitrogen Insertion to Bicyclo[2.2.1]heptanones;the photochemistry of Oximes of (+)ーFenchone and (+)ーCamphor" J.Chem.Soc.,Perkin Trans I.

  • [Publications] M.Tokuda: "New Efficient Electrochemical Allylation of Aldehydes and Ketones with a Cadmiumーmodified Electrode" Chem.Lett.461-462 (1990)

  • [Publications] H.Suginome: "Photoinduced Molecular Transformations.110.Formation of Furoquinolinones <via>___ー βーscission of Cyclobutanoxyl Radicals generated from [2+2]Photoadducts of 4ーHydroxyー2ーquinolone and Acyclic and Cyclic Alkenes:Xーray Crystal Structure of(6aα,6bβ,10aβ,10bα.)ー (±)ー10bーAcetoxyー6a,6b,7,8,9,10,10a,10b=octahydroー5ーmethylbenzo[3,4] cyclobutal1,2ーC__ー]quinolinー6(5H__ー)ーone" J.Org.Chem.55. 4933-4943 (1990)

  • [Publications] H.Suginome: "Transformation of Epiandrosterone into 3ーOxaー,3ーThiaー,3ーSelenaー,and 3ーAzaー17ーoxaandrostanes of the 5αーSeries based on βーScission of Alkoxyl Radicals" Steroids. 55. 353-359 (1990)

  • [Publications] H.Suginome: "Photoinduced Molecular Transformations.112.Transformation of Steroids into RingーA aromatized Steroids and 19ーNorsteroids involving a Regioselective βーScission of Alkoxyl Radicals:Synthesis of Two Marine Matural Products,19ーNorー5αーcholestanー3βーo1 and 19ーNorcholestー4ーenー3ーone,and New Synthesis of Estrone and 19ーNortestosterore" J.Chem.Soc.Perkin Trans.I. 2199-2205 (1990)

  • [Publications] H.Suginome: "Photoinduced Molecular Transformations.113.Oneーstep Transformations of Cyclic Ethers into ωーIodoalkyl Formates and of Aldehyde Cyclic Acetals into Monoesters of α,ωーAlkanediols by Iodoxyl Radical" J.Chem.Soc.Perkin Trans.I. 2825-2829 (1990)

  • [Publications] K.Kobayashi: "An Efficient Synthesis of 5,7ーDihydroxyー4ーmethyliobenzofuranー1(3H__ー)ーone,a Metabolite of <aspergillus flavus>___ー and a key Intermediate in the Synthesis of Mycophenolic Acid" Bull.Chem.Soc.Jpn.63. 2435-2437 (1990)

  • [Publications] M.Tokuda: "Stereoselective Synthesis of 4ー or 5ー Substituted 2ーBenzyl and 2ーBenzoylpyrrolidines by Means of Anodic Oxidation of σー Alkenylamines" Tetrahedron.

  • [Publications] M.Tokuda: "Regiocontrolled Allylation of Carbonyl Compounds by Electrochemical Reduction of Allylic Halides.Electroorganic SynthesisーFestscript in honor of Manuel Baizer (成書、分担)"

  • [Publications] 徳田 昌生: "反応性金属を陽極として用いる有機合成" 化学と工業. 43. 1980-1983 (1990)

  • [Publications] K.Kobayashi: "Oneーstep Synthesis of 1H__ーーBenz[f__ー]indoleー4,9ーdiones by New Rogioーselective Photoaddition of 2ーAminoー1,4ーnaphthoquinone with Various Alkenes and its Application to OneーStep Synthesis of Kinamucin Skeletor" Angew.Chem.

  • [Publications] K.Kobayashi: "New Oneーstep Synthesis of 2,3ーDihydronaphtho[2,3ーb__ー]ー4,9ーdiones by Regioselective Photoaddition of 2ーHydroxyー1,4ーnaphthoquinones with Various Alkenes and its Application to a Twoーstep Synthesis of Maturinone" J.Org.Chem.

  • [Publications] K.Kobayashi: "Photoinduced Molecular Transformations,Part 122.New Short Step General Synthesis of Isobenzofuranー1(3H__ー)ーones (phthalides) based on a Songle or Double βーScission of Alkoxyl Radicals generated from lーEthylー1,2ーdibydrobenzocyclobutenーlーols and from 1,3ー Dihydroisobenzofuranーlーols;Synthesis of Some Natural Phthalides" Tetrahedron.

  • [Publications] H.Suginome: "OneーStep Formation of 3,4ーFuroー2ーquinolinones by a New Regioーselective [2+3] Photoaddition of 4ーHydroxyーmethoxy quinolinー2ーone with Acyclic and Cyclic Alkenes" Tetrahedron Lett.

  • [Publications] K.Kobayashi: "Photoinduced Molecular Transformations 123.A New Route to γーSubstituted γーLactones and σーSubstituted σーLactones based on the Regioselective βーScission of Alkoxyl Radicals generated from Transannular Hemiacetals" J.Chem.Soc.Perkin Trans.I.

  • [Publications] H.Suginome: "Supramolecular Assembries:New Developments in Bifunetional Chemistry Ed.by Y.Murakami (分担)" Mita press, 340 (1990)

  • [Publications] H.Suginome: "Advanced Molecular Conversion Ed.by N.Sonoda (分担)" MYU k.k., 359 (1991)

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Published: 1993-08-11   Modified: 2016-04-21  

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