1992 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 Institution	Hokkaido 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	電極反応 / 光化学反応 / アルコキシルラジカル / リグナン / セスキテルペン / ステロイド / オキシム / カルボキシル化反応
Research Abstract	交付申請書記載の各項目順に成果を記す。 1・〔3+2〕光付加によるアネレーション新たに、2-ヒドロキシ-ノ,4-フェナントレンキノンとフェニルアセチンの位置選択的光付加によりフェナントロ〔2,3-6〕フラン-4,11-ジオン滂導体の生成、2-メルカプトナフトキノンとアルケンの光付加によるヒドロナフト〔2,3-6)チオフエン-4,9-ジオン類の生成を見出した。 2・アルコキシルラジカルのベータ開製の有機合成への応用新たにフルコキシルラジカルのβ-開製をキーステップとして、非対称天然リグナンである(±)-メチルピペリトール、セスキテルペンである(±)カリオフィレン、(±)イソカリオフィレンを全合成した。また、同様の手法を用いてセスキテルペンであるα-ヒマチヤレンの骨格を合成した。アルコキシルラジカルの開製反応を用いて2-ヒドロキシテトラヒドロピランからアルキル置換ピロリジンを合成する新手法を開発した。 3・ステロイド系不飽和オキシムの光による分子内転位反応 β,γ体への光異性化、メタノールの二重結合への立体特異的光付加の機構を重水素標識化実験により解明した。 4・電極反応を用いる新規有機化学プロセスの開発反応性電極を用いる置換ハロゲン化プロパルギルと炭酸ガスの反応による電解カルボキシル化反応、電解調製活性亜鉛を用いるカルボニル化合物のイソプレニル反応等を開発した。 5・その他〔2+2〕光付加-ベータ開製による複業環の合成、不飽和アミンのアニオン的環化によるシス-2置換ピロリジンの合成法を開発した。

Research Products
(20 results)

All Other

All Publications (20 results)

[Publications] K.Kobayashi: "Photounduced Molecular Transformations. 128. Regioselective [2+2] Photocycloaddition of 3-Acetoxyquiolin-2(1H)-one with Alkenes and Formation of Furo [2,3-c] qyionlin-4(5H)-ones, 1-Benzazocine-2,3-....." J.Org.Chem.57. 599-606 (1992)
[Publications] K.Kobayadhi: "One-Step Symthesis of 2,3-Dihydroanthra[2,3-b]furan-4,11-Diones and 1H-Naphtho[2,3-f] indole-4,11-Diones by [2+3] Photoaddition of 2-Hydroxy-or 2-Amino-1,4-Anthracenedions with Cyclic and Acyclic.." Heterocycles. 33. 553-562 (1992)
[Publications] 杉野目浩: "フリーラジカルと高選択的有機合成" 化学と工業. 2014-2018 (1992)
[Publications] H.Suginome: "Photoinduced Molecular Transformations. Part 130. Novel StereospecificPhotorearrangement and Stereospecific Addition of Methanol in Steroidal α,β-Unsaturated Cyclic Ketone Oximes" J.Chem.Soc.Perkin Trans.1. 427-432 (1992)
[Publications] H.Suginome: "Photoinduced Molecular Transformations.Part 131.Synthesis of 18-Norsteroids,Deoxofukujusonorone and the Related Steroids, Based on a Selectice β-Scission of Alkoxyl Radicals as the Key Step" J.Chem.Soc.Perkin Trans.1. 1837-1842 (1992)
[Publications] H.Syginome: "Photoinduced Molecular Transformations.Part 132.A Two-Step Intramolecular Transposition of 17β-Acetyl Group of pergnan-20-one to the C-18 through Type II Reaction of the Excited Carbonyl...." J.Chem.Soc.Perkin Trans.1. 1843-1848 (1992)
[Publications] H.Suginome: "Photoinduced Molecular Transformations. Part 133.A New Photoinduced Deconjugation of Steroidal α,β-Unsaturated Cyclic Ketone Oxime into the β,γ-Unsaturated Isomer involving ....." J.Chem.Soc.Perkin Trans.1. 1849-1854 (1992)
[Publications] K.Kobayashi: "New General Synthesis of tert-Butyl 3-Amino-2-naphthalenecarboxylates by an Electrocyclic Reaction of o-Quinonedimethides generated from tert-Buty (Z)-3-Amino-3...." J.Chem.Soc.Chem.Commun.780-781 (1992)
[Publications] H.Suginome: "Photoinduced Molecular Transformations.Part 134. Photoinduced Stereospecific Addition of Methanol to 5β-Cholest-1-en-3-one Oxime and Photoinduced Decomhugation of its 1-Methyl Derivative..." J.Chem.Soc.Perkin Trans.1. 3103-3110 (1992)
[Publications] H.Suginome: "Efficient Formation of Spiroterahydrofuran Ring by the Ionic Cyclization of Bishomoallyl Tertiary Alcohols via Their Hypoiodites" J.Chem.Soc.Perkin Trans.1. 2917-2923 (1992)
[Publications] K Kobayashi: "Photoinduced Molecular Transformations. Part 135. New Synthesis of Taiwanin C and Justicidin E based on a Radical Cascade Process involving β-Scission of Alkoxyl Radicals Generated from 3-Aryl....." J.Chem.Soc.Perkin Trans.1. 3111-3124 (1992)
[Publications] H.Suginome: "Photoinduced Molecular Transformations. Part 136. Reactions of Alkoxyl Radicals Generated from Hypoiodites of 3β-Hydroxy-7-oxa- ^5-Steroids. Synthesis of Some Functionalized Oxasteroids" J.Chem.Soc.Perkin Trans.1. 3119-3124 (1992)
[Publications] H.Fujita: "Stereoselective Cyclization of δ-Alkenylamines catalyzed with Butyllithium. Synthesis of cis-N-Methyl-2,5-disubstituted Pyrrolidines" Tetrahedron Lett.6359-6362 (1992)
[Publications] K.Kobayashi: "Photoinduced Molecular Transformations. Part 137. A New General Synthesis of 3-Substituted (1H)-3,4-Dihydrobenzo[2]pyran-1-ones,(3,4-Dihydroisocoumarins),via Radical and Photochemical..." J.Chem.Soc.Perkin Trans.1. 111-115 (1993)
[Publications] K.Kobayashi: "Photoinduced Molecular Transformations.Part 138.A New Route to Dibenzo[a,d]cycloalkanes and Their Naphtho-analogyes via Ring Expansion of Benzocyclobutenols involving Selective β-Scission of ....." J.Chem.Soc.Perkin Trans.1.
[Publications] M.Tokuda: "New Total Synthesis of (-)-N-Methylanisomycin by Anodic Cyclization of δ-Alkenylamine" Tetrahedron.
[Publications] K.Kobayashi: "One-step Synthesis of 2,3-Dihydronaphtho[2,3-bz]thiophene-4, 9-diones by a New Regioselective [3+2] Photoaddition of Photogenerated 2-Mercapto-1,4-naphthoquinone with Alkenes" J.Chem.Soc.,Chem.Commun.
[Publications] H.Suginome: "New Developments in Photoinduced Radical Reactions in Organic Synthesis "Modern Methodology in Organic Synthesis"" Kodansha, 19 (1992)
[Publications] H.Suginome: ""Photochemistry of Esrers,and Their Thio Analogues "in the Chemistry of Functional Groups Series Edited by Saul Patai "Chemistry of Acid Derivatives" Supplemesnt B2: Part 2." John Wiley & Sons.Ltd., 90 (1992)
[Publications] 杉野目浩: "スポーツト化学" 大日本図書, 12 (1992)

1992 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

Principal Investigator

杉野目 浩 北海道大学, 工学部, 教授 (00000779)

Research Products

[Publications] K.Kobayashi: "Photounduced Molecular Transformations. 128. Regioselective [2+2] Photocycloaddition of 3-Acetoxyquiolin-2(1H)-one with Alkenes and Formation of Furo [2,3-c] qyionlin-4(5H)-ones, 1-Benzazocine-2,3-....." J.Org.Chem.57. 599-606 (1992)

[Publications] K.Kobayadhi: "One-Step Symthesis of 2,3-Dihydroanthra[2,3-b]furan-4,11-Diones and 1H-Naphtho[2,3-f] indole-4,11-Diones by [2+3] Photoaddition of 2-Hydroxy-or 2-Amino-1,4-Anthracenedions with Cyclic and Acyclic.." Heterocycles. 33. 553-562 (1992)

[Publications] 杉野目 浩: "フリーラジカルと高選択的有機合成" 化学と工業. 2014-2018 (1992)

[Publications] H.Suginome: "Photoinduced Molecular Transformations. Part 130. Novel StereospecificPhotorearrangement and Stereospecific Addition of Methanol in Steroidal α,β-Unsaturated Cyclic Ketone Oximes" J.Chem.Soc.Perkin Trans.1. 427-432 (1992)

[Publications] H.Suginome: "Photoinduced Molecular Transformations.Part 131.Synthesis of 18-Norsteroids,Deoxofukujusonorone and the Related Steroids, Based on a Selectice β-Scission of Alkoxyl Radicals as the Key Step" J.Chem.Soc.Perkin Trans.1. 1837-1842 (1992)

[Publications] H.Syginome: "Photoinduced Molecular Transformations.Part 132.A Two-Step Intramolecular Transposition of 17β-Acetyl Group of pergnan-20-one to the C-18 through Type II Reaction of the Excited Carbonyl...." J.Chem.Soc.Perkin Trans.1. 1843-1848 (1992)

[Publications] H.Suginome: "Photoinduced Molecular Transformations. Part 133.A New Photoinduced Deconjugation of Steroidal α,β-Unsaturated Cyclic Ketone Oxime into the β,γ-Unsaturated Isomer involving ....." J.Chem.Soc.Perkin Trans.1. 1849-1854 (1992)

[Publications] K.Kobayashi: "New General Synthesis of tert-Butyl 3-Amino-2-naphthalenecarboxylates by an Electrocyclic Reaction of o-Quinonedimethides generated from tert-Buty (Z)-3-Amino-3...." J.Chem.Soc.Chem.Commun.780-781 (1992)

[Publications] H.Suginome: "Photoinduced Molecular Transformations.Part 134. Photoinduced Stereospecific Addition of Methanol to 5β-Cholest-1-en-3-one Oxime and Photoinduced Decomhugation of its 1-Methyl Derivative..." J.Chem.Soc.Perkin Trans.1. 3103-3110 (1992)

[Publications] H.Suginome: "Efficient Formation of Spiroterahydrofuran Ring by the Ionic Cyclization of Bishomoallyl Tertiary Alcohols via Their Hypoiodites" J.Chem.Soc.Perkin Trans.1. 2917-2923 (1992)

[Publications] K Kobayashi: "Photoinduced Molecular Transformations. Part 135. New Synthesis of Taiwanin C and Justicidin E based on a Radical Cascade Process involving β-Scission of Alkoxyl Radicals Generated from 3-Aryl....." J.Chem.Soc.Perkin Trans.1. 3111-3124 (1992)

[Publications] H.Suginome: "Photoinduced Molecular Transformations. Part 136. Reactions of Alkoxyl Radicals Generated from Hypoiodites of 3β-Hydroxy-7-oxa- ^5-Steroids. Synthesis of Some Functionalized Oxasteroids" J.Chem.Soc.Perkin Trans.1. 3119-3124 (1992)

[Publications] H.Fujita: "Stereoselective Cyclization of δ-Alkenylamines catalyzed with Butyllithium. Synthesis of cis-N-Methyl-2,5-disubstituted Pyrrolidines" Tetrahedron Lett.6359-6362 (1992)

[Publications] K.Kobayashi: "Photoinduced Molecular Transformations. Part 137. A New General Synthesis of 3-Substituted (1H)-3,4-Dihydrobenzo[2]pyran-1-ones,(3,4-Dihydroisocoumarins),via Radical and Photochemical..." J.Chem.Soc.Perkin Trans.1. 111-115 (1993)

[Publications] K.Kobayashi: "Photoinduced Molecular Transformations.Part 138.A New Route to Dibenzo[a,d]cycloalkanes and Their Naphtho-analogyes via Ring Expansion of Benzocyclobutenols involving Selective β-Scission of ....." J.Chem.Soc.Perkin Trans.1.

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

[Publications] K.Kobayashi: "One-step Synthesis of 2,3-Dihydronaphtho[2,3-bz]thiophene-4, 9-diones by a New Regioselective [3+2] Photoaddition of Photogenerated 2-Mercapto-1,4-naphthoquinone with Alkenes" J.Chem.Soc.,Chem.Commun.

[Publications] H.Suginome: "New Developments in Photoinduced Radical Reactions in Organic Synthesis "Modern Methodology in Organic Synthesis"" Kodansha, 19 (1992)

[Publications] H.Suginome: ""Photochemistry of Esrers,and Their Thio Analogues "in the Chemistry of Functional Groups Series Edited by Saul Patai "Chemistry of Acid Derivatives" Supplemesnt B2: Part 2." John Wiley & Sons.Ltd., 90 (1992)

[Publications] 杉野目 浩: "スポーツト化学" 大日本図書, 12 (1992)

杉野目浩北海道大学, 工学部, 教授 (00000779)

[Publications] 杉野目浩: "フリーラジカルと高選択的有機合成" 化学と工業. 2014-2018 (1992)

[Publications] 杉野目浩: "スポーツト化学" 大日本図書, 12 (1992)