1994 Fiscal Year Annual Research Report

合成等価体創製のための分子設計と有機合成への応用開発研究

Research Project

Project/Area Number	05554022
Research Institution	University of Tsukuba
Principal Investigator	細見彰筑波大学, 化学系, 教授 (00004440)
Co-Investigator(Kenkyū-buntansha)	顕谷忠俊住友化学工業株式会社, 有機合成研究所, 主席研究員富永義則長崎大学, 薬学部, 助手 (70100881) 三浦勝清筑波大学, 化学系, 助手 (20251035) 北條信筑波大学, 化学系, 講師 (50229150)
Keywords	合成等価体 / 有機合成 / 1,3-双極子試薬 / 立体特異的合成 / テトラヒドロフラン
Research Abstract	本研究では新しい1,3-双極子反応剤,特に他の方法では得難いカルボニルイリド等価体と見做せるもしくは前駆体となる合成反応剤を設計し,それら反応剤の環化付加反応による複素環化合物の立体特異的な短段階合成法を確立できた.即ち,本年度はケイ素の特性を活かした高選択的合成,新規反応の開発研究等を行った.とくに,不安定化学種を安定な有機金属分子中に閉じ込め,必要なときに取り出せるような新規反応剤を設計し創製すると共に高選択的な有機合成反応に応用する研究では,これまで発生法が限られ合成化学的な利用が不十分であったカルボニルイリドの生成法の確立に伴い,これまでにない[3+2]環化付加反応によって立体特異的にテトラヒドロフランやジヒドロフランの一段階合成法が達成できた.本新規カルボニルイリドの合成法を利用して生理活性化合物であるリグナンの短段階での合成にも成功した.本反応は1)出発物質であるクロロメチル(シリルメチル)エーテルは対応するシリメチルアルコールとホルマリンの混合物に塩化水素ガスを通すことにより容易に得られる.2)活性化剤としてフッ化セシウムを用いて,温和な反応条件下反応を達成できる.3)フマル酸エステル,アクリル酸エステルなどの活性アルケンとの反応は高収率でテトラヒドロフラン誘導隊を立体特異的に与える.4)活性アルキンとの反応では高収率でテトラヒドロフランを与える.5)スチレンや通常のアルキル基置換のアルケン,さらにはビニルエーテルやアリルアセタートなどの不活性アルケンとも良好に反応して環化生成物を与える,などの特徴を持つ.

Research Products
(13 results)

All Other

All Publications (13 results)

[Publications] Akira HOSOMI: "A Novel and Efficient Generation of Functionalized Vinylcopper Reagents and their Reactions with Electrophiles.Synthesis of β-Methylthiobutenolides" Chem.Lett.3. 437-440 (1994)
[Publications] Akira HOSOMI: "Reductive Cupration of α-Cyanoketenedithioacetals.Generation of Functionalized(E)-Vinylcopper Reagents and their Reactions with Electrophiles" Bull.Chem.Soc.Jpn.67. 1495-1498 (1994)
[Publications] Akira HOSOMI: "Reaction of 2-Oxiranylallylsilanes with Acetals.Direct Introduction of a Vinyloxirane Moiety" J.Organometal.Chem.473. C1-C3 (1994)
[Publications] Akira HOSOMI: "Introduction of Electrophiles to the α-Position of α,β-Unsaturated Aldehydes and Ketones by Sequential Conjugate Aminosilylation-Alkylation-Deamination" Chem.Lett.4. 719-722 (1994)
[Publications] Akira HOSOMI: "The Preparation of N-Acylpyrazoles and their Behavior toward Alcohol" Synthesis. 1. 61-65 (1994)
[Publications] Akira HOSOMI: "Ozonolysis of Substituted Isoxazoles" Heterocycles. 37. 1075-1082 (1994)
[Publications] Akira HOSOMI: "Photocycloaddition of Benzothiazole-2-thiones to Alkenes" Helv.Chim.Acta. 77. 981-987 (1994)
[Publications] Akira HOSOMI: "Aminolysis of N-Acylpyrazoles" Heterocycles. 38. 1407-1412 (1994)
[Publications] Akira HOSOMI: "Heteroarylthiomethylsilanes.Synthesis and Application to Heteroarylthiomethylation of Carbonyl Compounds" Heteroatom Chem.5. 229-234 (1994)
[Publications] Akira HOSOMI: "Direct Generation and Reactions of Sulfur-Substituted Allylcoppers Reagents by a Novel Reduction Reaction Using Organocuprate" J.Chem.Soc.Chem.Commun.(印刷中). (1994)
[Publications] Akira HOSOMI: "Stereoselective Synthesis of Di-and Trisubstituted Alkenes via Intramolecular Addition of Vinyl Radicals to Alkenes" Tetrahedron Lett. 35. 9605-9608 (1994)
[Publications] Akira HOSOMI: "Divergent Stereoselectivity in the Reduction of α,β-Epoxy Ketones Using Hydridosilicates" Tetrahedron Lett. 35(印刷中). (1994)
[Publications] Akira HOSOMI: "Encyclopedia of Reagents for Organic Synthesis." John Wiley & Sons,Ed.by L.A.Paquette, 1333 (1994)

1994 Fiscal Year Annual Research Report

合成等価体創製のための分子設計と有機合成への応用開発研究

Principal Investigator

細見 彰 筑波大学, 化学系, 教授 (00004440)

Research Products

[Publications] Akira HOSOMI: "A Novel and Efficient Generation of Functionalized Vinylcopper Reagents and their Reactions with Electrophiles.Synthesis of β-Methylthiobutenolides" Chem.Lett.3. 437-440 (1994)

[Publications] Akira HOSOMI: "Reductive Cupration of α-Cyanoketenedithioacetals.Generation of Functionalized(E)-Vinylcopper Reagents and their Reactions with Electrophiles" Bull.Chem.Soc.Jpn.67. 1495-1498 (1994)

[Publications] Akira HOSOMI: "Reaction of 2-Oxiranylallylsilanes with Acetals.Direct Introduction of a Vinyloxirane Moiety" J.Organometal.Chem.473. C1-C3 (1994)

[Publications] Akira HOSOMI: "Introduction of Electrophiles to the α-Position of α,β-Unsaturated Aldehydes and Ketones by Sequential Conjugate Aminosilylation-Alkylation-Deamination" Chem.Lett.4. 719-722 (1994)

[Publications] Akira HOSOMI: "The Preparation of N-Acylpyrazoles and their Behavior toward Alcohol" Synthesis. 1. 61-65 (1994)

[Publications] Akira HOSOMI: "Ozonolysis of Substituted Isoxazoles" Heterocycles. 37. 1075-1082 (1994)

[Publications] Akira HOSOMI: "Photocycloaddition of Benzothiazole-2-thiones to Alkenes" Helv.Chim.Acta. 77. 981-987 (1994)

[Publications] Akira HOSOMI: "Aminolysis of N-Acylpyrazoles" Heterocycles. 38. 1407-1412 (1994)

[Publications] Akira HOSOMI: "Heteroarylthiomethylsilanes.Synthesis and Application to Heteroarylthiomethylation of Carbonyl Compounds" Heteroatom Chem.5. 229-234 (1994)

[Publications] Akira HOSOMI: "Direct Generation and Reactions of Sulfur-Substituted Allylcoppers Reagents by a Novel Reduction Reaction Using Organocuprate" J.Chem.Soc.Chem.Commun.(印刷中). (1994)

[Publications] Akira HOSOMI: "Stereoselective Synthesis of Di-and Trisubstituted Alkenes via Intramolecular Addition of Vinyl Radicals to Alkenes" Tetrahedron Lett. 35. 9605-9608 (1994)

[Publications] Akira HOSOMI: "Divergent Stereoselectivity in the Reduction of α,β-Epoxy Ketones Using Hydridosilicates" Tetrahedron Lett. 35(印刷中). (1994)

[Publications] Akira HOSOMI: "Encyclopedia of Reagents for Organic Synthesis." John Wiley & Sons,Ed.by L.A.Paquette, 1333 (1994)

細見彰筑波大学, 化学系, 教授 (00004440)