1989 Fiscal Year Annual Research Report

新増炭素手法による分子変換

Research Project

Project/Area Number	01607005
Research Institution	Osaka University
Principal Investigator	大城芳樹大阪大学, 工学部, 教授 (70028984)
Co-Investigator(Kenkyū-buntansha)	村井真二大阪大学, 工学部, 教授 (00029050) 園田昇大阪大学, 工学部, 教授 (20083983) 桑嶋功東京工業大学, 理学部, 教授 (50016086) 北尾悌次郎大阪府立大学, 工学部, 教授 (10081324) 秋葉欣哉広島大学, 理学部, 教授 (20011538)
Keywords	増炭素反応 / 分子変換 / ヘテロ環合成 / 立体選択的合成 / 環変換 / 触媒反応 / カルボニル化 / カルボニルアニオン
Research Abstract	現在不可能視されている物質変換法の実現や、多段階間接法による変換法の超短縮化を目的とし、新反応試剤や新触媒の開発、反応基質の活性化や新活性中間体の発生法の確立、多官能分子の化学修飾や分子形状に基因する新しい分子変換法の開発と、それらの合成化学的応用を系統的に展開した。本年度の成果を以下に要約する。 (1)多官能高歪み三員環の開環に基づく三原子組込み増炭素型のヘテロ環合成法を開発した。(2)ケイ素とルイス酸の特性を利用する反応場を設計し、選択的かつ超高率的環拡大骨格変換法を確立した。(3)カルコゲン元素を触媒とする超高率的かつ高選択的カルボニル化反応を開拓した。(4)カルボニルアニオンのエノラートへの分子内変換という新手法により、非従来型炭素鎮延長手法を確立した。(5)シロキシベンゾピリリウム塩を活用する位置選択的な高効率一段階増環反応を見出した。(6)五配位アリルシリケートによる位置特異的かつ高立体選択的アリル化反応を明らかにした。(7)硫黄官能基をもつプロパンカルボン酸による光学活性シクロプロパンカルボン酸の高率的合成法を開発した。(8)フェニルチオ基とメトキシ基に挟まれた1,1ー双極子等価な新規増炭素反応剤を開発した。(9)フッ素原子の特性を活用する含フッ素ヘテロ環の新合成法の開拓と応用を展開した。(10)有機クロム反応剤による高度な官能基、位置および立体選択的合成法を見出した。(11)渡環的DielsーAlder反応を利用した超高率的ステロイド骨格合成法を確立した。(12)新増炭素反応による積層型ポルフィリン多量体の簡便かつ選択的合成法を開発した。(13)リンの特性を活用する新増炭素試薬を開発し高効率的縮環形成法を確立した。以上の結果は新規な超高率的増炭素反応を開拓し、応用範囲の広い新方法論として展開したものである。その成果は化学関連学術分野だけでなく、それを基盤とする各産業分野の発展に大いに貢献するものである。

Research Products
(22 results)

All Other

All Publications (22 results)

[Publications] K.Akiba et al.: "Silver Ion Promoted Rearrangement of 4ーAry1ーand 4ーAlkeny1ー3ーbromoー4,6ーdimethy1ー3,4ーdihydroー2ーpyrones" J.Org.Chem. 54. 1935-1940 (1989)
[Publications] K.Akiba et.al: "(4+2)Type Cycloaddition of Chromones with α,βーUnsaturated Ketones Mediated by tーButyldimethylsilyl Triflate:Oneーpot Preparation of Xanthones Derivatives" Heterocycles. 29. 35-38 (1989)
[Publications] M.Hojo et al.: "Convenient Synthesis of 1,1,1ーTrifluoroー4,5ーdiazaー2,4ーAlkadienes and 1ーArylー3,3.3ーtrifluoroー1ーpropanones" Synthesis. 43-45 (1989)
[Publications] M.Kira et al.: "Allylation of αーHydroxy Ketones with Allyltrifluorosilanes in the Presence of Triethylamine.Stereochemical Regulation Involving Chelated Bicyclic Transition States" J.Am.Chem.Soc.111. 6429-6431 (1989)
[Publications] M.Kira et al.: "Highly Stereoselective Allylation of Aldehydes with Pentacoordinate Allylsilicates in Hydroxylic Media.Discrimination between Linear and αーBranched Alkanals" J.Am,.Chem.Soc.112. 257-260 (1989)
[Publications] T.Kitao et al.: "Synthesis and Properties of N,N'ーand N,CoーVinylene Linked Bisporphyrins" Chem.Lett.671-674 (1989)
[Publications] T.Kirao et al.: "The Reaction of Cobalt(III)Porphyrins with αーDiazoーβーDicarbonyl Compounds" Chem.Lett.885-888 (1989)
[Publications] A.Kaji et al.: "Regioselective and Stereospecific Palladium(0)ーcatalyzed Reactions of 4ーChloroaectoxyalkー2ーenoic Esters with Carbon and Nitrogen Nucleophiles" J.Chem.Soc.,Perkin Trans.
[Publications] I.Kuwajima et al.: "A Highly Efficient EightーMemberedーRing Cyclization for Costruction of the Taxane Carbon Framework" J.Am.Chem.Soc.111. 8277-8279 (1989)
[Publications] I.Kuwajima et al.: "SiliconーBased Nucleophile Mediated OneーCarbon Ring Expansion of 1ー(Trimethylsilyl)cycloalkanecarbaldehydes" Tetrahedron Lett.30. 6551-6554 (1989)
[Publications] T.Minami et al.: "New Synthesis of Cyclobutane Annelated Compounds by the Use of a(1ーCyclobutenyl)ーtriphenylphosphonium Salt" J.Org.Chem.54. 974-977 (1989)
[Publications] T.Minami et al.: "〔Cycloalkyl(phenylseleno)methylene〕triphenylphosphoranes:Synthesis and Reactions of(Phenylseleno)alkenes" Bull.Chem.Soc.Jpn.
[Publications] S.Murai et al.: "Cobalt Carbonyl Catalyzed Reactions of Cyclic Ethers with a Hydrosilane and Carbon Monoxide.A New Synthetic Reaction Equivalent to Nucleophilic Oxymethylation" J.Am.Chem.Soc.111. 7938-7946 (1989)
[Publications] S.Murai et al.: "Intramolecular Conversion of Acyllithium,Formal〔2+1〕and〔4+1〕Cycloaddition of Carbon Monoxide with 1ー(Silyl)Vinyllithium and 2ーPhenylー1ー(Solyl)Vinyllithium Leading to Cyclopropanone Enolate and Indanone Enolate"
[Publications] Y.Ohshiro et al.: "RingーEnlargement of Diaziridinone:Lewis Acid Pronoted Addition of Nitriles Leading to Triazolinone" J.Org.Chem.
[Publications] Y.Ohshiro et al.: "Synthesis of βーBromobutenolide from 2,2ーDibromocyclopropane Carboxylate" Chem.Lett.
[Publications] J.Otera et al.: "Methoxy(phenylthio)(trimethylsilyl)methane as a OneーCarbon Homologation Reagent:Efficient 1,4ーAddition of a Foumyl or a Carboxy Anion Equinvalent to Cyclic αーEnones Concomitant with in Situ αーAlkylation" J.Org.Chem.54. 5003-5007 (1989)
[Publications] J.Otera et al.: "A Versatile Method for Allylic Sulfide Synthesis" Tetrahedron Lett.30. 2821-2824 (1989)
[Publications] N.Sonoda et al.: "A Mechanistic Study on the SeleniumーCatalyzed Carbonylation of Secondary Amines with Carbon Monoxide" J.Phys.Org.Chem. 2. 359-362 (1989)
[Publications] N.Sonoda et al.: "A New Acess to Acylーand Aroyllithiums via LithiumーTellurium Exchange" J.Am.Chem.Soc.112. 455-456 (1990)
[Publications] K.Utimoto et al.: "Stereoselective Addition of αーChloro Allylic Chromium Reagents to Aldehydes" Tetrahedron Lett.30. 4389-4392 (1989)
[Publications] K.Yamamoto et al.: "Efficient Approach to the OppolzerーKanetani Intermediate for Estrone Methyl Ether Using the Conjugate AdditionーEnolate Methylation of the Cyclopentenone Containing an αーAppended Benzocyclobutane Moiety" Tetrahedron Lett.30. 4999-5002 (1989)

1989 Fiscal Year Annual Research Report

新増炭素手法による分子変換

Principal Investigator

大城 芳樹 大阪大学, 工学部, 教授 (70028984)

Research Products

[Publications] K.Akiba et al.: "Silver Ion Promoted Rearrangement of 4ーAry1ーand 4ーAlkeny1ー3ーbromoー4,6ーdimethy1ー3,4ーdihydroー2ーpyrones" J.Org.Chem. 54. 1935-1940 (1989)

[Publications] K.Akiba et.al: "(4+2)Type Cycloaddition of Chromones with α,βーUnsaturated Ketones Mediated by tーButyldimethylsilyl Triflate:Oneーpot Preparation of Xanthones Derivatives" Heterocycles. 29. 35-38 (1989)

[Publications] M.Hojo et al.: "Convenient Synthesis of 1,1,1ーTrifluoroー4,5ーdiazaー2,4ーAlkadienes and 1ーArylー3,3.3ーtrifluoroー1ーpropanones" Synthesis. 43-45 (1989)

[Publications] M.Kira et al.: "Allylation of αーHydroxy Ketones with Allyltrifluorosilanes in the Presence of Triethylamine.Stereochemical Regulation Involving Chelated Bicyclic Transition States" J.Am.Chem.Soc.111. 6429-6431 (1989)

[Publications] M.Kira et al.: "Highly Stereoselective Allylation of Aldehydes with Pentacoordinate Allylsilicates in Hydroxylic Media.Discrimination between Linear and αーBranched Alkanals" J.Am,.Chem.Soc.112. 257-260 (1989)

[Publications] T.Kitao et al.: "Synthesis and Properties of N,N'ーand N,CoーVinylene Linked Bisporphyrins" Chem.Lett.671-674 (1989)

[Publications] T.Kirao et al.: "The Reaction of Cobalt(III)Porphyrins with αーDiazoーβーDicarbonyl Compounds" Chem.Lett.885-888 (1989)

[Publications] A.Kaji et al.: "Regioselective and Stereospecific Palladium(0)ーcatalyzed Reactions of 4ーChloroaectoxyalkー2ーenoic Esters with Carbon and Nitrogen Nucleophiles" J.Chem.Soc.,Perkin Trans.

[Publications] I.Kuwajima et al.: "A Highly Efficient EightーMemberedーRing Cyclization for Costruction of the Taxane Carbon Framework" J.Am.Chem.Soc.111. 8277-8279 (1989)

[Publications] I.Kuwajima et al.: "SiliconーBased Nucleophile Mediated OneーCarbon Ring Expansion of 1ー(Trimethylsilyl)cycloalkanecarbaldehydes" Tetrahedron Lett.30. 6551-6554 (1989)

[Publications] T.Minami et al.: "New Synthesis of Cyclobutane Annelated Compounds by the Use of a(1ーCyclobutenyl)ーtriphenylphosphonium Salt" J.Org.Chem.54. 974-977 (1989)

[Publications] T.Minami et al.: "〔Cycloalkyl(phenylseleno)methylene〕triphenylphosphoranes:Synthesis and Reactions of(Phenylseleno)alkenes" Bull.Chem.Soc.Jpn.

[Publications] S.Murai et al.: "Cobalt Carbonyl Catalyzed Reactions of Cyclic Ethers with a Hydrosilane and Carbon Monoxide.A New Synthetic Reaction Equivalent to Nucleophilic Oxymethylation" J.Am.Chem.Soc.111. 7938-7946 (1989)

[Publications] S.Murai et al.: "Intramolecular Conversion of Acyllithium,Formal〔2+1〕and〔4+1〕Cycloaddition of Carbon Monoxide with 1ー(Silyl)Vinyllithium and 2ーPhenylー1ー(Solyl)Vinyllithium Leading to Cyclopropanone Enolate and Indanone Enolate"

[Publications] Y.Ohshiro et al.: "RingーEnlargement of Diaziridinone:Lewis Acid Pronoted Addition of Nitriles Leading to Triazolinone" J.Org.Chem.

[Publications] Y.Ohshiro et al.: "Synthesis of βーBromobutenolide from 2,2ーDibromocyclopropane Carboxylate" Chem.Lett.

[Publications] J.Otera et al.: "Methoxy(phenylthio)(trimethylsilyl)methane as a OneーCarbon Homologation Reagent:Efficient 1,4ーAddition of a Foumyl or a Carboxy Anion Equinvalent to Cyclic αーEnones Concomitant with in Situ αーAlkylation" J.Org.Chem.54. 5003-5007 (1989)

[Publications] J.Otera et al.: "A Versatile Method for Allylic Sulfide Synthesis" Tetrahedron Lett.30. 2821-2824 (1989)

[Publications] N.Sonoda et al.: "A Mechanistic Study on the SeleniumーCatalyzed Carbonylation of Secondary Amines with Carbon Monoxide" J.Phys.Org.Chem. 2. 359-362 (1989)

[Publications] N.Sonoda et al.: "A New Acess to Acylーand Aroyllithiums via LithiumーTellurium Exchange" J.Am.Chem.Soc.112. 455-456 (1990)

[Publications] K.Utimoto et al.: "Stereoselective Addition of αーChloro Allylic Chromium Reagents to Aldehydes" Tetrahedron Lett.30. 4389-4392 (1989)

[Publications] K.Yamamoto et al.: "Efficient Approach to the OppolzerーKanetani Intermediate for Estrone Methyl Ether Using the Conjugate AdditionーEnolate Methylation of the Cyclopentenone Containing an αーAppended Benzocyclobutane Moiety" Tetrahedron Lett.30. 4999-5002 (1989)

大城芳樹大阪大学, 工学部, 教授 (70028984)