1997 Fiscal Year Annual Research Report

インターエレメント化合物の新機能開発

Research Project

Project/Area Number	09239102
Research Category	Grant-in-Aid for Scientific Research on Priority Areas
Research Institution	Kyoto University
Principal Investigator	檜山爲次郎京都大学, 工学研究科, 教授 (90026295)
Co-Investigator(Kenkyū-buntansha)	長野哲雄東京大学, 薬学部, 教授 (20111552) 横山正明大阪大学, 工学研究科, 教授 (90029281) 小川昭弥大阪大学, 工学研究科, 助教授 (30183031) 落合正仁徳島大学, 薬学部, 教授 (50127065)
Keywords	インターエレメント化合物 / 酸化的脱硫フッ素化 / フルオロシリカート / モノカルボニルヨードニウムイリド / カルコゲン原子 / ポリシラン / 金コロイド / スーパーオキシド
Research Abstract	この研究では,インターエレメント化合物の未知なる機能をひきだし,積極的に活用することをめざし,インターエレメント結合を切断し,基質へ官能基を導入したり炭素骨格を構築する有機合成の新反応を開発,インターエレメント化合物を利用する機能材料,機能素子への展開,生体反応や生命現象を制御する可能性を探ることを目的としている。本年度の成果は,(1)イオン性インターエレメント化合物の設計と合成化学的応用をめざし,インターエレメント性ハロスルホニウムイオンやフルオロシリカートを反応系内で発生させ酸化的脱硫フッ素化反応や,ケイ素-ケイ素結合の切断を利用する炭素-ケイ素結合生成の新反応を開発した。(2)モノカルボニルヨードニウムイリドを発生させることに初めて成功し,アルデヒドへのアルキリデン移動反応によりα,β-エポキシケトンご合成することに成功した。(3)硫酸やセレンなどのカルコゲン原子と遷移金属とのインターエレメント結合の反応特性を検討し,パラジウム触媒によるカルコゲン-カルコゲン結合,カルコゲン-水素結合のアルキンへの位置および立体選択的付加反応を見つけるとともに、一酸化炭素との組み合わせによる増炭素型付加反応の開発に成功した。(4)金/ポリシラン積層膜に金コロイドを形成させ,これを触媒とするポリシランの熱酸化反応をおこなった。また,金コロイドの形成機構,光記録媒体への応用を検討した。(5)インターエレメント化合物を合成し,その構造と一酸化窒素(NO),スーパーオキシドの生体内での発生と阻害にかかわる活性の相関を検討し,NOの検出試薬の開発に成功した。

Research Products

(24 results)

All Other

All Publications (24 results)

[Publications] 檜山爲次郎: "Copper (I) Salt Promoted Homo-Coupling Reaction of Organosilanes" Chem.Commun.6. 1039-1040 (1997)
[Publications] 檜山爲次郎: "Synthesis and Electro-optical Properties of Novel Liquid Crystals Having a Cyclohexyl Trifluoromethyl Ether Moiety" Chem.Lett.827-828 (1997)
[Publications] 檜山爲次郎: "TBAHF2 and TBAH2F3 as Activating Agents of Organosilanes" Synlett. 6. 693-694 (1997)
[Publications] 檜山爲次郎: "Cu (I) /Pd (0) -Catalyzed Cross-Coupling Reaction of Alkynylsilanes with Arly on Alkenyl Triflates : "Sila"-Sonogashira-Hagihara Coupling" Chem.Lett.12. 1233-1234 (1997)
[Publications] 檜山爲次郎: "Copper (I) Salt Mediated 1,4-Reduction of α,β-Unsaturated Ketones Using Hydrosilanes" Chem.Commun.22. 2159-2160 (1997)
[Publications] 落合正仁: "Generation and Reaction of Monocarbonyl Iodonium Yides : Ester Exchange of Z- (β-Acetoxyvinyl) iodonium Salts with Lithium Ethoxide and Synthesis of α,β-Epoxy Ketones" J.Am.Chem.Soc.119・48. 11598-11604 (1997)
[Publications] 小川昭弥: "Palladium (0) -Catalyzed Regio- and Stereoselective Addition of Heteroatom Compounds Beaxing Si-Se,Ge-Se,and Si-Ge Bonds to Phenylacetylene" J.Organomet.Chem.
[Publications] 小川昭弥: "Highly Regio Selective Thioselenation of Acetylenes By Using a (PhS)_2- (PhSe)_2 Binary System" J.Org.Chem.
[Publications] 小川昭弥: "Diphenyl Diselenide-Assisted Dithiolation of 1,3-Dienes with Diphenyl Disulfide upon Irradiation with Near-UV Light" Tetrahedron Lett.
[Publications] 横山正明: "Colloid Formation from Vacuum Deposited Au Thin Layer on a UV-light Pre-exposed Polysilane Film." Chem.Lett.397-398 (1997)
[Publications] 横山正明: "金/ポリシラン積層膜における金コロイド形成とその光記録メディアへの応用" 応用物理学会・有機分子・バイオエレクトロニクス分科会会誌. 8・4. 189-198 (1997)
[Publications] 横山正明: "Au Colloid Formation in Polysilane/Au layered Film and Its Application as Novel Optical Recording Media" Mol.Lid.Cryst.Communications.
[Publications] 落合正仁: "α-Vinylation of 1,3-Dicarbonyl Compound with Alkenyl (aryl) iodonium Terafluoroborates : Effects of Substituents on the Aromatic Ring and of Radical Inhibitors." J.Org.Chem.62・7. 2130-2138 (1997)
[Publications] 落合正仁: "Acetolysis of Styryl and l-Decenyl Iodonium Salts. Occurrence of Two-Step Mechanism Via Vinylenephenonium Ion and One-Step Inversion Mechanism." J.Am.Chem.Soc. 119・20. 4785-4786 (1997)
[Publications] 落合正仁: "Oxidation of Sulfides to Sulfoxides with Hypervalent (tert-Butylperoxy) iodanes." J.Org.Chem.62・13. 4253-4259 (1997)
[Publications] 落合正仁: "Nucleophilic Vinylic Substitutions of (Z)-(β-Haloal Kenyl) Phenyliodonium Salts with Sodium Benzenesulfinate : First Evidence of a Michael Addition of Nucleophiles to Alkenyliodonium Salts at the CB Atom." J.Org.Chem.62・23. 8001-8008 (1997)
[Publications] 小川昭弥: "Palladium-Catalyzed Carbonylative Lactonization of Propargyl Alcohols with Organic Dichalcogenides and Carbon Monoxide." J.Org.Chem.62・24. 8361-8365 (1997)
[Publications] 小川昭弥: "Highly Regioselective Hydrothiocarboxylation of Acetylenes with Carbon Monoxide and Thiols Catalyzed by Pt (PPh_3)_4" J.Am.Chem.Soc.119・50. 12380-12381 (1997)
[Publications] 長野哲雄: ""Singlet Oxygen Production from Fullerene Derivatires : Effect of Sequential Functionalization of Fullerene Core" Chem.Commun.21-22 (1997)
[Publications] 長野哲雄: "The Regio-and Stereo Selective Oxidation of Steroids with 2,6-Dichloropyridine N-Oxide Catalyzed by Ruthenium Porphyrines." Chem.Commun.801-802 (1997)
[Publications] 長野哲雄: "Inhibitoty Effects of a Fullerence Derivative,Dimalonic Acid C_<60>,on Nitric Oxide-Induced Relaxation of Rabbit Aorta." European Journal Pharmacology. 327. 175-181 (1997)
[Publications] 長野哲雄: "Real-time Measurement of Nitric Oxide Production in Rat Brain by the Combination of Luminol-H202 Chemiluminescenceand Microdialysis" Neuroscience Letters. 233. 157-159 (1997)
[Publications] 長野哲雄: "Pronounced Axial Thiolate Ligand Effect on the Reactivity of High-valent Oxo-iron Porphyrin Intermediate." J.Am.Chem.Soc. 119. 12008-12009 (1997)
[Publications] 長野哲雄: "活性酸素増産剤としての超原子価化合物のデザイン・合成・生物活性評価" 季刊化学総説,超原子価を持つ有機典型元素化合物. 34. 195-205 (1998)

1997 Fiscal Year Annual Research Report

インターエレメント化合物の新機能開発

Principal Investigator

檜山 爲次郎 京都大学, 工学研究科, 教授 (90026295)

Research Products

[Publications] 檜山 爲次郎: "Copper (I) Salt Promoted Homo-Coupling Reaction of Organosilanes" Chem.Commun.6. 1039-1040 (1997)

[Publications] 檜山 爲次郎: "Synthesis and Electro-optical Properties of Novel Liquid Crystals Having a Cyclohexyl Trifluoromethyl Ether Moiety" Chem.Lett.827-828 (1997)

[Publications] 檜山 爲次郎: "TBAHF2 and TBAH2F3 as Activating Agents of Organosilanes" Synlett. 6. 693-694 (1997)

[Publications] 檜山 爲次郎: "Cu (I) /Pd (0) -Catalyzed Cross-Coupling Reaction of Alkynylsilanes with Arly on Alkenyl Triflates : "Sila"-Sonogashira-Hagihara Coupling" Chem.Lett.12. 1233-1234 (1997)

[Publications] 檜山 爲次郎: "Copper (I) Salt Mediated 1,4-Reduction of α,β-Unsaturated Ketones Using Hydrosilanes" Chem.Commun.22. 2159-2160 (1997)

[Publications] 落合 正仁: "Generation and Reaction of Monocarbonyl Iodonium Yides : Ester Exchange of Z- (β-Acetoxyvinyl) iodonium Salts with Lithium Ethoxide and Synthesis of α,β-Epoxy Ketones" J.Am.Chem.Soc.119・48. 11598-11604 (1997)

[Publications] 小川 昭弥: "Palladium (0) -Catalyzed Regio- and Stereoselective Addition of Heteroatom Compounds Beaxing Si-Se,Ge-Se,and Si-Ge Bonds to Phenylacetylene" J.Organomet.Chem.

[Publications] 小川 昭弥: "Highly Regio Selective Thioselenation of Acetylenes By Using a (PhS)_2- (PhSe)_2 Binary System" J.Org.Chem.

[Publications] 小川 昭弥: "Diphenyl Diselenide-Assisted Dithiolation of 1,3-Dienes with Diphenyl Disulfide upon Irradiation with Near-UV Light" Tetrahedron Lett.

[Publications] 横山 正明: "Colloid Formation from Vacuum Deposited Au Thin Layer on a UV-light Pre-exposed Polysilane Film." Chem.Lett.397-398 (1997)

[Publications] 横山 正明: "金/ポリシラン積層膜における金コロイド形成とその光記録メディアへの応用" 応用物理学会・有機分子・バイオエレクトロニクス分科会会誌. 8・4. 189-198 (1997)

[Publications] 横山 正明: "Au Colloid Formation in Polysilane/Au layered Film and Its Application as Novel Optical Recording Media" Mol.Lid.Cryst.Communications.

[Publications] 落合 正仁: "α-Vinylation of 1,3-Dicarbonyl Compound with Alkenyl (aryl) iodonium Terafluoroborates : Effects of Substituents on the Aromatic Ring and of Radical Inhibitors." J.Org.Chem.62・7. 2130-2138 (1997)

[Publications] 落合 正仁: "Acetolysis of Styryl and l-Decenyl Iodonium Salts. Occurrence of Two-Step Mechanism Via Vinylenephenonium Ion and One-Step Inversion Mechanism." J.Am.Chem.Soc. 119・20. 4785-4786 (1997)

[Publications] 落合 正仁: "Oxidation of Sulfides to Sulfoxides with Hypervalent (tert-Butylperoxy) iodanes." J.Org.Chem.62・13. 4253-4259 (1997)

[Publications] 落合 正仁: "Nucleophilic Vinylic Substitutions of (Z)-(β-Haloal Kenyl) Phenyliodonium Salts with Sodium Benzenesulfinate : First Evidence of a Michael Addition of Nucleophiles to Alkenyliodonium Salts at the CB Atom." J.Org.Chem.62・23. 8001-8008 (1997)

[Publications] 小川 昭弥: "Palladium-Catalyzed Carbonylative Lactonization of Propargyl Alcohols with Organic Dichalcogenides and Carbon Monoxide." J.Org.Chem.62・24. 8361-8365 (1997)

[Publications] 小川 昭弥: "Highly Regioselective Hydrothiocarboxylation of Acetylenes with Carbon Monoxide and Thiols Catalyzed by Pt (PPh_3)_4" J.Am.Chem.Soc.119・50. 12380-12381 (1997)

[Publications] 長野 哲雄: ""Singlet Oxygen Production from Fullerene Derivatires : Effect of Sequential Functionalization of Fullerene Core" Chem.Commun.21-22 (1997)

[Publications] 長野 哲雄: "The Regio-and Stereo Selective Oxidation of Steroids with 2,6-Dichloropyridine N-Oxide Catalyzed by Ruthenium Porphyrines." Chem.Commun.801-802 (1997)

[Publications] 長野 哲雄: "Inhibitoty Effects of a Fullerence Derivative,Dimalonic Acid C_<60>,on Nitric Oxide-Induced Relaxation of Rabbit Aorta." European Journal Pharmacology. 327. 175-181 (1997)

[Publications] 長野 哲雄: "Real-time Measurement of Nitric Oxide Production in Rat Brain by the Combination of Luminol-H202 Chemiluminescenceand Microdialysis" Neuroscience Letters. 233. 157-159 (1997)

[Publications] 長野 哲雄: "Pronounced Axial Thiolate Ligand Effect on the Reactivity of High-valent Oxo-iron Porphyrin Intermediate." J.Am.Chem.Soc. 119. 12008-12009 (1997)

[Publications] 長野 哲雄: "活性酸素増産剤としての超原子価化合物のデザイン・合成・生物活性評価" 季刊化学総説,超原子価を持つ有機典型元素化合物. 34. 195-205 (1998)

檜山爲次郎京都大学, 工学研究科, 教授 (90026295)

[Publications] 檜山爲次郎: "Copper (I) Salt Promoted Homo-Coupling Reaction of Organosilanes" Chem.Commun.6. 1039-1040 (1997)

[Publications] 檜山爲次郎: "Synthesis and Electro-optical Properties of Novel Liquid Crystals Having a Cyclohexyl Trifluoromethyl Ether Moiety" Chem.Lett.827-828 (1997)

[Publications] 檜山爲次郎: "TBAHF2 and TBAH2F3 as Activating Agents of Organosilanes" Synlett. 6. 693-694 (1997)

[Publications] 檜山爲次郎: "Cu (I) /Pd (0) -Catalyzed Cross-Coupling Reaction of Alkynylsilanes with Arly on Alkenyl Triflates : "Sila"-Sonogashira-Hagihara Coupling" Chem.Lett.12. 1233-1234 (1997)

[Publications] 檜山爲次郎: "Copper (I) Salt Mediated 1,4-Reduction of α,β-Unsaturated Ketones Using Hydrosilanes" Chem.Commun.22. 2159-2160 (1997)

[Publications] 落合正仁: "Generation and Reaction of Monocarbonyl Iodonium Yides : Ester Exchange of Z- (β-Acetoxyvinyl) iodonium Salts with Lithium Ethoxide and Synthesis of α,β-Epoxy Ketones" J.Am.Chem.Soc.119・48. 11598-11604 (1997)

[Publications] 小川昭弥: "Palladium (0) -Catalyzed Regio- and Stereoselective Addition of Heteroatom Compounds Beaxing Si-Se,Ge-Se,and Si-Ge Bonds to Phenylacetylene" J.Organomet.Chem.

[Publications] 小川昭弥: "Highly Regio Selective Thioselenation of Acetylenes By Using a (PhS)_2- (PhSe)_2 Binary System" J.Org.Chem.

[Publications] 小川昭弥: "Diphenyl Diselenide-Assisted Dithiolation of 1,3-Dienes with Diphenyl Disulfide upon Irradiation with Near-UV Light" Tetrahedron Lett.

[Publications] 横山正明: "Colloid Formation from Vacuum Deposited Au Thin Layer on a UV-light Pre-exposed Polysilane Film." Chem.Lett.397-398 (1997)

[Publications] 横山正明: "金/ポリシラン積層膜における金コロイド形成とその光記録メディアへの応用" 応用物理学会・有機分子・バイオエレクトロニクス分科会会誌. 8・4. 189-198 (1997)

[Publications] 横山正明: "Au Colloid Formation in Polysilane/Au layered Film and Its Application as Novel Optical Recording Media" Mol.Lid.Cryst.Communications.

[Publications] 落合正仁: "α-Vinylation of 1,3-Dicarbonyl Compound with Alkenyl (aryl) iodonium Terafluoroborates : Effects of Substituents on the Aromatic Ring and of Radical Inhibitors." J.Org.Chem.62・7. 2130-2138 (1997)

[Publications] 落合正仁: "Acetolysis of Styryl and l-Decenyl Iodonium Salts. Occurrence of Two-Step Mechanism Via Vinylenephenonium Ion and One-Step Inversion Mechanism." J.Am.Chem.Soc. 119・20. 4785-4786 (1997)

[Publications] 落合正仁: "Oxidation of Sulfides to Sulfoxides with Hypervalent (tert-Butylperoxy) iodanes." J.Org.Chem.62・13. 4253-4259 (1997)

[Publications] 落合正仁: "Nucleophilic Vinylic Substitutions of (Z)-(β-Haloal Kenyl) Phenyliodonium Salts with Sodium Benzenesulfinate : First Evidence of a Michael Addition of Nucleophiles to Alkenyliodonium Salts at the CB Atom." J.Org.Chem.62・23. 8001-8008 (1997)

[Publications] 小川昭弥: "Palladium-Catalyzed Carbonylative Lactonization of Propargyl Alcohols with Organic Dichalcogenides and Carbon Monoxide." J.Org.Chem.62・24. 8361-8365 (1997)

[Publications] 小川昭弥: "Highly Regioselective Hydrothiocarboxylation of Acetylenes with Carbon Monoxide and Thiols Catalyzed by Pt (PPh_3)_4" J.Am.Chem.Soc.119・50. 12380-12381 (1997)

[Publications] 長野哲雄: ""Singlet Oxygen Production from Fullerene Derivatires : Effect of Sequential Functionalization of Fullerene Core" Chem.Commun.21-22 (1997)

[Publications] 長野哲雄: "The Regio-and Stereo Selective Oxidation of Steroids with 2,6-Dichloropyridine N-Oxide Catalyzed by Ruthenium Porphyrines." Chem.Commun.801-802 (1997)

[Publications] 長野哲雄: "Inhibitoty Effects of a Fullerence Derivative,Dimalonic Acid C_<60>,on Nitric Oxide-Induced Relaxation of Rabbit Aorta." European Journal Pharmacology. 327. 175-181 (1997)

[Publications] 長野哲雄: "Real-time Measurement of Nitric Oxide Production in Rat Brain by the Combination of Luminol-H202 Chemiluminescenceand Microdialysis" Neuroscience Letters. 233. 157-159 (1997)

[Publications] 長野哲雄: "Pronounced Axial Thiolate Ligand Effect on the Reactivity of High-valent Oxo-iron Porphyrin Intermediate." J.Am.Chem.Soc. 119. 12008-12009 (1997)

[Publications] 長野哲雄: "活性酸素増産剤としての超原子価化合物のデザイン・合成・生物活性評価" 季刊化学総説,超原子価を持つ有機典型元素化合物. 34. 195-205 (1998)