Superacid-catalyzed reactions and the application of supercritical fluid

超酸催化反应及超临界流体的应用

• 批准号: 13554023
• 负责人: OHWADA Tomohiko
• 金额: $ 5.44万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13554023/
• 关键词: superacids; aromatic compounds; Pictet-Spengler reaction; CO2 supercritical fluid; stereoselction; Superelectrophile; intramolecular cyclization; nitroalkanes; ブレンステッド酸; 芳香族求電子置換反応; 超臨界流体; 環化反応; 超求電子試薬; 4H-1,2-ベンツオキサジン; 超強酸; 芳香族求電子反応; 二酸化炭

New superacid-catalyed reactions and their features such as regioselectivity and stereoseterctivity were studied. Destabilized carbenium ions substituted with genuine electron-withdrawing groups such as carbenium, oxonium, ammonium groups were proposed to be involved. These cations constitute reactive superelectrophiles in a novel type of Friedel-Crafts reactions. We attempted to use CO_2 supercritical fluid conditions with a combination of superacid catalyst. We understood the development of new reaction system compatible with the superacid. We studied (1) Regioselective Superacid-Catalyzed Electrocyclization of Diphenylmethyl Cations. Fluorenes, Phenanthrol and Benzofuran Cyclizations (2) Stereoselectivity of Superacid-Catalyzed Pictet-Spengler Cyclization Reactions (3) 4H-l,2-Benzoxazines with Electron-withdrawing Substituents on the Benzene Ring. Synthesis and Application as Potent Intermediates for Oxygen-Functionalized Aromatic Compounds

研究了新型超强酸催化反应及其区域选择性和立体选择性等特点。被真正的吸电子基团如正碳离子、氧离子、铵基取代的失稳正碳离子被认为参与了反应。这些阳离子构成了一种新型的Friedel-Crafts反应中的反应性超亲电体。我们尝试用CO_2超临界流体条件与超强酸催化剂的组合。我们了解了与超强酸相容的新反应体系的发展。我们研究了（1）区域选择性超强酸催化二苯甲基阳离子的电环化反应。芴、邻菲咯和苯并呋喃的环化反应（2）超强酸催化的Pictet-Spengler环化反应的立体选择性（3）苯环上有吸电子取代基的4 H-1，2-苯并恶嗪含氧芳香族化合物的合成及其作为中间体的应用

项目成果

Yoshida, N., Ohwada, T.: "Regioselective Superacid-Catalyzed Electrocyclization of Diphenylmethyl Cations. Fluorenes, Phenanthrol and Benzofuran Cyclizations"Synthesis. 1487-1494 (2001)

Yoshida, N., Ohwada, T.：“二苯甲基阳离子的区域选择性超强酸催化电环化。芴、菲酚和苯并呋喃环化”合成。

Nakamura, S., Tanaka, M., Taniguchi, T., Uchiyama, M., Ohwada, T.: "Stereoselectivity of Superacdd-Catalyzed Pictet-Spengler Cyclization Reactions"Organic Letters.. in press. (2003)

Nakamura, S.、Tanaka, M.、Taniguchi, T.、Uchiyama, M.、Ohwada, T.：“超酸催化 Pictet-Spengler 环化反应的立体选择性”有机快报.. 正在出版。

Yoshida N., Ohwada.T.: "Regioselective Superacid-Catalyzed Electrocyclization of Diphenylmelhyl Cations. Fluorenes, Phenanthrol and Benzofuran Cyclizations"Synthesis. 1487-1494 (2001)

Yoshida N.，Ohwada.T.：“二苯基甲基阳离子的区域选择性超酸催化电环化。芴、菲酚和苯并呋喃环化”合成。

Nakamura, S., Uchiyama, M., Ohwada, T.: "4H-1,2-Benzoxazines with Electron-withdrawing Substituents on the Benzene Ring. Synthesis and Application as Potent Intermediates for Oxygen-Functionalized Aromatic Compounds"J. Am. Chem. Soc.. (in press). (2003)

Nakamura, S.、Uchiyama, M.、Ohwada, T.：“苯环上带有吸电子取代基的 4H-1,2-苯并恶嗪。作为氧官能化芳香族化合物的有效中间体的合成和应用”J。

Nakamura, S., Tanaka, M., Taniguchi, T., Uchiyama, M., Ohwada, T.: "Stereoselectivity of Superacid-Catalyzed Pictet-Spengler Cyclization Reactions"Organic Letters. (in press). (2003)

Nakamura, S.、Tanaka, M.、Taniguchi, T.、Uchiyama, M.、Ohwada, T.：“超酸催化 Pictet-Spengler 环化反应的立体选择性”有机快报。