New development of synthesis of aromatic heterocycles using A novel palladium-phosphine ligand reagent

新型钯膦配体试剂合成芳香杂环的新进展

• 批准号: 11672103
• 负责人: HARAYAMA Takashi
• 金额: $ 2.05万
• 依托单位: OKAYAMA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11672103/
• 关键词: Palladium reagent; benzo [c] phenanthridine; chelerythrine; Aryl-aryl coupling; 12-methoxydihydrochelerythrine; norchelerythrine; trisphaeridine; benzo [d] naphthopyran; アリール-アルケン結合反応; 二座配位リガンド; フェナンスリジン; 二座配位リンリガンド

1) Investigation of general synthetic method for chelerythrine type alkaloidA novel palladium reagent prepared from equimolar palladium acetate, DPPP, and tributylphophine was useful for the inernal biaryl coupling reaction of benzanilide possessing not only triflate but also halogen as a leaving group. By using this novel Pd reagent, benzo [c] phenanthridine alkaloids, chelerythrine, 12-methoxydihydrochelerythrine, and norchelerythrine were synthesized in good yields.. Benzo [d] naphtopyranones, arnottin I, was also synthesized by using typical Heck's reaction conditions.2) Mechanistic aspect of novel Palladium reagent [palladium acetate, DPPP, and tributylphophine]It was found out that molar ratio of Pd : phosphine=1 : 3 is essentially necessary for biaryl coupling reaction3) Synthesis of phenolic benzo [c] phenanthridine alkaloidFagaridine was synthesized in a good yield via biaryl coupling reaction of benzanilide protected by isopropyl group followed by reduction and acid treatment.4) Synthetic studies on Amaryllidaceae alkaloid, trisphaeridinePhenanthridine alkaloid, trisphaeridine, was synthesized via biaryl coupling reaction using palladium reagent.

1)白屈菜红碱类化合物合成方法的研究以等摩尔的乙酸钯、DPPP和三丁基膦为原料，合成了一种新的钯试剂，用于含三氟甲磺酸根和卤素的苯甲酰苯胺的联芳基偶联反应。用该钯试剂以较高的收率合成了苯并[c]菲啶生物碱、白屈菜红碱、12-甲氧基二氢白屈菜红碱和去甲白屈菜红碱。2）新型钯试剂[乙酸钯、DPPP和三丁基膦]的反应机理研究发现，当Pd：膦的摩尔比为1：1时，催化剂的活性最高。3）酚苯并[c]的合成通过异丙基保护的苯甲酰苯胺的联芳基偶联反应，再经还原和酸处理，以较好的产率合成了菲啶类化合物Fagaridine。4）石蒜科生物碱，三色堇碱菲啶类生物碱，三色堇碱，采用钯试剂通过联芳基偶联反应合成了2，3-二芳基-1，3-二甲基-1，4-二甲基-1，5-二甲基-1，4-

项目成果

Takashi Harayama, Hisashi Akamatsu, Kana Okamura, Taeko Miyagoe, Toshihiko Akiyama, Hitoshi Abe, Yasuo Takaeuchi: "Synthesis of Trisphaeridine and Norchelerythrine, through Palldium-catalyzed Aryl-aryl coupling Reaction"J.Chem.Soc., Perkin Trans.. 1(5). 5

Takashi Harayama、Hisashi Akamatsu、Kana Okamura、Taeko Miyagoe、Toshihiko Akiyama、Hitoshi Abe、Yasuo Takaeuchi：“通过钯催化的芳基-芳基偶联反应合成 Trisphaeridine 和 Norchelerythrine”J.Chem.Soc.，Perkin Trans.. 1

Takashi Harayama, , Toshihiko Akiyama, Hisashi Akamatsu, Kazuko Kawano, Hitoshi Abe, Yasuo Takeuchi: "Total Synthesis of Benzo [c] phenanthridine Alkaloids, Chelerythrine and 12-Methoxydihydrochelerythrine, by a Palladium-assisted Internal Biaryl Coupling

Takashi Harayama、Toshihiko Akiyama、Hisashi Akamatsu、Kazuko Kawano、Hitoshi Abe、Yasuo Takeuchi：“通过钯辅助内部联芳基偶联全合成苯并 [c] 菲啶生物碱、白屈菜红碱和 12-甲氧基二氢白屈菜红碱

Takashi Harayama, Hirotake Yasuda, Toshihiko Akiyama, Yasuo Takeuchi, Hitoshi Abe: "Synthesis of Arnottin I through a Palladium-Mediated Aryl-Aryl Coupling Reaction"Chem.Pharm.Bull.. 48(6). 861-864 (2000)

Takashi Harayama、Hirotake Yasuda、Toshihiko Akiyama、Yasuo Takeuchi、Hitoshi Abe：“通过钯介导的芳基-芳基偶联反应合成 Arnottin I”Chem.Pharm.Bull.. 48(6)。

Takashi HARAYAMA: "Synthesis of Amottin I through a Palladium-Mediated Aryl-Aryl Coupling Reaction"Chemical and Pharmaceutical Bulletin. 48(6). 861-864 (2000)

Takashi HARAYAMA：“通过钯介导的芳基-芳基偶联反应合成 Amotin I”化学和制药通报。

Takashi HARAYAMA: "Synthesis of Trisphaeridine and Norchelerythrine through Palladium-Catalysed Aryl-aryl Coupling Reaction"Journal of Chemical Society, Perkin Transaction I. (5). 523-528 (2001)

Takashi HARAYAMA：“通过钯催化的芳基-芳基偶联反应合成 Trisphaeridine 和正白屈菜红碱”，化学会杂志，Perkin Transaction I. (5)。