Development of Sustainable Process for Molecular Transformation Using Lewis Acid/Transition Metal Catalysts

使用路易斯酸/过渡金属催化剂开发可持续的分子转化工艺

• 批准号: 14002001
• 负责人: YAMAMOTO Yoshinori
• 金额: $ 374.4万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Specially Promoted Research
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2006
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14002001/
• 关键词: Lewis Acid Catalyst; Transition Metal Catalyst; Convergent Process; Bis-π-allylpalladium; Pronuclcophile; Addition Reaction; C-H Bond Activation; Polycyclic Ether; 芳香環化; メチレンアジリジン; 分子内反応; 不斉合成; ヘテロ環; 両機能性触媒; 縮環芳香族化合物; インドリチジンアルカロイド; メチレンシク

Stereocontroll via σ-π chelation was achieved by using group 13 Lewis acids. During this study, we found that some palladium (II) species act not only as transition metal catalyst but also as Lewis acid catalyst. Based on this finding, total syntheses of natural products, BCH-2051 and vibsanol, were achieved. Furthermore, antibiotics, (+)-ochromycinoneand (+)-rubiginone B2, were synthesized by using novel Au catalyst.Asymmetric allylation of imine derivatives was achieved by using optically active bis-π-allylpalladium, and the reaction was applied to the preparation of a synthetic intermediate of DMP-777. As a related reaction, novel synthetic method for cyanoindoles via three component coupling was developed. We found that the intramolecular reaction of amines and alkynes give nitrogen heterocycles in the presence of palladium/acetic acid catalyst. This reaction was applied to the total synthesis of an alkaloid, 209D.α-Allylation of hetero-aromatics and ketones were achieved by using methylenecyclopropane and palladium catalyst. On the other hand, the reaction with methyleneaziridine provided pyrrole derivatives having a pyridine or benzene ring.Total syntheses of marine polycyclic ethers, gambierol and brevetoxin B, were achieved via the intramolecular allylation followed by ring-closing metathesis.

通过使用 13 族路易斯酸实现了通过 σ-π 螯合的立体控制。在这项研究中，我们发现一些钯 (II) 物质不仅充当过渡金属催化剂，而且还充当路易斯酸催化剂。此外，利用新型Au合成了抗生素(+)-ochromycinone和(+)-rubiginone B2。利用光学活性双π-烯丙基钯实现了亚胺衍生物的不对称烯丙基化，并将该反应应用于合成中间体DMP-777的制备。作为相关反应，三组分偶联合成氰基吲哚的新方法。我们发现，在钯/乙酸催化剂存在下，胺和炔的分子内反应生成氮杂环。利用亚甲基环丙烷和钯催化剂，实现了生物碱、209D.α-杂芳烃和酮的烯丙基化，与亚甲基氮丙啶反应得到含有吡啶或苯环的吡咯衍生物。 brevetoxin B，是通过分子内烯丙基化然后闭环实现的复分解。

项目成果

Gold-Catalyzed Intramolecular Carbothiolation of Alkynes : Synthesis of 2, 3-Disubstituted benzothiophenes from (α-Alkoxy Alkyl)(ortho-ALkynyl Phenyl)Sulfides.

金催化的炔烃分子内碳硫基化：从 (α-烷氧基烷基)(邻炔基苯基)硫化物合成 2, 3-二取代苯并噻吩。

• 发表时间: 2006
• 作者: I. Nakamura

Synthesis of Imidazoles through the Copper-Catalyzed Cross-Cycloaddition between Two Different Isocyanides.

通过铜催化两种不同异氰化物之间的交叉环加成合成咪唑。

• 发表时间: 2006
• 作者: C. Kanazawa; S. Kamijo; Y. Yamamoto
• 通讯作者: Y. Yamamoto

Palladium-Catalyzed Decarboxylative Aza-Michael Addition-Allylation Reactions between Allyl Carbamates and Activated Olefins. Generation of Quaternary Carbon Adjacent to Secondary Amine Carbon Center.

钯催化氨基甲酸烯丙酯和活化烯烃之间的脱羧氮杂迈克尔加成-烯丙基化反应。

• 发表时间: 2006
• 作者: N. T. Patil; Z. Huo; Y. Yamamoto
• 通讯作者: Y. Yamamoto

Synthesis of Organosilicon Polymers by Using the Lewis Acid-Catalyzed trans-Allylsilylation of Alkynes.

利用路易斯酸催化炔烃的反式烯丙基硅烷化合成有机硅聚合物。

• 发表时间: 2005
• 作者: N. Asao

Intramolecular Hydroamination of Alkynes Catalyzed by Pd(PPh_3)_4/Triphenylphosphine under Neutral Conditions.

中性条件下 Pd(PPh_3)_4/三苯基膦催化炔烃分子内氢胺化。

• 发表时间: 2005
• 作者: G. B. Bajracharya; Z. Huo; Y. Yamamoto
• 通讯作者: Y. Yamamoto