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

Facile deallylation protocols for the preparation of N-unsubstituted triazoles and tetrazoles.

• DOI: 10.1002/chin.200551113
• 发表时间: 2005-07
• 期刊: The Journal of organic chemistry
• 作者: S. Kamijo;Z. Huo;T. Jin;C. Kanazawa;Yoshinori Yamamoto

A route to 2-substituted tetrahydroquinolines via palladium-catalyzed intramolecular hydroamination of anilino-alkynes.

• DOI: 10.1021/jo0708137
• 发表时间: 2007-07
• 期刊: The Journal of organic chemistry
• 作者: N. Patil;Huanyou Wu;Yoshinori Yamamoto

An efficient, facile, and general synthesis of 1H-indazoles by 1,3-dipolar cycloaddition of arynes with diazomethane derivatives

• DOI: 10.1002/anie.200700101
• 发表时间: 2007-01-01
• 期刊: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
• 影响因子: 16.6
• 作者: Jin, Tienan;Yamamoto, Yoshinori
• 通讯作者: Yamamoto, Yoshinori

Synthesis of imidazoles through the copper-catalyzed cross-cycloaddition between two different isocyanides

• DOI: 10.1021/ja0617439
• 发表时间: 2006-08-23
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Kanazawa, Chikashi;Kamijo, Shin;Yamamoto, Yoshinori
• 通讯作者: Yamamoto, Yoshinori

Synthesis of 1-substituted tetrazoles via the acid-catalyzed [3+2] cycloaddition between isocyanides and trimethylsilyl azide

• DOI: 10.1016/j.tetlet.2004.10.103
• 发表时间: 2004-12-13
• 期刊: TETRAHEDRON LETTERS
• 影响因子: 1.8
• 作者: Jin, TN;Kamijo, S;Yamamoto, Y
• 通讯作者: Yamamoto, Y