Ke Lei, Chen Zhilong
School of Pharmacy, Huazhong University of Science and Technology (HUST), 13 Hangkong Road, Wuhan, Hubei, 430030, P. R. China.
Commun Chem. 2020 Apr 20;3(1):48. doi: 10.1038/s42004-020-0295-0.
The concise construction of diene scaffolds is quite useful in the synthesis of polyenes. Many diene building blocks have been developed based on Suzuki, Still and Hiyama couplings. Herein, the commercially available and environmentally friendly compound dienedioic acid is used as a diene building block. Broad substrate scope, good functional group tolerance, and late-stage derivatization of complex drug molecules are achieved. Different moieties can be conveniently introduced to both sides. Piperine and the methyl ester of azoxymycin C are each prepared in three steps. Additionally, one product shows promising anticancer activities in leukemia K562 and MV-4-11 cells. Mechanistic studies indicate that the reaction proceeds through a Heck-decarboxylate coupling procedure, and the carboxylic group acts as a directing group to promote the reaction and control regioselectivity. Our research suggests that dienedioic acid can serve as a good alternative for diene preparation via a directed Heck-decarboxylate coupling.
二烯骨架的简洁构建在多烯的合成中非常有用。基于铃木、斯蒂尔和日山偶联反应,已经开发了许多二烯构建模块。在此,市售且环境友好的化合物二烯二酸被用作二烯构建模块。实现了广泛的底物范围、良好的官能团耐受性以及复杂药物分子的后期衍生化。不同的部分可以方便地引入到两侧。胡椒碱和氮氧化霉素C甲酯均通过三步制备。此外,一种产物在白血病K562和MV - 4 - 11细胞中显示出有前景的抗癌活性。机理研究表明该反应通过Heck - 脱羧偶联过程进行,羧基作为导向基团促进反应并控制区域选择性。我们的研究表明,二烯二酸可作为通过定向Heck - 脱羧偶联制备二烯的良好替代物。