Skeletal Optimization of Cytotoxic Lipidic Dialkynylcarbinols
作者:Maroua Bourkhis、Hafida Gaspard、Pauline Rullière、Diana K. C. de Almeida、Dymytrii Listunov、Etienne Joly、Raoudha Abderrahim、Marcos C. de Mattos、Maria C. F. de Oliveira、Valérie Maraval、Remi Chauvin、Yves Génisson
DOI:10.1002/cmdc.201800118
日期:2018.6.6
out in both the DAC and BAC series. The critical impact of the length of the lipidic skeleton was first confirmed in the racemic series, with the highest cytotoxic activity observed for C17 to C18 backbones. Enantiomerically enriched samples were prepared by asymmetric synthesis of the optimal C18 DAC and C17 BAC derivatives. Samples with upgraded enantiomeric purity were alternatively produced by enzymatic
与生物启发的合成炔属脂质的药理学潜力的最新研究一致,在确定末端二炔基甲醇(DAC)和丁二炔基炔醇(BAC)部分为功能性抗肿瘤药效单位后,这项工作专门解决了碳骨架长度的问题。因此,在DAC和BAC系列中均进行了脂肪族链长的系统变化。脂质骨架长度的关键影响首先在外消旋系列中得到证实,其中C 17至C 18骨架的细胞毒活性最高。对映体富集的样品通过最佳C 18 DAC和C 17的不对称合成制备BAC衍生物。可替代地,通过酶促动力学拆分产生具有提高的对映体纯度的样品。具有S 构型的Eutomer对HCT116癌细胞的细胞毒性IC 50值低至15 n m,是该系列药物迄今为止达到的最高活性水平。
Carbon−Carbon Bond Cleavage of Diynes through the Hydroamination with Transition Metal Catalysts
作者:Tomohiro Shimada、Yoshinori Yamamoto
DOI:10.1021/ja034105o
日期:2003.6.1
The C-Cbondcleavage of terminal and internal diynes takes place readily in the presence of catalytic amounts of Ru3(CO)12 or Pd(NO3)2 and of 2-aminophenol, giving the corresponding benzoxazoles and ketones in good to high yields. There are two different modes of the bondcleavage: (a) an alkyne C-C triple bond is cleaved, and (b) the C-C single bond between the two alkyne groups is cleaved.
在催化量的 Ru3(CO)12 或 Pd(NO3)2 和 2-氨基苯酚存在下,末端和内部二炔的 CC 键断裂很容易发生,从而以良好或高产率得到相应的苯并恶唑和酮。有两种不同的键断裂模式:(a) 炔烃 CC 三键断裂,和 (b) 两个炔基之间的 CC 单键断裂。
Selectivity for Alkynyl or Allenyl Imidamides and Imidates in Copper-Catalyzed Reactions of Terminal 1,3-Diynes and Azides
作者:Sourav Ghorai、Daesung Lee
DOI:10.1021/acs.orglett.0c03861
日期:2021.2.5
Copper-catalyzed reactions of terminal 1,3-diynes with electron-deficient azides to generate either 3-alkynyl or 2,3-dienyl imidamides and imidates are described. The selectivity depends on the diyne substituents and the nucleophile that reacts with the ketenimide intermediate generated from the corresponding triazole precursor. Reactions of 1,3-diynes containing a propargylic acetate afford [3]cumulenyl