Division of Natural Product Chemistry, Indian Institute of Chemical Technology, Hyderabad 500007, India.
Org Biomol Chem. 2013 May 7;11(17):2847-58. doi: 10.1039/c3ob27508f. Epub 2013 Mar 11.
The stereoselective synthesis of a C9-C19 fragment of the potent antitumor agent peloruside A is disclosed. The C11 stereogenic centre was created by a vinylogous Mukaiyama aldol reaction following Carreira's protocol, with excellent stereocontrol. The C13 stereogenic centre was introduced by a substrate controlled reduction. The C15 stereocentre was fashioned using Noyori's asymmetric transfer hydrogenation while the Z-trisubstituted double bond was formed by a regioselective hydrostannation of an alkyne followed by methylation of the resultant vinyl stannane using Lipshutz's protocol. The C18 chiral centre was introduced by a chemoenzymatic route.
本文报道了强效抗肿瘤药物佩罗利德斯 A 的 C9-C19 片段的立体选择性合成。C11 立体中心是通过 Carreira 的方案中的 vinylogous Mukaiyama 羟醛反应形成的，具有出色的立体控制。C13 立体中心是通过底物控制还原引入的。C15 立体中心是通过 Noyori 的不对称转移氢化形成的，而 Z-三取代双键是通过炔烃的区域选择性氢化，然后使用 Lipshutz 的方案将所得的乙烯基锡烷甲基化形成的。C18 手性中心是通过化学酶法途径引入的。
