Shenzhen Grubbs Institute , Southern University of Science and Technology (SUSTech) , Shenzhen , 518055 , China.
The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering , California Institute of Technology , Pasadena , California 91125 , United States.
Org Lett. 2018 Jul 6;20(13):3793-3796. doi: 10.1021/acs.orglett.8b01387. Epub 2018 Jun 13.
An approach to synthesize the pentacyclic framework of the polyol diterpenoid ryanodol is reported. The ABC tricycle was constructed by a Co-mediated Pauson-Khand reaction, and both radical and anionic cyclization pathways were developed to form the E-ring. In addition, a reaction sequence involving SeO-mediated enone oxidation and hydroxyl-directed oxy-Michael addition was developed to introduce the A-ring oxidation. The feasibility of forming the bridging D-ring by an oxidative dearomatization was established.
本文报道了一种合成多醇二萜瑞香毒素五环骨架的方法。通过 Co 介导的 Pauson-Khand 反应构建了 ABC 三环,并且开发了自由基和阴离子环化途径来形成 E 环。此外,还开发了一种涉及 SeO 介导的烯酮氧化和羟基导向的氧迈克尔加成的反应序列,以引入 A 环氧化。通过氧化去芳构化形成桥接 D 环的可行性得到了确立。