Stereoselective Access to Polypropionates Expedited by the Double Hydroboration of Allenes: Total Synthesis of Antitumor (−)-Pironetin  

作　　者：Lin Yang Luyao Kong Qi Gu Shunjie Shao Guo-Qiang Lin Ran Hong 

机构地区：[1]CAS Key Laboratory of Synthetic Chemistry of Natural Substances,Center for Excellence in Molecular Synthesis,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,Shanghai 200032 [2]University of Chinese Academy of Sciences,Beijing 100049

出　　处：《CCS Chemistry》2021年第2期769-779,共11页中国化学会会刊（英文）

基　　金：support obtained from the Chinese Academy of Sciences(QYZDY-SSWSLH026 and XDB20020000)and the Drug Innovation Major Project(2018ZX09711001-005)is highly appreciated.The authors thank Zuming Lin for assisting with the experiments and Dr.Xiaoli Bao(SJTU)and Jie Sun(SIOC)for performing the X-ray analysis.

摘　　要：Polyketides,a large class of secondary metabolites,have been of long-standing interest to the synthetic community due to their intriguing biological activities and structural versatility and complexity.A typical structural unit of various natural products,polypropionate,has prompted enormous efforts in the development of novel synthetic methods and strategies in the past five decades.In this study,a non-aldol-type approach based on double hydroboration of allenes has been developed to provide a powerful method for the stereodivergent construction of various polyol stereotriads and stereotetrads that are amenable for synthesizing polypropionates.The stereochemical control is possibly attributable to the boronate complex that aligned itself as a rigid conformation for the second stereoselective hydroboration reaction by suppressing the barotropic rearrangement of allylborane intermediates.The feasibility of preparing the key polypropionate motif facilitates the efficient synthesis of(-)-pironetin,a potentα-tubulin inhibitor halting the cell cycle at M phase.

关 键 词：ALLENE boronate complex hydroboration polypropionate total synthesis 

分 类 号：O62[理学—有机化学]