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 

作者机构：CAS Key Laboratory of Synthetic Chemistry of Natural SubstancesCenter for Excellence in Molecular SynthesisShanghai Institute of Organic ChemistryChinese Academy of SciencesShanghai 200032 University of Chinese Academy of SciencesBeijing 100049 

出 版 物：《CCS Chemistry》 (中国化学会会刊（英文）)

年 卷 期：2021年第3卷第2期

页      面：769-779页

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 

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 

主　　题：allene boronate complex hydroboration,polypropionate total synthesis 

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 *** 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 *** 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 *** feasibility of preparing the key polypropionate motif facilitates the efficient synthesis of(-)-pironetin,a potentα-tubulin inhibitor halting the cell cycle at M phase.