Lasonolide A was identified as a potent antitumor macrolide towards various cancer cell lines.The two tetrahydropyrans bearing multiple stereogenic centers as well as the polyvene linkage attracted a dozen synthetic r...Lasonolide A was identified as a potent antitumor macrolide towards various cancer cell lines.The two tetrahydropyrans bearing multiple stereogenic centers as well as the polyvene linkage attracted a dozen synthetic research groups to launch the total syn-thesis.Based on the synthetic methods developed in our group,namely,the hydroboration of allene and its subsequent allylation as well as the iterative hydroboration of allene and oxidation,the polyol subunits were efficiently constructed and then integrated into the final target.A new Julia olefination reagent,double-headed sulfone,was designed to promote the rapid coupling of two aldehydes bearing multiple functional groups to secure the whole carbon framework.Another highlight of our approach is the application of a traceless protecting group,9-BBN(9-borabicyclo[3.3.1]nonane),to hide the secondary alcohol for debenzylation,and for the first time,to mask the carboxylic acid for Julia olefination under strong basic conditions.展开更多
Macrolactones play a critical role in pharmaceuticals and agrochemicals.Numerous efforts have been devoted to developing synthetic methods for them.We highlighted a recent progress for building macrocycles(≥12-member...Macrolactones play a critical role in pharmaceuticals and agrochemicals.Numerous efforts have been devoted to developing synthetic methods for them.We highlighted a recent progress for building macrocycles(≥12-membered)via bench-stable vinyl ester(VE)intermediates,which have been underdeveloped for half century.展开更多
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 struc...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.展开更多
基金the Drug Innovation Major Project(2018ZX09711001-005)the National Natural Science Foundation of China(91856202)+2 种基金the National Key R&D Program of China(2019YFA09005000)the Strategic Priority Research Program(XDB20000000)the Key Research Program of Frontier Sciences(QYZDYSSWSLH026)of the Chinese Academy of Sciences is highly appreciated.We also thank Jie Sun(SIOC,CAS)for the X-ray analysis.
文摘Lasonolide A was identified as a potent antitumor macrolide towards various cancer cell lines.The two tetrahydropyrans bearing multiple stereogenic centers as well as the polyvene linkage attracted a dozen synthetic research groups to launch the total syn-thesis.Based on the synthetic methods developed in our group,namely,the hydroboration of allene and its subsequent allylation as well as the iterative hydroboration of allene and oxidation,the polyol subunits were efficiently constructed and then integrated into the final target.A new Julia olefination reagent,double-headed sulfone,was designed to promote the rapid coupling of two aldehydes bearing multiple functional groups to secure the whole carbon framework.Another highlight of our approach is the application of a traceless protecting group,9-BBN(9-borabicyclo[3.3.1]nonane),to hide the secondary alcohol for debenzylation,and for the first time,to mask the carboxylic acid for Julia olefination under strong basic conditions.
基金the financial support from the Drug Innovation Major Project(No.2018ZX09711001-005)the Program of Shanghai Academic Research Leader(No.20XD1404700)+1 种基金the Key Research Program of Frontier Sciences(No.QYZDY-SSWSLH026)the Strategic Priority Research Program(No.XDB20000000)of the Chinese Academy of Sciences.
文摘Macrolactones play a critical role in pharmaceuticals and agrochemicals.Numerous efforts have been devoted to developing synthetic methods for them.We highlighted a recent progress for building macrocycles(≥12-membered)via bench-stable vinyl ester(VE)intermediates,which have been underdeveloped for half century.
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.
文摘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.
