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Asymmetric Total Synthesis of Propindilactone G,Part 2: Enantioselective Construction of the Fully Functionalized BCDE Ring System |
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| Authors: | Jia‐Jun Zhang Dr Lin You Dr Yue‐Fan Wang Yuan‐He Li Xin‐Ting Liang Bo Zhang Dr Shou‐Liang Yang Qi Su Prof Dr Jia‐Hua Chen Prof Dr Zhen Yang |
| Institution: | 1. State Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, Beijing National Laboratory for Molecular Science (BNLMS), Peking-Tsinghua Center for Life Sciences, and, Department of Chemistry, Peking University, Beijing, P.?R. China;2. +86)?10‐6275‐9105;3. Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Shenzhen Graduate School, Peking University, Shenzhen, P.?R. China;4. Key Laboratory of Marine Drugs, Chinese Ministry of Education, School of Medicine and Pharmacy, Ocean University of China, Qingdao, P.?R. China |
| Abstract: | The enantioselective synthesis of the fully functionalized BCDE tetracyclic ring system of propindilactone G ( A ) is reported. Several synthetic methods were developed and applied to achieve this goal, including: 1) an asymmetric Diels–Alder reaction in the presence of Hayashi′s catalyst for the synthesis of optically pure key intermediate 3 ; 2) an intramolecular Pauson–Khand reaction (PKR) for the stereoselective synthesis of the BCDE ring with an all‐carbon chiral quaternary center at the C13 position by using the TMS‐substituted acetylene as the substrate; and 3) Pd‐catalyzed reductive hydrogenolysis for the stereoselective synthesis of the fully functionalized BCDE tetracyclic ring system. The chemistry developed herein provided a greater understanding of the total synthesis propindilactone G ( A ) and its analogues. |
| Keywords: | hydrogenolysis natural products Pauson– Khand reaction propindilactone G total synthesis |