title: Asymmetric Total Synthesis of Propindilactone G, Part 2: Enantioselective Construction of the Fully Functionalized BCDE Ring System.
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.
authors.affiliation: 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, 202 Chengfu Road, Beijing, 100871, P. R. China.
authors.forename: Jia-Jun
authors.initials: JJ
authors.lastname: Zhang
authors.affiliation: 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, 202 Chengfu Road, Beijing, 100871, P. R. China.
authors.forename: Lin
authors.initials: L
authors.lastname: You
authors.affiliation: 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, 202 Chengfu Road, Beijing, 100871, P. R. China.
authors.forename: Yue-Fan
authors.initials: YF
authors.lastname: Wang
authors.affiliation: 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, 202 Chengfu Road, Beijing, 100871, P. R. China.
authors.forename: Yuan-He
authors.initials: YH
authors.lastname: Li
authors.affiliation: 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, 202 Chengfu Road, Beijing, 100871, P. R. China.
authors.forename: Xin-Ting
authors.initials: XT
authors.lastname: Liang
authors.affiliation: 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, 202 Chengfu Road, Beijing, 100871, P. R. China.
authors.forename: Bo
authors.initials: B
authors.lastname: Zhang
authors.affiliation: 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, 202 Chengfu Road, Beijing, 100871, P. R. China.
authors.forename: Shou-Liang
authors.initials: SL
authors.lastname: Yang
authors.affiliation: 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, 202 Chengfu Road, Beijing, 100871, P. R. China.
authors.forename: Qi
authors.initials: Q
authors.lastname: Su
authors.affiliation: 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, 202 Chengfu Road, Beijing, 100871, P. R. China. jhchen@pku.edu.cn.
authors.forename: Jia-Hua
authors.initials: JH
authors.lastname: Chen
authors.affiliation: 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, 202 Chengfu Road, Beijing, 100871, P. R. China. zyang@pku.edu.cn.|Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Shenzhen Graduate School, Peking University, Shenzhen, 518055, P. R. China. zyang@pku.edu.cn.|Key Laboratory of Marine Drugs, Chinese Ministry of Education, School of Medicine and Pharmacy, Ocean University of China, 5 Yushan Road, Qingdao, P. R. China. zyang@pku.edu.cn.
authors.forename: Zhen
authors.initials: Z
authors.lastname: Yang
mesh_terms: D002384:Catalysis; D061565:Cycloaddition Reaction; D006576:Heterocyclic Compounds, 4 or More Rings / Q000138:chemical synthesis* / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D013237:Stereoisomerism; D014315:Triterpenes / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D006576:Heterocyclic Compounds, 4 or More Rings; D014315:Triterpenes; C000621059:propindilactone G
keywords: Pauson-Khand reaction; hydrogenolysis; natural products; propindilactone G; total synthesis