title: Diastereoselective total synthesis of (±)-schindilactone a, Part 3: The final phase and completion.
abstract: The final phase for the total synthesis of (±)-schindilactone A (1) is described herein. Two independent synthetic approaches were developed that featured Pd-thiourea-catalyzed cascade carbonylative annulation reactions to construct intermediate 3 and a RCM reaction to make intermediate 4. Other important steps that enabled the completion of the synthesis included: 1) A Ag-mediated ring-expansion reaction to form vinyl bromide 17 from dibromocyclopropane 30; 2) a Pd-catalyzed coupling reaction of vinyl bromide 17 with a copper enolate to synthesize ketoester 16; 3) a RCM reaction to generate oxabicyclononenol 10 from diene 11; 4) a cyclopentenone fragment in substrate 8 was constructed through a Co-thiourea-catalyzed Pauson-Khand reaction (PKR); 5) a Dieckmann-type condensation to successfully form the A ring of schindilactone A (1). The chemistry developed for the total synthesis of schindilactone A (1) will shed light on the synthesis of other family members of schindilactone A.
authors: Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, Beijing National Laboratory for Molecular Science and Peking-Tsinghua Center for Life Sciences at College of Chemistry of Peking University, Chengfu Road, 202, Beijing, 100871, China.
authors: Wei-Wu
authors: WW
authors: Ren
authors: Zhi-Xing
authors: ZX
authors: Chen
authors: Qing
authors: Q
authors: Xiao
authors: Yong
authors: Y
authors: Li
authors: Tian-Wen
authors: TW
authors: Sun
authors: Zi-Yang
authors: ZY
authors: Zhang
authors: Qin-Da
authors: QD
authors: Ye
authors: Fan-Ke
authors: FK
authors: Meng
authors: Lin
authors: L
authors: You
authors: Ming-Zhe
authors: MZ
authors: Zhao
authors: Ling-Min
authors: LM
authors: Xu
authors: Ye-Feng
authors: YF
authors: Tang
authors: Jia-Hua
authors: JH
authors: Chen
authors: Zhen
authors: Z
authors: Yang
mesh_terms: D002384:Catalysis; D018360:Crystallography, X-Ray; D061565:Cycloaddition Reaction; D008968:Molecular Conformation; D010165:Palladium / Q000737:chemistry; D013237:Stereoisomerism; D013890:Thiourea / Q000737:chemistry; D014315:Triterpenes / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D014315:Triterpenes; C568579:schindilactone A; D010165:Palladium; D013890:Thiourea