Diastereoselective Total Synthesis of (±)-Schindilactone A, Part 3: The Final Phase and Completion

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 imp...

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Published in:Chemistry, an Asian journal an Asian journal, 2012-10, Vol.7 (10), p.2341-2350
Main Authors: Ren, Wei-Wu, Chen, Zhi-Xing, Xiao, Qing, Li, Yong, Sun, Tian-Wen, Zhang, Zi-Yang, Ye, Qin-Da, Meng, Fan-Ke, You, Lin, Zhao, Ming-Zhe, Xu, Ling-Min, Tang, Ye-Feng, Chen, Jia-Hua, Yang, Zhen
Format: Article
Language:English
Subjects:
Catalysis
Crystallography, X-Ray
Cycloaddition Reaction
fused-ring systems
Molecular Conformation
natural products
Palladium - chemistry
schindilactone A
Stereoisomerism
synthetic methods
Thiourea - chemistry
total synthesis
Triterpenes - chemical synthesis
Triterpenes - chemistry
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Summary: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. Three to get ready, now…︁ The completion of the total synthesis of (±)‐schindilactone A is reported. The chemistry developed for the total synthesis of schindilactone A will shed light on the synthesis of other family members of schindilactone A.
ISSN:1861-4728
1861-471X
DOI:10.1002/asia.201200365