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

作者：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

来源：Chemistry-An Asian Journal, 2012, 7(10): 2341-2350.

DOI：10.1002/asia.201200365

• fused-ring systems
• natural products
• schindilactone A
• synthetic methods
• total synthesis

The final phase for the total synthesis of (+/-)-schindilactone A (1) is described herein. Two independent synthetic approaches were developed that featured Pdthiourea-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 Cothiourea-catalyzed PausonKhand 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.

• 出版日期2012-10
• 单位北京大学; 北京大学深圳研究生院