Asymmetric total synthesis of (-)-lingzhiol via a Rh-catalysed [3+2] cycloaddition

作者：Long, Rong; Huang, Jun; Shao, Wenbin; Liu, Song; Lan, Yu^*; Gong, Jianxian; Yang, Zhen

来源：Nature Communications, 2014, 5(1): 5707.

DOI：10.1038/ncomms6707

• ELECTRON-DEFICIENT OLEFINS
• ENANTIOSELECTIVE CONSTRUCTION
• FUNCTIONALIZED CYCLOPENTENES
• CONJUGATE ADDITION
• COMPLEXES
• REAGENTS
• ALLENES
• ACIDS
• ARYL
• 2,3-BUTADIENOATES

The development of efficient reactions for the one-pot construction of bicyclic ring systems bearing two quaternary carbon centres at their bridgehead positions represents a significant challenge to synthetic chemistry. The development of new methods capable of overcoming this challenge is highly desirable, because this motif can be found in a wide range of natural products with significant biological activities. Herein, we report an efficient [3+2] cycloaddition reaction between an enal and an alleno rhodium species, which was generated in situ from the corresponding enynol via a retro metal-propargylation reaction, to give [3.3.0] and [3.4.0] bicyclic systems bearing two quaternary atoms at their bridgehead positions. The developed chemistry has been successfully applied to the asymmetric total synthesis of natural product (-)-lingzhiol (4) for the first time in 17 steps.

• 出版日期2014-12
• 单位北京大学深圳研究生院; 重庆大学; 北京大学; 中国海洋大学