通过 Rh 催化的 [3+2] 环加成反应不对称全合成 (-)- 灵菌红素。
Asymmetric total synthesis of (-)-lingzhiol via a Rh-catalysed [3+2] cycloaddition.
机构信息
1] Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen 518055, China [2] Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, Beijing National Laboratory for Molecular Science (BNLMS), and Peking-Tsinghua Center for Life Sciences and Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871, China [3].
1] Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen 518055, China [2] Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, Beijing National Laboratory for Molecular Science (BNLMS), and Peking-Tsinghua Center for Life Sciences and Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871, China.
出版信息
Nat Commun. 2014 Dec 8;5:5707. doi: 10.1038/ncomms6707.
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.
一锅法构建桥环双环体系，同时在桥头位置构建两个季碳原子中心，这对合成化学来说是一个巨大的挑战。发展能够克服这一挑战的新方法是非常可取的，因为这个结构单元存在于具有显著生物活性的广泛的天然产物中。在此，我们报告了一种有效的[3+2]环加成反应，醛与烯丙基铑物种反应，烯丙基铑物种通过相应的烯炔醇的反金属丙炔基化反应原位生成，生成了在桥头位置带有两个季碳原子的[3.3.0]和[3.4.0]双环体系。该方法已成功应用于天然产物(-)-灵菌酚（4）的首次不对称全合成，共 17 步。
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