Zhu Yu, Zheng Jie, Evans P Andrew
Department of Chemistry, Queen's University, 90 Bader Lane, Kingston, ONK7L 3N6, Canada.
Xiangya School of Pharmaceutical Sciences, Central South University, Changsha410013, Hunan, P. R. of China.
J Am Chem Soc. 2023 Feb 6. doi: 10.1021/jacs.2c10923.
The development of an intramolecular rhodium-catalyzed [(3+2+2)] carbocyclization reaction of alkylidenecyclopropanes (ACPs) tethered to 1,4- and 1,5-skipped dienes is described. This transformation offers a new approach for the construction of bridged tricyclic compounds with up to three quaternary centers, which are suitable for the synthesis of challenging bioactive natural products. For instance, the synthetic utility of this transformation is illustrated through a concise asymmetric total synthesis of the sesquiterpene (+)-zizaene in ten steps from a commercially available starting material.
本文描述了一种分子内铑催化的、将亚烷基环丙烷（ACPs）与1,4-和1,5-间隔二烯相连的[(3+2+2)]碳环化反应的发展。这种转化为构建具有多达三个季碳中心的桥连三环化合物提供了一种新方法，这些化合物适用于具有挑战性的生物活性天然产物的合成。例如，通过从市售起始原料经十步简洁的不对称全合成倍半萜（+）-紫穗槐烯，说明了这种转化的合成效用。
