上海交通大学丁同梅团队报道了级联Nazarov环化和环膨胀反应中结构性质扩展到不同角度的三环，以及马德拉酮的全合成。相关研究成果于2024年8月6日发表在《德国应用化学》。

研究人员开发了级联Nazarov环化/二环膨胀反应，用于精确合成角融合的M/5/N（M=5,6；N=49,13）三环骨架。由于环应变的释放，第一环的优先膨胀在转化中起着至关重要的作用，而底物上存在的取代基的性质是另一个影响因素。

这种开创性的级联反应具有底物范围广（33个实例）、反应时间短、收率高达95%和区域选择性显著（>20:1）的特点。利用这种级联反应的合成应用，研究人员首次成功地完成了名为马德波隆酮的简洁全合成。

附：英文原文

Title: Expansion of Structure Property in Cascade Nazarov Cyclization and Cycloexpansion Reaction to Diverse Angular Tricycles and Total Synthesis of Nominal Madreporanone

Author: Kun Fang, Bao-Heng Dou, Fu-Min Zhang, Yun-Peng Wang, Zi-Rui Shan, Xiao-Yu Wang, Si-Hua Hou, Yongqiang Tu, Tong-Mei Ding

Issue&Volume: 2024-08-06

Abstract: A cascade Nazarov cyclization/dicycloexpansions reaction was developed for the precise synthesis of the angularly fused M/5/N (M = 5, 6; N = 49, 13) tricyclic skeletons. The prioritized expansion of the first ring played a critical role in the transformations, due to the release of ring strain, and the nature of the substituents present on the substrate is another influencing factor. This pioneering cascade reaction features broad substrates scope (33 examples), short reaction time, exceptional yields (up to 95%), and remarkable regioselectivities (> 20:1). Exploiting the synthetic application of this cascade reaction, we successfully executed a succinct total synthesis of nominal madreporanone for the first time.

DOI: 10.1002/anie.202412337

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202412337