南开大学资伟伟研究小组的最新研究，提出了分子内2-氨基烯基阳离子-二烯(4 + 3)环加成构建三维复杂性。相关论文于2025年1月14日发表于国际顶尖学术期刊《德国应用化学》杂志上。

这项研究中描述了一种铜催化分子内2-氨基烯基阳离子-二烯(4 + 3)环加成反应的方法。通过以1,3-二烯系链乙基亚甲基环氨基甲酸酯为底物，该课题组能够构建多种含环庚烷的多环支架，这些支架存在于许多生物活性分子中。

这些环加成产物具有丰富的功能，可以进行多种化学转化。通过天然产物(±)-薄荷酮和(±)-薄荷酚的全合成，说明了该方法的合成效用。机理研究表明，环加成是通过协调的[4π + 2π]机制进行的，并且有利于内选择途径。

据介绍，快速构建富含C(sp3)的三维多环的可靠方法在有机合成和药物化学中有着很高的需求。虽然有多种成熟的体系用于合成五元或六元多环，但缺乏获得多种含环庚烷的多环支架的催化平台。

附：英文原文

Title: Building Three-Dimensional Complexity by Intramolecular 2-Aminoallyl Cation–Diene (4 + 3) Cycloaddition

Author: Lulu Shen, Tianzhu Qin, Chongling Jiao, Weiwei Zi

Issue&Volume: 2025-01-14

Abstract: Reliable methods for rapidly constructing C(sp3)-rich three-dimensional polycycles are in high demand for organic synthesis and medicinal chemistry. Although there are various mature systems for synthesizing five- or six-membered polycycles, a catalytic platform for accessing diverse cycloheptanoid-containing polycyclic scaffolds is lacking. Herein, we describe a method for copper-catalyzed intramolecular 2-aminoallyl cation–diene (4 + 3) cycloaddition reactions. By using 1,3-diene-tethered ethynyl methylene cyclic carbamates as substrates, we were able to construct various cycloheptanoid-containing polycyclic scaffolds, which are present in many bioactive molecules. The cycloaddition products were rich in functionality that could undergo various chemical transformations. The synthetic utility of the method was illustrated by total synthesis of the natural products (±)-mint ketone and (±)-aphanamol I. Mechanistic studies indicated that the cycloadditions proceed via a concerted [4π + 2π] mechanism and that an endo-selective pathway is favored.

DOI: 10.1002/anie.202423405

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202423405