关于[2.2.1]-和[2.1.1]同三蝶烯的意外形成
On the Unexpected Formation of [2.2.1]- and [2.1.1]Homotriblattanes.
作者信息
Samkian Adrian E, Nguyen Hanh T, Vanderwal Christopher D, Stoltz Brian M
机构信息
Warren and Katharine Schlinger Laboratory of Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, MC 101-20, Pasadena, California 91125, United States.
Department of Chemistry, 1102 Natural Sciences II, University of California, Irvine, California 92697, United States.
出版信息
Tetrahedron Lett. 2025 Jul 15;164. doi: 10.1016/j.tetlet.2025.155591. Epub 2025 Apr 11.
A new class of polycyclic caged compounds, the [2.n.1]homotriblattanes, is described herein. These scaffolds are accessed through a concise, three-step sequence featuring an unexpected radical cyclization of α-bromocyclopropyl ketones. Their structures and stereochemical assignments were confirmed by a combination of 2D NMR and X-ray crystallography. DFT studies provide mechanistic insight into their formation and the side products formed en route. This study expands the known chemical space of polycyclic cages and offers a new entry point into highly complex 3-dimensional frameworks.
本文描述了一类新型的多环笼状化合物，即[2.n.1]同三碟烷。这些骨架通过一个简洁的三步序列获得，该序列的特点是α-溴环丙基酮发生意外的自由基环化反应。它们的结构和立体化学归属通过二维核磁共振（2D NMR）和X射线晶体学相结合的方法得以确认。密度泛函理论（DFT）研究为它们的形成以及反应过程中形成的副产物提供了机理上的见解。这项研究扩展了多环笼状化合物已知的化学空间，并为进入高度复杂的三维骨架提供了一个新的切入点。
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