Exploring Cuneanes as Potential Benzene Isosteres and Energetic Materials: Scope and Mechanistic Investigations into Regioselective Rearrangements from Cubanes
Exploring Cuneanes as Potential Benzene Isosteres and Energetic Materials: Scope and Mechanistic Investigations into Regioselective Rearrangements from Cubanes
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探索古巴烷作为潜在苯等排体和含能材料：古巴烷区域选择性重排的范围和机制研究
DOI：
10.1021/jacs.3c03226
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发表时间：
2023
影响因子：
15
通讯作者：
Stephenson, Corey R.
中科院分区：
文献类型：
--
作者：
Son, Jeong-Yu;Aikonen, Santeri;Morgan, Nathan;Harmata, Alexander S.;Sabatini, Jesse J.;Sausa, Rosario C.;Byrd, Edward F.;Ess, Daniel H.;Paton, Robert S.;Stephenson, Corey R.
立方烷是一种应变烃，可以通过金属催化立方烷异构化得到。六烷的碳原子定义了一个有六个面的点群多面体──两个三角形面、两个四边形面和两个五边形面。烷骨架的刚度、应变和独特的出口向量使其成为合成功能性小分子和材料的潜在支架。然而，以前有限的合成cune烷的努力主要集中在单取代或冗余取代系统，如过甲基化，全氟化和双（羟甲基化）cune烷。这类化合物，特别是旋转对称的冗余取代烷，作为合成复杂分子的基础材料的潜力有限。可靠、可预测和选择性地合成具有更复杂取代模式的多取代烷将促进对该环体系的无数应用研究。在此，我们报道了不对称1,4-二取代的古巴烷在agi催化下的区域选择性异构化。深入的DFT计算提供了一个电荷控制的区域选择性模型，直接的动力学模拟表明，非经典碳正离子的调用是短暂的，动态效应增强了电荷模型。
Cuneane is a strained hydrocarbon that can be accessed via metal-catalyzed isomerization of cubane. The carbon atoms of cuneane define a polyhedron of theC2vpoint group with six faces─two triangular, two quadrilateral, and two pentagonal. The rigidity, strain, and unique exit vectors of the cuneane skeleton make it a potential scaffold of interest for the synthesis of functional small molecules and materials. However, the limited previous synthetic efforts toward cuneanes have focused on monosubstituted or redundantly substituted systems such as permethylated, perfluorinated, and bis(hydroxymethylated) cuneanes. Such compounds, particularly rotationally symmetric redundantly substituted cuneanes, have limited potential as building blocks for the synthesis of complex molecules. Reliable, predictable, and selective syntheses of polysubstituted cuneanes bearing more complex substitution patterns would facilitate the study of this ring system in myriad applications. Herein, we report the regioselective, AgI-catalyzed isomerization of asymmetrically 1,4-disubstituted cubanes to cuneanes. In-depth DFT calculations provide a charge-controlled regioselectivity model, and direct dynamics simulations indicate that the nonclassical carbocation invoked is short-lived and dynamic effects augment the charge model.