Reactions of 2-Aryl-1,3-Dithianes and [1.1.1]Propellane.
Reactions of 2-Aryl-1,3-Dithianes and [1.1.1]Propellane.
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DOI：
10.1002/anie.201905531
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发表时间：
2019-08
影响因子：
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通讯作者：
Nisalak Trongsiriwat;Youge Pu;Yexenia Nieves-Quinones;Russell A Shelp;M. Kozlowski;P. Walsh
中科院分区：
文献类型：
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作者：
Nisalak Trongsiriwat;Youge Pu;Yexenia Nieves-Quinones;Russell A Shelp;M. Kozlowski;P. Walsh
双环[1.1.1]戊烷（BCPs）最近被发现是芳香环的生物电子等排体，引起了药物化学家的兴趣。为了研究这类相对较新的生物电子等排体的生物活性，将BCP掺入靶分子的可靠方法是非常需要的，正如近年来一系列BCP合成方法所反映的那样。在这项工作中，我们公开了一种合成含BCP的二噻烷的通用方法，该方法在脱保护后，提供了获得药用丰富的二芳基酮的BCP类似物的途径。广泛的2-芳基-1，3-二噻烷，包括几种杂环衍生物，与[1.1.1]螺桨烷反应，以良好至优异的产率得到26种新的衍生物。二噻烷部分进一步转化为各种官能团证明了产品的耐用性。计算结果表明，2-芳基-1，3-二噻烷与[1.1.1]螺桨烷的反应是通过双电子途径进行的.
Bicyclo[1.1.1]pentanes (BCPs) have sparked the interest of medicinal chemists due to their recent discovery as bioisosteres of aromatic rings. To study the biological activity of this relatively new class of bioisosteres, reliable methods to incorporate BCPs into target molecules are in high demand, as reflected by a flurry of methods for BCP synthesis in recent years. In this work, we disclose a general method for the synthesis of BCP-containing dithianes which, upon deprotection, provide access to BCP analogues of medicinally abundant diarylketones. A broad scope of 2-aryl-1,3-dithianes, including several heterocyclic derivatives, react with [1.1.1]propellane to afford 26 new derivatives in good to excellent yields. Further transformation of the dithiane portion into a variety of functional groups demonstrates the robustness of the products. A computational study indicates that the reaction of 2-aryl-1,3-dithianes and [1.1.1]propellane proceeds via a two-electron pathway.