Dual C-F, C-H Functionalization via Photocatalysis: Access to Multifluorinated Biaryls.
Dual C-F, C-H Functionalization via Photocatalysis: Access to Multifluorinated Biaryls.
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DOI：
10.1021/jacs.5b13450
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发表时间：
2016-03-02
影响因子：
15
通讯作者：
Weaver JD
中科院分区：
文献类型：
--
作者：
Senaweera S;Weaver JD
多氟联芳烃是一类具有挑战性的重要分子。由于与选择性氟化有关的困难，这类分子代表着一个巨大的合成挑战。选择性氟化联芳烃的另一种方法是将已经在所需位置上具有C-F键的芳烃偶联。这一战略经常被使用，严重依赖于使用有机金属和卤化物(或假卤化物)来实现耦合的传统交叉耦合战略。在这里，我们报道了通过全氟芳烃的C-F键和另一种芳烃的C-H键的直接官能化进行光催化偶联的条件，以提供一条合成多氟联芳基的便捷途径。温和的条件和良好的官能团耐受性使其具有广泛的范围-包括获得碱性杂环的抗微米级产物。最后，我们展示了C-F功能化方法的价值，通过光催化和SNAR化学的协同使用，利用高氟含量来系统地构建包含2-5个Caryl-F键的复杂的联芳基。
Multifluorinated biaryls are challenging to synthesize and yet an important class of molecules. Owing to the difficulty associated with selective fluorination, this class of molecules represent a formidable synthetic challenge. An alternative approach to selective fluorination of biaryls is to couple an arene which already possess C–F bonds in the desired location. This strategy has been regularly utilized, relying heavily on traditional cross-coupling strategies which employ organometallics and halides (or pseudohalides) in order to achieve the coupling. Herein, we report conditions for the photocatalytic coupling via the direct functionalization of the C–F bond of a perfluoroarene and C–H bond of the other arene to provide an expedient route to multifluorinated biaryls. The mild conditions and good functional group tolerance enable a broad scope-including access to the anti-Minisci product of basic heterocycles. Finally, we demonstrate the value of the C–F functionalization approach by utilizing the high fluorine content to systematically build complex biaryls that contain between 2–5 Caryl–F bonds via synergistic use of photocatalysis and SNAr chemistry.