Modular Dual-Tasked C-H Methylation via the Catellani Strategy
Modular Dual-Tasked C-H Methylation via the Catellani Strategy
复制标题
通过 Catellani 策略进行模块化双任务 C-H 甲基化
DOI：
10.1021/jacs.9b07857
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发表时间：
2019-10-09
影响因子：
15
通讯作者：
Zhou, Qianghui
中科院分区：
文献类型：
--
作者：
Gao, Qianwen;Shang, Yong;Zhou, Qianghui
我们报告了一个双任务的甲基化，这是基于合作钯/双烯催化。容易获得的（杂）芳基卤化物（39碘化物和4溴化物）和廉价的MeOTs或磷酸三甲酯分别用作底物和甲基化试剂。六种类型的“ipso”末端可以模块化地与这种“邻位”C-H甲基化偶联，从而构成用于制备多样化甲基化芳烃的通用甲基化工具箱。该工具箱具有廉价的甲基来源，出色的官能团耐受性，简单的反应程序和可扩展性。重要的是，它可以通过转换为相应的试剂CD 3 OTs或（CH 3 OTs）-C-13而顺利地扩展到同位素标记的甲基化。此外，该工具箱可以应用于具有完全立体保留的生物相关底物的后期修饰。我们相信，我们的双任务甲基化工具箱的这些突出和实用的功能将受到学术和工业研究人员的欢迎。
We report a dual-tasked methylation that is based on cooperative palladium/norbornene catalysis. Readily available (hetero)aryl halides (39 iodides and 4 bromides) and inexpensive MeOTs or trimethylphosphate are utilized as the substrates and methylating reagent, respectively. Six types of "ipso" terminations can modularly couple with this "ortho" C-H methylation to constitute a versatile methylation toolbox for preparing diversified methylated arenes. This toolbox features inexpensive methyl sources, excellent functional-group tolerance, simple reaction procedures, and scalability. Importantly, it can be uneventfully extended to isotope-labeled methylation by switching to the corresponding reagents CD3OTs or (CH3OTs)-C-13. Moreover, this toolbox can be applied to late-stage modification of biorelevant substrates with complete stereoretention. We believe these salient and practical features of our dual-tasked methylation toolbox will be welcomed by academic and industrial researchers.