Abstract：
Although the 3 d transition-metal catalyzed C-H functionalization have been extensively employed to promote the formation of valuable carbon-carbon bonds, the persistent problems, including the use of sensitive Grignard reagents and the rigorous operations (solvent-drying, inert gas protection, metal pre-activation and RMgX addition rate control), still leave great room for further development of sustainable methodologies. Herein, we report a mechanochemical technology toward in-situ preparation of highly sensitive organomagnesium reagents, and thus building two general 3 d transition-metal catalytic platforms that enables regioselective arylation and alkylation of indoles with a wide variety of halides (including those containing post transformable functionalities and heteroaromatic rings). This mechanochemical strategy also brings unique reactivity and high step-economy in producing functionalized N-free indole products.
摘要：
尽管3d过渡金属催化的C-H官能化已被广泛用于促进有价值的碳-碳键的形成，持续存在的问题，包括使用敏感的格氏试剂和严格的操作(溶剂干燥，惰性气体保护,金属预活化和RMgX添加速率控制)，仍然为可持续方法的进一步发展留下了很大的空间。在这里，我们报道了一种用于原位制备高灵敏度有机镁试剂的机械化学技术，并因此建立了两个通用的3d过渡金属催化平台，该平台能够使吲哚与多种卤化物（包括包含可转化后的官能团和杂芳环的那些）进行区域选择性芳基化和烷基化。这种机械化学策略还在生产官能化的无N吲哚产品中带来了独特的反应性和高的阶梯经济性。
