锰催化的碳碳键生成反应研究进展

Progress on Mn-Catalyzed C-C Bond-Forming Reactions

迄今为止,贵金属(铑、钯、钌等)在过渡金属催化的碳碳键生成反应中发挥着主导作用,然而使用廉价金属催化剂更符合可持续发展的要求。锰是地壳中含量排第三位的过渡金属,价格便宜,环境危害性小,有潜力成为贵金属催化剂的替代品并发挥其自身独特的反应性。尽管锰参与的当量反应有大量文献报道,目前锰催化的反应尤其是碳碳键生成反应的发展还不成熟,如何实现高效的催化循环是锰催化领域面临的主要难题之一。本文对锰催化的付-克烷基化反应、格氏试剂的酰化反应、偶联反应、碳金属化反应、自由基反应和碳氢键活化反应进行了综述。

So far,noble transition-metal(e.g.Rh,Pd,and Ru) catalysts have played a leading role in the area of C-C bond-forming reactions.However,from the viewpoint of sustainable development,it is desirable for chemists to develop more economic alternatives to these precious metals.In line with this,manganese is naturally abundant and inexpensive,and can be promising candidates for the catalyst development in C-C bond-forming reactions.Although Mn-mediated stoichiometric reactions have been well documented,considerably fewer examples of Mn-catalyzed reactions,especially C-C bond-forming ones,have been disclosed until recently,and significant challenges still remain to achieve efficient catalytic turnover.Herein the Mn-catalyzed C-C bond-forming reactions are reviewed,which can be roughly classified into six types:Friedel-Crafts alkylation reactions,acylation reactions of Grignard reagents,coupling reactions,carbometalation reactions,radical reactions and C-H activation reactions.