Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China.
BNLMS, CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China.
Angew Chem Int Ed Engl. 2016 Apr 18;55(17):5268-71. doi: 10.1002/anie.201600365. Epub 2016 Mar 22.
Stoichiometric C-H bond activation of arenes mediated by iron carbonyls was reported by Pauson as early as in 1965, yet the catalytic C-H transformations have not been developed. Herein, an iron-catalyzed annulation of N-H imines and internal alkynes to furnish cis-3,4-dihydroisoquinolines is described, and represents the first iron-carbonyl-catalyzed C-H activation reaction of arenes. Remarkablely, this is also the first redox-neutral [4+2] annulation of imines and alkynes proceeding by C-H activation. The reaction also features only cis stereoselectivity and excellent atom economy as neither base, nor external ligand, nor additive is required. Experimental and theoretical studies reveal an oxidative addition mechanism for C-H bond activation to afford a dinuclear ferracycle and a synergetic diiron-promoted H-transfer to the alkyne as the turnover-determining step.
早在 1965 年，Pauson 就报道了铁羰基介导的芳基的化学计量 C-H 键活化，但催化 C-H 转化尚未得到发展。本文描述了铁催化的 N-H 亚胺和内部炔烃的环化反应，生成顺式-3,4-二氢异喹啉，这代表了芳基的首例铁-羰基催化 C-H 活化反应。值得注意的是，这也是首例通过 C-H 活化进行的氧化还原中性[4+2]环化反应。该反应还具有独特的顺式立体选择性和出色的原子经济性，因为既不需要碱、也不需要外部配体、也不需要添加剂。实验和理论研究揭示了 C-H 键活化的氧化加成机制，生成双核铁环和协同双铁促进的 H 转移到炔烃，这是周转决定步骤。
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