Iron-Carbonyl-Catalyzed Redox-Neutral [4+2] Annulation of N−H Imines and Internal Alkynes by C−H Bond Activation
Teng Jia
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
Search for more papers by this authorChongyang Zhao
BNLMS, CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190 China
Search for more papers by this authorDr. Ruoyu He
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
Search for more papers by this authorCorresponding Author
Prof. Dr. Hui Chen
BNLMS, CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Congyang Wang
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
Search for more papers by this authorTeng Jia
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
Search for more papers by this authorChongyang Zhao
BNLMS, CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190 China
Search for more papers by this authorDr. Ruoyu He
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
Search for more papers by this authorCorresponding Author
Prof. Dr. Hui Chen
BNLMS, CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Congyang Wang
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
Search for more papers by this authorGraphical Abstract
Double dose of iron: The titled redox-neutral [4+2] annulations to furnish cis-3,4-dihydroisoquinolines were achieved by using iron catalysis. Mechanistic studies show the synergy of dinuclear iron in the C−H bond activation and turnover-limiting hydrogen-transfer steps. The reaction demonstrates excellent atom economy and exclusive cis stereoselectivity.
Abstract
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.
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