Synergistic Heterobimetallic Manifold for Expedient Manganese(I)-Catalyzed C−H Cyanation

• Published in: Chemistry : a European journal Vol. 22; no. 50; pp. 17958 - 17961
• Main Authors: Liu, Weiping, Richter, Sven C., Mei, Ruhuai, Feldt, Milica, Ackermann, Lutz
• Format: Journal Article
• Language: English
• Published: WEINHEIM Blackwell Publishing Ltd 12.12.2016; Wiley; Wiley Subscription Services, Inc
• Subjects: Activation; amino acid; Amino acids; Carbon-carbon composites; Catalysis; Catalysts; Chemical bonds; Chemistry; Chemistry, Multidisciplinary; cyanation; C−H activation; heterocycle; manganese; Manifolds; Physical Sciences; Pyrroles; Science & Technology; ACTIVATION; amino acid; CARBON-CARBON BONDS; heterocycle; ALKYNES; manganese; INDOLES; FUNCTIONALIZATION; cyanation; HYDROGEN; C-H activation; RHODIUM-CATALYZED CYANATION; N-TYPE REACTIONS; AMINO-ACIDS; C−H activation
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201604621

The manganese‐catalyzed cyanation of inert C−H bonds was achieved within a heterobimetallic catalysis regime. The manganese(I) catalysis proved widely applicable and enabled C−H cyanations on indoles, pyrroles and thiophenes by facile C−H manganesation. The robustness of the manganese catalyst set the stage for the racemization‐free C−H cyanation of amino acids with excellent levels of positional and chemo selectivity by the new cyanating agent NCFS. Experimental and computational mechanistic studies provided strong support for a synergistic heterobimetallic activation mode, facilitating the key C−C formation. Two for you: A synergistic heterobimetallic reaction manifold set the stage for manganese(I)‐catalyzed C−H cyanations with ample scope. Mechanistic studies highlighted the multi‐catalytic nature for the key C−C forming elementary step.