Polycyclization Enabled by Relay Catalysis: One‐Pot Manganese‐Catalyzed C−H Allylation and Silver‐Catalyzed Povarov Reaction

• Published in: ChemSusChem Vol. 10; no. 11; pp. 2360 - 2364
• Main Authors: Chen, Shi‐Yong, Li, Qingjiang, Liu, Xu‐Ge, Wu, Jia‐Qiang, Zhang, Shang‐Shi, Wang, Honggen
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 09.06.2017
• Subjects: Allyl compounds; Allyl Compounds - chemistry; Bonding; Catalysis; Chemical reactions; Chemical synthesis; Cyclization; Cycloaddition; Cycloaddition Reaction - methods; C−H activation; Economics; Efficiency; Forming; Manganese; Manganese - chemistry; Relay; relay catalysis; silver; Silver - chemistry; Stereoisomerism; Stereoselectivity; relay catalysis; silver; cycloaddition; C−H activation; manganese
• ISSN: 1864-5631; 1864-564X; 1864-564X
• DOI: 10.1002/cssc.201700452

In this study, a MnI/AgI‐based relay catalysis process is described for the one‐pot synthesis of polycyclic products by a formal [3+2] and [4+2] cycloaddition reaction cascade. A manganese(I) complex catalyzed the first example of directed C−H allylation with allenes, setting the stage for an in situ Povarov cyclization catalyzed by silver(I). The reaction proceeds with high bond‐forming efficiency (three C−C bonds), broad substrate scope, high regio‐ and stereoselectivity, and 100 % atom economy. Relay good stuff: MnI/AgI‐based relay catalysis is used for the synthesis of polycycles by formal [3+2] and [4+2] cycloadditions in one pot with high bond‐forming efficiency (three C−C bonds), broad substrate scope, high regio‐ and stereoselectivity, and 100 % atom economy. The Mn‐catalyzed directed C−H allylation with allenes sets the stage for an in situ Povarov cyclization catalyzed by AgI.