10.1021/jo400246d.s004 Sandeep N. Raikar Sandeep N. Raikar Helena C. Malinakova Helena C. Malinakova Divergent Reaction Pathways of Homologous and Isosteric Propargyl Amides in Sequential Ru/Pd-Catalyzed Annulations for the Synthesis of Heterocycles American Chemical Society 2016 Ru Divergent Reaction Pathways terminal arylalkynes sequential addition RCM Heck cyclization enyne isosteric groups Isosteric Propargyl Amides ring size benzoyl chloride CH vs N heterocyclic dienes Pd catalysts cyclization pathways 2016-02-19 11:21:51 Dataset https://acs.figshare.com/articles/dataset/Divergent_Reaction_Pathways_of_Homologous_and_Isosteric_Propargyl_Amides_in_Sequential_Ru_Pd_Catalyzed_Annulations_for_the_Synthesis_of_Heterocycles/2422387 Cu-catalyzed three-component coupling of imines with benzoyl chloride and terminal arylalkynes followed by enyne ring-closing metathesis (RCM) and Heck cyclization afforded medicinally relevant benzoindolines, cyclopropane-fused indenopyridines, pyrroloquinolines, or 1,7-tetrahydrophenanthrolines via divergent cyclization pathways. Unexpectedly, the Pd-catalyzed cyclization of heterocyclic dienes proceeded via regiodivergent 5-exo or 6-endo pathways depending on the ring size (<i>n</i> = 1, 2) or the presence of isosteric groups (CH vs N). A one-pot protocol for the enyne–RCM/Heck annulation featuring a sequential addition of the Ru and Pd catalysts was developed maximizing the synthetic efficiency.