title: Divergent C-H Insertion-Cyclization Cascades of N-Allyl Ynamides.
abstract: Gold carbene reactivity patterns were accessed by ynamide insertion into a C(sp(3) )H bond. A substantial increase in molecular complexity occurred through the cascade polycyclization of N-allyl ynamides to form fused nitrogen-heterocycle scaffolds. Exquisite selectivity was observed despite several competing pathways in an efficient gold-catalyzed synthesis of densely functionalized C(sp(3) )-rich polycycles and a copper-catalyzed synthesis of fused pyridine derivatives. The respective gold-keteniminium and ketenimine activation pathways have been explored through a structure-reactivity study, and isotopic labeling identified turnover-limiting CH bond-cleavage in both processes.
authors.affiliation: School of Chemistry, University of Birmingham, Birmingham (UK).
authors.forename: Holly V
authors.initials: HV
authors.lastname: Adcock
authors.affiliation: School of Chemistry, University of Birmingham, Birmingham (UK).
authors.forename: Elli
authors.initials: E
authors.lastname: Chatzopoulou
authors.affiliation: School of Chemistry, University of Birmingham, Birmingham (UK). p.w.davies@bham.ac.uk.
authors.forename: Paul W
authors.initials: PW
authors.lastname: Davies
keywords: carbenes; cyclopropanation; gold; nitrogen heterocycles; ynamides