title: The Quest for Palladium-Catalysed Alkyl-Nitrogen Bond Formation.
abstract: Our interest in the development of transition-metal catalysis for the realisation of vicinal diamination reactions of alkenes started about a decade ago. A number of successful transformations in this area have been developed using palladium catalysis. As a challenging aspect of major importance, the palladium-catalysed coupling of alkyl-nitrogen bonds constitutes the second step in diaminations of alkenes. We here discuss the details that led us to consider high-oxidation-state palladium catalysis as a key feature in such C-N bond-forming reactions. This work discusses both our own contributions and the ones from colleagues and combines the discussion of catalytic reactions and stoichiometric control experiments. It demonstrates that reductive alkyl-nitrogen bond formation from palladium(IV) proceeds with a low activation barrier and through a linear transition state of nucleophilic displacement.
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ) The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007, Tarragona, Spain.|ICREA, Pg. Lluís Companys 23, 08010, Barcelona, Spain.
authors.forename: Kilian
authors.initials: K
authors.lastname: Muñiz
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ) The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007, Tarragona, Spain.
authors.forename: Claudio
authors.initials: C
authors.lastname: Martínez
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ) The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007, Tarragona, Spain.
authors.forename: Álvaro
authors.initials: Á
authors.lastname: Iglesias
keywords: alkenes; amination; oxidation; palladium; reductive elimination