Abstract
Oxidative allylic C–H functionalization is a powerful tool to streamline organic synthesis as it minimizes the need for functional group activation and generates alkenyl-substituted products amenable to further chemical modifications. The intramolecular variants can be used to construct functionalized ring structures but remain limited in scope and by their frequent requirement for noble metal catalysts and stoichiometric chemical oxidants. Here we report an oxidant-free, electrocatalytic approach to achieve intramolecular oxidative allylic C–H amination and alkylation by employing tailored cobalt-salen complexes as catalysts. These reactions proceed through a radical mechanism and display broad tolerance of functional groups and alkene substitution patterns, allowing efficient coupling of di-, tri- and even tetrasubstituted alkenes with N- and C-nucleophiles to furnish high-value heterocyclic and carbocyclic structures.
Highlights
Oxidative allylic C–H functionalization is a powerful tool to streamline organic synthesis as it minimizes the need for functional group activation and generates alkenyl-substituted products amenable to further chemical modifications
Catalytic allylic C–H functionalizations are attractive transformations because they maximize step- and atom-economy and the retained or newly formed alkenyl moiety is available for versatile further transformations[1,2,3]
Intramolecular variants of these transformations can provide rapid access to functionalized hetero- and carbocycles. These allylic C–H functionalization reactions are generally catalyzed by noble metals such as Pd, Ru, and Ir and involve either the formation of an allylmetal complex via C–H activation followed by it being attacked by a tethered nucleophile, or sequential nucleometallation and βhydride elimination (Fig. 1a)[1,2,3]
Summary
Oxidative allylic C–H functionalization is a powerful tool to streamline organic synthesis as it minimizes the need for functional group activation and generates alkenyl-substituted products amenable to further chemical modifications. We have accomplished Cu(II)-catalyzed intramolecular allylic C–H amination with DMP as the terminal oxidant (Fig. 1c)[21]. 3° alkyl radicals are oxidized to carbocations by the Cu(II) salts, resulting in by-product formation and yield reduction[23].
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
