De novo syntheses of amides often generate stoichiometric amounts of waste. Thus, recent progress in the field has focused on precious metal catalyzed, oxidative protocols to generate such functionalities. However, simple tertiary alkyl amines cannot be used as starting materials in these protocols. The research described herein enables the oxidative synthesis of amides from simple, noncyclic tertiary alkyl amines under synthetically useful, mild conditions through a biologically inspired approach: Fe-catalyzed Cα-H functionalization. Mechanistic investigations provide insight into reaction intermediates and allow the development of a mild Cα-H cyanation method using the same catalyst system. The protocol was further applied to oxidize the drug Lidocaine, demonstrating the potential utility of the developed chemistry for metabolite synthesis.
De novo syntheses of amides often generate stoichiometric amounts of waste.Thus,recent progress in the field has focused on precious metal catalyzed, oxidative protocols to generate such functionalities.H owever,s imple tertiary alkyl amines cannot be used as starting materials in these protocols. The researchd escribed herein enables the oxidative synthesis of amides from simple,n oncyclic tertiary alkyla mines under synthetically useful, mild conditions through ab iologically inspired approach:F e-catalyzed C a ÀHf unctionalization. Mechanistic investigations provide insight into reaction intermediates and allow the development of amild C a ÀHcyanation method using the same catalyst system. The protocol was further applied to oxidize the drug Lidocaine,d emonstrating the potential utility of the developed chemistry for metabolite synthesis.
Benzoyl tert‐butyl peroxide is shown to be an efficient oxidant for the selective mono‐oxidation of tertiary amines to amides using FeCl3 as catalyst and picolinic acid as co‐catalyst.
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