biostudies-literatureGay BLDivision of ChemistryAmgenUniversity of Texas at AustinStephen F. Austin State UniversityWelch FoundationNational Institute of General Medical SciencesNIGMS NIH HHSEli Lilly and CompanyNovartis18939-18947https://www.ebi.ac.uk/biostudies/studies/S-EPMC10772865biostudies-literatureUnknown145(34)Aminoboration of simple alkenes with nitrogen nucleophiles remains an unsolved problem in synthetic chemistry; this transformation can be catalyzed by palladium <i>via</i> aminopalladation followed by transmetalation with a diboron reagent. However, this catalytic process faces inherent challenges with instability of the alkylpalladium(II) intermediate toward β-hydride elimination. Herein, we report a palladium/iron cocatalyzed aminoboration, which enables this transformation. We demonstrate these conditions on a variety of alkenes and norbornenes with an array of common nitrogen nucleophiles. In the developed strategy, the iron cocatalyst is crucial to achieving the desired reactivity by serving as a halophilic Lewis acid to release the transmetalation-active cationic alkylpalladium interJournal of the American Chemical SocietyPalladium and Iron Cocatalyzed Aerobic Alkene Aminoboration.PMC10772865R01 GM111480FG-2016-6568R35 GM1250292155133Tarasewicz AWang YNNeidig MLCooke DJGary JBGay BLZhang BBhatt SMilem EGHull KLfalsePalladium and Iron Cocatalyzed Aerobic Alkene Aminoboration.Aminoboration of simple alkenes with nitrogen nucleophiles remains an unsolved problem in synthetic chemistry; this transformation can be catalyzed by palladium <i>via</i> aminopalladation followed by transmetalation with a diboron reagent. However, this catalytic process faces inherent challenges with instability of the alkylpalladium(II) intermediate toward β-hydride elimination. Herein, we report a palladium/iron cocatalyzed aminoboration, which enables this transformation. We demonstrate these conditions on a variety of alkenes and norbornenes with an array of common nitrogen nucleophiles. In the developed strategy, the iron cocatalyst is crucial to achieving the desired reactivity by serving as a halophilic Lewis acid to release the transmetalation-active cationic alkylpalladium inter2023-01-01T00:00:00Z2023 Aug2025-05-18T12:53:32.54Z2025-05-18T12:53:32.54ZS-EPMC107728653758410710.1021/jacs.3c05790