biostudies-literatureDorsheimer JRBristol-Myers SquibbNational Institute of General Medical SciencesNIGMS NIH HHS19294-19299https://www.ebi.ac.uk/biostudies/studies/S-EPMC8919398biostudies-literatureUnknown143(46)We report a method to activate α-3° amines for deaminative arylation via condensation with an electron-rich aldehyde and merge this reactivity with nickel metallaphotoredox to generate benzylic quaternary centers, a common motif in pharmaceuticals and natural products. The reaction is accelerated by added ammonium salts. Evidence is provided in support of two roles for the additive: inhibition of nickel black formation and acceleration of the overall reaction rate. We demonstrate a robust scope of amine and haloarene coupling partners and show an expedited synthesis of ALK2 inhibitors.Journal of the American Chemical SocietyDual Nickel/Photoredox-Catalyzed Deaminative Cross-Coupling of Sterically Hindered Primary Amines.PMC8919398R01 GM125206Gm125206Dorsheimer JRAshley MARovis TfalseDual Nickel/Photoredox-Catalyzed Deaminative Cross-Coupling of Sterically Hindered Primary Amines.We report a method to activate α-3° amines for deaminative arylation via condensation with an electron-rich aldehyde and merge this reactivity with nickel metallaphotoredox to generate benzylic quaternary centers, a common motif in pharmaceuticals and natural products. The reaction is accelerated by added ammonium salts. Evidence is provided in support of two roles for the additive: inhibition of nickel black formation and acceleration of the overall reaction rate. We demonstrate a robust scope of amine and haloarene coupling partners and show an expedited synthesis of ALK2 inhibitors.2021-01-01T00:00:00Z2021 Nov2025-04-25T19:28:52.53Z2025-04-06T08:01:55.656ZS-EPMC89193983476736010.1021/jacs.1c10150