Iron-Catalyzed Cross-Electrophile\nCoupling for the\nFormation of All-Carbon Quaternary Centers

Quaternary carbon centers are desirable targets for drug\ndiscovery\nand complex molecule synthesis, yet the synthesis of these motifs\nwithin traditional cross-coupling paradigms remains a significant\nchallenge due to competing β-hydride elimination pathways. In\ncontrast, the bimolecular homolytic substitution (S<sub>H</sub>2)\nmechanism offers a unique and attractive alternative pathway. Metal\nporphyrin complexes have emerged as privileged catalysts owing to\ntheir ability to selectively form primary metal–alkyl complexes,\nthereby eliminating the challenges associated with tertiary alkyl\ncomplexation with a metal center. Herein, we report an iron-catalyzed\ncross-electrophile coupling of tertiary bromides and primary alkyl\nelectrophiles for the formation of all-carbon quaternary centers through\na biomimetic S<sub>H</sub>2 mechanism.