Stereoselective\nFe-Catalyzed Decoupled Cross-Couplings:\nChiral Vinyl Oxazolidinones as Effective Radical Lynchpins for Diastereoselective\nC(sp<sup>2</sup>)–C(sp<sup>3</sup>) Bond Formation

Modular, catalytic, and stereoselective methods for the\ndicarbofunctionalization\nof alkenes can streamline the synthesis of chiral active pharmaceutical\ningredients (APIs) and agrochemicals. However, despite the inherent\nattractive properties of iron as catalysts for practical pharmaceutical\nsynthesis (i.e., less expensive, more abundant, less toxic, and lower\ncarbon footprint in comparison to other transition metals), iron-based\ncatalytic methods that enable highly stereoselective dicarbofunctionalization\nof alkenes are lacking. Herein, we report the use of readily available\nchiral vinyl oxazolidinones as effective chiral radical lynchpins\nto enable practical and diastereoselective (up to 1:78 dr) Fe-catalyzed\ndicarbofunctionalization with fluoroalkyl halides and hetero(aryl)\nGrignard reagents. Experimental and computational mechanistic studies\nare carried out to elucidate the origin of stereoinduction and to\nbuild a stereochemical model for the rational reaction design.