C–H to C–N Cross-Coupling of Sulfonamides with Olefins

Cross-coupling of nitrogen with hydrocarbons under fragment coupling conditions stands to significantly impact chemical synthesis. Herein, we disclose a C­(sp3)–N fragment coupling reaction between terminal olefins and N-triflyl protected aliphatic and aromatic amines via Pd­(II)/SOX (sulfoxide-oxazoline) catalyzed intermolecular allylic C–H amination. A range of (56) allylic amines are furnished in good yields (avg. 75%) and excellent regio- and stereoselectivity (avg. >20:1 linear:branched, >20:1 E:Z). Mechanistic studies reveal that the SOX ligand framework is effective at promoting functionalization by supporting cationic π-allyl Pd.