Pd and Fe Cocatalyzed\nSynthesis of Remotely Borylated\nAza-Heterocycles

We report the intramolecular 1,<i>n-</i>aminoboration\nfor the simultaneous synthesis of aza-heterocycles with distal carbon–boron\nbonds. Pd-catalyzed remote 1,<i>n-</i>aminoboration occurs\nwith 1,2-disubstituted alkenes; upon aminopalladation of the olefin,\nchain walking generates the terminal Pd-alkyl intermediate, which\nselectively undergoes Fe-catalyzed borylation. Terminal bishomoallylic\namines, amides, carbamates, and ureas afford the borylated pyrrolidines\nand lactams through 1,2-aminoboration. Forty-one examples of 1,<i>n</i>-borylated heterocycles are presented with yields up to\n92%. Derivatization of the products is explored: cross-coupling, amination,\nand oxidation to access unnatural amino alcohols and acids.