Fe/Mn-Synergistic Promoted C(sp3)–Bi Cross-Coupling of Alkyl Chlorides with Chlorobismuthanes to Access Air-Stable Alkylbismuthanes

Alkylating bismuthanes containing C(sp3)–Bi bonds were first disclosed as early as 1850, but their development remains severely limited, especially the synthetic method. Herein, we developed the first Fe/Mn-synergistic promoted C(sp3)–Bi cross-coupling of alkyl halides with chlorobismuthanes, which can access alkylbismuthanes in satisfactory yields with various functional group compatibility (cyano, ester, aldehyde, and amide). Inactivated alkyl chlorides/bromides, as well as cyclic and acyclic alkyl electrophiles, smoothly yielded the corresponding products. Gram-scale synthesis and late-stage modification of drug molecules were also conducted. The synthesized alkylbismuthanes also could be alkylation reagents toward C(sp3)–C(sp2), C(sp3)–Se, C(sp3)–S, and C(sp3)–N bonds.