This work describes the first Ni-catalyzed cross-electrophile coupling of alkylpyridinium salts, derived from the corresponding amines, with aryl iodide, bromoalkyne or bromoalkyl coupling partners. C(sp)-C(sp<sup>3</sup>), C(sp<sup>2</sup>)-C(sp<sup>3</sup>) and C(sp<sup>3</sup>)-C(sp<sup>3</sup>) bond formation was achieved to afford a variety of synthetically useful arenes, alkynes and alkanes in good yields from<b>2</b>-<b>33</b>. The advantages of the methodology are showcased in the two-step synthesis of the key lactonic moiety of (+)-Compactin and (+)-Mevinolin from commercially available starting materials. A one-pot procedure without isolation of alkylpyridinium tetrafluoroborate salt was also demonstrated to be successful. This work represents a new strategy for the cross-coupling reaction of two electrophiles, and also provides a complementary and highly valuable vista for the current methodologies of alkyl arene/alkyne/alkane synthesis.
