In this talk, I will discuss our investigations towards the development of an efficient method for the chemo-, regio-, and diastereo-selective synthesis of gem-diborylalkanes, based on a novel late-stage-desymmetrization for the access of chiral gem-diborylalkanes. The knowledge gained from this approach provided us with an in-depth understanding of their reactivity for additional transformations. This enabled the development of optimized reaction conditions for C–B functionalization in order to construct new C–C bond, which is based on the rationally designed protocol for palladium-catalyzed cross-coupling reaction.