Any attempt to facilitate a new generation of C-B bonds represents a useful tool in organic synthesis. In addition, if that approach highlights the nucleophilic character of boryl moieties in the absence of transition metal complexes, the challenge to create new reactive platforms becomes an opportunity. We have been deeply involved in the experimental and theoretical validation of C-B bond formation by means of alkoxide activation of tetra-alkoxy diboron reagents and here is presented a convenient guide to understand the concept and the applications.