Alkyl boronic acids and their esters are of great importance in chemical science. For example, the compound class is widely used in organic synthesis for, e.g., the powerful Suzuki-Miyaura cross-coupling as well as for Chan-Lam couplings. In the context of medicinal chemistry, the introduction of boronic acids can improve activity and/or pharmacokinetic properties, whereas the reversible dynamic covalent bonds of boronic esters have enabled the synthesis of self-healing macromolecular materials. There are various synthetic routes to organoboron compounds, e.g., hydroboration of olefins, addition of organometallic nucleophiles to boron electrophiles. Furthermore, borylative cross-couplings using transition metal catalysis are known for starting materials such as aryl and alkyl halides redox active N-hydroxyphthalimide (NHPI) esters (RAE's), and derivatives of amines, alcohols and thiols. In context of the latter, sulfonium salts are the most common precursors for desulfurative borylations. Aryl alkyl thioethers have also been reported as substrates, with full selectivity for borylation of the aryl side-chain (Figure ). While these methods commonly display good functional group tolerance and wide substrate scopes, transition-metal based procedures can be costly as well as create problems in, e.g., the pharmaceutical industry where removal of trace metal residues from the final products is critical. For this reason, cost effective, simple, and metal free synthetic procedures are in high demand.