A strategy for transition metal‐free cross‐coupling of alkyl nitroso‐carbamates and boronic acids is reported. The N‐nitroso carbamates are easily prepared from the corresponding amine in two simple steps. This method allows for the synthesis of a wide variety of secondary boronates, benzylic boronates and formal Csp3−Csp2 cross‐coupling products under operationally simple conditions. Functional group tolerance is also demonstrated and applied in the modification of lysine to make non‐canonical amino acids.