Synthesis of Secondary Boronates via Deaminative Cross-Coupling of Alkyl Nitroso Carbamates and Boronic Acids

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. A strategy for the coupling of N-nitroso carbamates with organo boronic acids is presented. The method allows for the formal deaminative coupling of widely available amines. In particular, the coupling of lysine is presented, which allows for the synthesis of non-canonical amino acids. image