Copper-induced ammonia N–H functionalization

Abstract

The activation of ammonia has been achieved with the aid of the Tp^MsCu core (Tp^Ms = hydrotris(3-mesityl-pyrazolyl)borate). Complexes of the general composition Tp^MsCu(amine) (1–4) including the ammonia adduct Tp^MsCu(NH₃) (1) have been synthesized and fully spectroscopical- and structurally characterized. Coordinated ammonia in 1 has been reacted with Ph₃CPF₆ yielding Tp^MsCu(NH₂CPh₃) (5) as a result of N–H cleavage and N–C bond formation. In a parallel manner the catalytic functionalization of ammonia with ethyl diazoacetate leading to glycinate derivatives has been developed with Tp^MsCu(THF) as the catalyst, in the first example of this transformation with ammonia and a copper-based system.