Sulfur and nitrogen (half-)mustard carbonate analogues are a new class of compounds, easily synthesized by methoxycarbonylation reaction of the parent alcohols with dialkyl carbonates. In this work, their reactivity as novel, green electrophiles is reported. Reactions have been conducted in autoclave conditions at high temperature (180°C), under pressure and in absence of any base, as well as, in neat at atmospheric pressure, lower temperature (150°C) and in the presence of a catalytic amount of a base. Several nucleophiles have been investigated resulting, in some cases, in unexpected compounds, i.e., six-membered heterocycle piperidine. Reaction mechanism and kinetics have been studied confirming that these compounds retain the anchimeric effect of their mustard gas analogues, without being toxic. Noteworthy, a symmetrical nitrogen mustard carbonate has also been employed as reagent in the preparation of a new family of macrocycles i.e., azacrowns, before not easily accessible.