The aminolysis of EDC in solution was succinctly investigated by Goldstein et al. in 1971. They studied the reaction of EDC with butylamine (BA) at 50 °C in DMF (0.2 mol L -1 ), using NMR spectrometry. For [BA] = 2[EDC] (i.e. [NH2] = [CC] where CC = cyclic carbonate), they observed that the reaction follows a second order kinetics up to a conversion of ~ 47% for the global CC functions. Then the reaction stops. It was assumed that after the ring opening of one of the two CC of EDC, the remaining CC was unreactive. This assumption was based on the hypothesis of the mutual influence of the vicinal CC units that exert a strong inductive effect on each other. This effect fades away after the first ring opening, and the remaining CC is much less reactive. Their hypothesis was supported by theoretical calculations of the kinetics rate constant of the CC aminolysis, which was found to be in close agreement with experimental results. However, the structure of the product obtained after the first ring opening reaction was not elucidated and the second ring opening reaction was not studied at all. In the present study, EDC was first reacted with 1 eq. of hexylamine (HA) in DMSO ([EDC] = 1 mol L -1 and [NH2] = 1/2[CC]) at 25 °C. As shown in Figure , many products can be expected depending on the chemo-and the regio-selectivity of the reaction. Mono-(1a, 1a') and/or di-hydroxyurethanes (2a, 2a', 2a'') can be obtained depending on whether only one or two of the CC functions of EDC are involved in the reaction. Moreover, the mono-and dihydroxyurethanes can be made of primary, (OH)I, and/or secondary alcohols, (OH)II, depending on the regioselectivity of the ring opening additions. The reaction progress was monitored by 1 H NMR spectroscopy (see the Supporting Information for experimental details). Figure represents the NMR spectra of the crude at t = 0 and after t = 4h of reaction. The proton signals a and b of EDC decreases rapidly, while new signals g, h, e, f and c increases concomitantly. Further analysis of the crude obtained after 4h of reaction ( 13 C, COSY and HSQC NMR, see the Supporting Information, Figure to S5) indicate that these new signals are attributed to the protons of the mono-hydroxyurethanes enantiomers 1a. The integral indicate that EDC is quantitatively transformed into 1a. Thus, the reaction is 100% chemoselective, with only one of the two CC functions of EDC being ring-opened. This result is in accordance with the prediction of the seminal work of Goldstein et al. To our delight, the reaction is also regiospecific, i.e., the ring opening reaction result in the formation of (OH)II exclusively. Examples of such selectivity in the regiocontrol of the uncatalyzed aminolysis of CC are extremely rare. As far as we know, only two reports show complete regiocontrol in the aminolysis of 5-members CC. They were both reported by the group of Endo et al. for the aminolysis of 𝛼𝛼-trifuoromethyland 𝛽𝛽-chloro-substituted CC. The same group demonstrated that the selectivity in favor of (OH)II formation increased as the electron-withdrawing ability of the 𝛼𝛼or 𝛽𝛽-substituent increases. Based on these results, they stated that the direction of the ring-opening aminolysis of 5-membered CC can be controlled by the electronic effect of substituent introduced on the carbonate ring. Thus, the regiospecificity observed for the aminolysis of EDC is in accordance with the strong mutual inductive effect that the vicinal CC units exert on each other.