Sequence-Controlled Polyhydroxyurethanes with Tunable Regioregularity Obtained from Sugar-Based Vicinal Bis-cyclic Carbonates

The carbonation of biosourced 1,2-diols is a sustainable avenue for the synthesis bis-five-membered cyclic carbonates (bis-5CCs), precursors valuable class polymers, example, polyhydroxyurethanes (PHUs). In this work, we performed direct optically pure sugar-based butadiene tetraols, namely, (i) meso-erythritol and (ii) its (S,S) diastereoisomer, (L)-threitol. corresponding vicinal bis-5CCs, erythritol dicarbonate (EDC) threitol (TDC), respectively, retain stereochemistry starting tetraols. comprehensive study their aminolysis reaction, in DMSO at room temperature, indicates that kinetics regio-orientation ring opening 5CC are very much dependent on stereochemistry. total EDC results formation hydroxyurethanes with an excess secondary hydroxyl groups, (OH)II, about 85%, against 60% TDC. Moreover, when considering two consecutive aminolyses (and TDC, respectively), kinetic rate constant first k1,EDC k1,TDC, respectively) 1 order magnitude higher than second aminolysis, k2,EDC ? k1,EDC/10 k2,TDC k1,TDC/10, respectively). We used feature to develop one-pot, two-step polymerization procedure, offering sequence-controlled PHUs. All experimental well supported by density functional theory calculations. end, comparative these diastereoisomers simple bis-5CCs provides new family PHUs tunable sequence- regioregularities.