Abstract
Levoglucosenone (LGO), a biobased platform molecule derived from cellulose waste, offers a versatile scaffold owing to its cyclic acetal bridge and reactive enone functionalities. Building on our previous work on stereoselective polymer formation from LGO, this study explores the incorporation of regioisomeric benzenedithiols (1,3- and 1,2-) via thia-Michael addition to afford structurally defined LGO-based monomers. These monomers were subsequently polycondensed with dicarboxylic dihydrazides to yield degradable polyhydrazones with well-defined stereochemistry. Notably, the regioisomeric structure of benzenedithiols induces a striking inversion of optical activity in the resulting polymers, demonstrating that the sign of the optical rotation can be controlled through monomer connectivity. This finding highlights a new strategy for tuning polymer properties from a single bio-based building block. The physicochemical, thermal, optical, and aqueous degradation properties of the resulting polymers were comprehensively characterized. In addition, the synthetic procedures have been optimized to improve sustainability by replacing hazardous solvents with greener alternatives.