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PreprintCC BY-NC-NDChemRxiv

Bio-Based Levoglucosenone Enables Regioisomer-Driven Inversion of Optical Activity in Polymers via Stereoselective Thia-Michael Addition of 1,2- and 1,3-Benzenedithiols

  • Francesco Raboni1,2
  • Shinji Kudo3
  • Takayuki Doi2
  • Alessandro Pellis1
  • Atsushi Tahara2,4
4 affiliations
  1. 1Department of Chemistry and Industrial Chemistry, Università degli Studi di Genova, Via Dodecaneso 31, Genova, Italy, 16146
  2. 2Graduate School of Pharmaceutical Sciences, Tohoku University, Aoba 6-3, Aramaki, Aoba-ku, Sendai, Miyagi, Japan, 980-8578
  3. 3Institute for Materials Chemistry and Engineering (IMCE, Kyushu University, Kasugakoen 6-1, Fukuoka, Japan, 816-8580
  4. 4Frontier Research Institute for Interdisciplinary Sciences (FRIS, Tohoku University, Aoba 6-3, Aramaki, Aoba-ku, Sendai, Miyagi, Japan, 980-8578
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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.

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Cite

BibTeXRIS
BibTeX
@misc{raboni2026biobased,
  title = {{Bio-Based Levoglucosenone Enables Regioisomer-Driven Inversion of Optical Activity in Polymers via Stereoselective Thia-Michael Addition of 1,2- and 1,3-Benzenedithiols}},
  author = {Francesco Raboni and Shinji Kudo and Takayuki Doi and Alessandro Pellis and Atsushi Tahara},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15009046/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009046/v1},
  note = {CC BY-NC-ND},
}
RIS
TY  - UNPB
TI  - Bio-Based Levoglucosenone Enables Regioisomer-Driven Inversion of Optical Activity in Polymers via Stereoselective Thia-Michael Addition of 1,2- and 1,3-Benzenedithiols
AU  - Francesco Raboni
AU  - Shinji Kudo
AU  - Takayuki Doi
AU  - Alessandro Pellis
AU  - Atsushi Tahara
PY  - 2026
DA  - 2026/09/18
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15009046/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009046/v1
AB  - 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.
ER  -