sc7b02756_si_001.pdf (554.66 kB)

Highly Recyclable Fluoride for Enhanced Cascade Hydrosilylation–Cyclization of Levulinates to γ‑Valerolactone at Low Temperatures

Download (554.66 kB)
journal contribution
posted on 25.09.2017 by Wenfeng Zhao, Tingting Yang, Hu Li, Weibo Wu, Zhongwei Wang, Chengjiang Fang, Shunmugavel Saravanamurugan, Song Yang
A facile and benign catalytic route has been developed to quantitatively yield γ-valerolactone (GVL; ca. 97%) from biomass-based levulinates at room temperature to 80 °C by using easily available polymethylhydrosiloxane (PMHS) and KF as the liquid H-donor and recyclable catalyst, respectively. No extra step was required to liberate GVL from the in situ-formed siloxane, and this catalytic system exhibited a lower activation energy (40.9 kJ/mol) compared to previously reported ones. The deuterium-labeled study further demonstrated the reaction proceeding through cascade hydrosilylation and cyclization with fluoride successively acting as the nucleophile and base. In addition, the PMHS-derived resin was extremely favorable to restrain the leaching of fluoride and maintain its constant activity for at least six cycles.

History

Exports