Chemoselective Hydrogenolysis of Urethanes to Formamides and Alcohols in the Presence of More Electrophilic Carbonyl Compounds

Authors

Takanori Iwasaki, Yuto Yamada, Naoki Naito, Kyoko Nozaki

Abstract

The development of methods for the chemical recycling of polyurethanes is recognized as an urgent issue. Herein, we report the Ir-catalyzed hydrogenolysis of the urethane C–O bond to produce formamides and alcohols, where both formamides and ester and amide functionalities are tolerated. The chemoselectivity observed is counterintuitive to the generally accepted electrophilicity order of carbonyl compounds. Hydrogenolysis of urea and isocyanurate, potential byproducts in the polycondensation process of polyurethanes, is also achieved alongside the selective degradation of polyurethanes themselves, which affords diformamides and diols. The time-course of the hydrogenative polyurethane degradation reveals that the bond cleavage occurs not from the terminal, but from any part of the polymer chain. The present catalysis offers a novel method for the recycling of polyurethane-containing polymer waste.

Journal of the American Chemical Society: https://pubs.acs.org/doi/10.1021/jacs.4c06553