Catalysis

Manganese Catalysed Dehydrogenative Synthesis of Urea Derivatives and Polyureas

Authors

Abstract

Urea derivatives are prevalent intermediates in the synthesis of resin precursors, dyes, agrochemicals, and pharmaceutical drugs. Furthermore, polyureas are useful plastics with applications in coating, adhesive, and biomedical industries and have a current annual market of USD 885 million. However, the conventional methods for the synthesis of urea derivatives and polyureas involve toxic reagents such as (di)isocyanates, phosgene, CO, and azides. We present here the synthesis of (poly)ureas using much less toxic reagents - (di)amines, and methanol via a catalytic dehydrogenative coupling process. The reaction is catalyzed by a pincer complex of an earth-abundant metal, manganese, and liberates H2 gas, valuable by itself, as the only by-product making the overall process atom-economic, and sustainable. A broad variety of symmetrical, and unsymmetrical urea derivatives and polyureas have been synthesized in moderate to quantitative yields using this catalytic protocol. Mechanistic insights have also been provided using experiments and DFT computation suggesting that the reaction proceeds via an isocyanate intermediate.

Content

Thumbnail image of Mn_urea_Dec 29_draft_preprint.pdf

Supplementary material

Thumbnail image of Mn_urea_SI_ADec 28_ for Preprint.pdf
Supporting information
Supporting information contains details of catalytic dehydrogenation, synthesis/characterization of (poly)ureas, mechanistic studies, NMR, IR, MALDI-TOF mass spectrometry and computational details.