Manganese-catalyzed dehydrogenative synthesis of urea derivatives and polyureas

Aniekan Owen, Annika Preiss, Angus Mcluskie, Chang Gao, Gavin Peters, Michael Buehl, Amit Kumar*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

16 Citations (Scopus)
9 Downloads (Pure)


Urea derivatives have significant applications in the synthesis of resin precursors, dyes, agrochemicals, and pharmaceutical drugs. Furthermore, polyureas are useful plastics with applications in coating, adhesive, and biomedical industries. 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 byproduct, making the overall process highly atom-economic. 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.
Original languageEnglish
Pages (from-to)6923-6933
JournalACS Catalysis
Early online date27 May 2022
Publication statusE-pub ahead of print - 27 May 2022


  • Catalysis
  • Dehydrogenation
  • Manganese
  • Methanol
  • Pincer
  • Polyurea
  • Urea


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