Isocyanate-Free Polyurea Synthesis via Ru-Catalyzed Carbene Insertion into the N-H Bonds of Urea

Felix J. De Zwart; Petrus C.M. Laan; Nicole S. Van Leeuwen; Eduard O. Bobylev; Erika R. Amstalden Van Hove; Simon Mathew; Ning Yan; Jitte Flapper; Keimpe J. Van Den Berg; Joost N.H. Reek; Bas De Bruin

doi:10.1021/acs.macromol.2c01457

Isocyanate-Free Polyurea Synthesis via Ru-Catalyzed Carbene Insertion into the N-H Bonds of Urea

Felix J. De Zwart, Petrus C.M. Laan, Nicole S. Van Leeuwen, Eduard O. Bobylev, Erika R. Amstalden Van Hove, Simon Mathew, Ning Yan, Jitte Flapper, Keimpe J. Van Den Berg, Joost N.H. Reek, Bas De Bruin^*

^*Corresponding author for this work

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Research output: Contribution to Journal › Article › Academic › peer-review

Abstract

Polyureas have widespread applications due to their unique material properties. Because of the toxicity of isocyanates, sustainable isocyanate-free routes to prepare polyureas are a field of active research. Current routes to isocyanate-free polyureas focus on constructing the urea moiety in the final polymerizing step. In this study we present a new isocyanate-free method to produce polyureas by Ru-catalyzed carbene insertion into the N-H bonds of urea itself in combination with a series of bis-diazo compounds as carbene precursors. The mechanism was investigated by kinetics and DFT studies, revealing the rate-determining step to be nucleophilic attack on a Ru-carbene moiety by urea. This study paves the way to use transition-metal-catalyzed reactions in alternative routes to polyureas.

Original language	English
Pages (from-to)	9690-9696
Number of pages	7
Journal	Macromolecules
Volume	55
Issue number	21
Early online date	17 Oct 2022
DOIs	https://doi.org/10.1021/acs.macromol.2c01457
Publication status	Published - 8 Nov 2022

Bibliographical note

Funding Information:
Financial support from the Advanced Research Center for Chemical Building Blocks (ARC CBBC, project 2018.015.C and 2019.021.A), which is cofounded and cofinanced by the Dutch Research Council (NWO) and The Netherlands Ministry of Economic Affairs and Climate Policy, is gratefully acknowledged. P.C.M.L. and N.Y. acknowledge the financial support from The Netherlands Organization for Scientific Research (NWO) VIDI program (VI.Vidi.192.045).

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© 2022 American Chemical Society. All rights reserved.

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title = "Isocyanate-Free Polyurea Synthesis via Ru-Catalyzed Carbene Insertion into the N-H Bonds of Urea",

abstract = "Polyureas have widespread applications due to their unique material properties. Because of the toxicity of isocyanates, sustainable isocyanate-free routes to prepare polyureas are a field of active research. Current routes to isocyanate-free polyureas focus on constructing the urea moiety in the final polymerizing step. In this study we present a new isocyanate-free method to produce polyureas by Ru-catalyzed carbene insertion into the N-H bonds of urea itself in combination with a series of bis-diazo compounds as carbene precursors. The mechanism was investigated by kinetics and DFT studies, revealing the rate-determining step to be nucleophilic attack on a Ru-carbene moiety by urea. This study paves the way to use transition-metal-catalyzed reactions in alternative routes to polyureas.",

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note = "Funding Information: Financial support from the Advanced Research Center for Chemical Building Blocks (ARC CBBC, project 2018.015.C and 2019.021.A), which is cofounded and cofinanced by the Dutch Research Council (NWO) and The Netherlands Ministry of Economic Affairs and Climate Policy, is gratefully acknowledged. P.C.M.L. and N.Y. acknowledge the financial support from The Netherlands Organization for Scientific Research (NWO) VIDI program (VI.Vidi.192.045). Publisher Copyright: {\textcopyright} 2022 American Chemical Society. All rights reserved.",

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AU - De Zwart, Felix J.

AU - Laan, Petrus C.M.

AU - Van Leeuwen, Nicole S.

AU - Bobylev, Eduard O.

AU - Amstalden Van Hove, Erika R.

AU - Mathew, Simon

AU - Yan, Ning

AU - Flapper, Jitte

AU - Van Den Berg, Keimpe J.

AU - Reek, Joost N.H.

AU - De Bruin, Bas

N1 - Funding Information: Financial support from the Advanced Research Center for Chemical Building Blocks (ARC CBBC, project 2018.015.C and 2019.021.A), which is cofounded and cofinanced by the Dutch Research Council (NWO) and The Netherlands Ministry of Economic Affairs and Climate Policy, is gratefully acknowledged. P.C.M.L. and N.Y. acknowledge the financial support from The Netherlands Organization for Scientific Research (NWO) VIDI program (VI.Vidi.192.045). Publisher Copyright: © 2022 American Chemical Society. All rights reserved.

PY - 2022/11/8

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N2 - Polyureas have widespread applications due to their unique material properties. Because of the toxicity of isocyanates, sustainable isocyanate-free routes to prepare polyureas are a field of active research. Current routes to isocyanate-free polyureas focus on constructing the urea moiety in the final polymerizing step. In this study we present a new isocyanate-free method to produce polyureas by Ru-catalyzed carbene insertion into the N-H bonds of urea itself in combination with a series of bis-diazo compounds as carbene precursors. The mechanism was investigated by kinetics and DFT studies, revealing the rate-determining step to be nucleophilic attack on a Ru-carbene moiety by urea. This study paves the way to use transition-metal-catalyzed reactions in alternative routes to polyureas.

AB - Polyureas have widespread applications due to their unique material properties. Because of the toxicity of isocyanates, sustainable isocyanate-free routes to prepare polyureas are a field of active research. Current routes to isocyanate-free polyureas focus on constructing the urea moiety in the final polymerizing step. In this study we present a new isocyanate-free method to produce polyureas by Ru-catalyzed carbene insertion into the N-H bonds of urea itself in combination with a series of bis-diazo compounds as carbene precursors. The mechanism was investigated by kinetics and DFT studies, revealing the rate-determining step to be nucleophilic attack on a Ru-carbene moiety by urea. This study paves the way to use transition-metal-catalyzed reactions in alternative routes to polyureas.

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Isocyanate-Free Polyurea Synthesis via Ru-Catalyzed Carbene Insertion into the N-H Bonds of Urea

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