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Turning carbon dioxide into dialkyl carbonates through guanidinium-assisted SN2 N2 ion-pair process

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Abstract
The synthesis of dialkyl carbonates, versatile compounds with applications in organic synthesis, pharmaceuticals, and polymers, has attracted considerable attention due to their environmentally benign nature. Here, we describe the selective bimolecular nucleophilic substitution (SN2) N 2) reaction between primary and secondary alkyl iodides with 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD)-based carbon dioxide-binding organic liquids. We show that TBD is a great candidate for bulk carbon dioxide and alcohol binding at 100 degrees C. degrees C. TBDbased carbonate salts are selective for SN2 N 2 processes, allowing them to work with highly reactive alkyl iodide while eliminating unwanted base quaternization either in acetonitrile or in bulk at both 21 degrees C degrees C and 65 degrees C. degrees C. The high reactivity of these TBD-based carbon dioxide-binding organic liquids toward backside SN2 N 2 processes at low temperature is explained by the presence of the TBD.H+ + guanidinium, revealing a unique metal-free cation-assisted SN2 N 2 ion-pair process.
Keywords
METAL-FREE SYNTHESIS, DIMETHYL CARBONATE, ORGANIC CARBONATES, S(N)2 REACTIONS, CO2, AMINOLYSIS, CATALYSTS, LIQUIDS, TEMPERATURE, SOLUBILITY

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MLA
Delcorps, Juliette, et al. “Turning Carbon Dioxide into Dialkyl Carbonates through Guanidinium-Assisted SN2 N2 Ion-Pair Process.” CELL REPORTS PHYSICAL SCIENCE, vol. 5, no. 7, 2024, doi:10.1016/j.xcrp.2024.102057.
APA
Delcorps, J., Singh Rawat, K., Wells, M., Ben Ayed, E., Grignard, B., Detrembleur, C., … Coulembier, O. (2024). Turning carbon dioxide into dialkyl carbonates through guanidinium-assisted SN2 N2 ion-pair process. CELL REPORTS PHYSICAL SCIENCE, 5(7). https://doi.org/10.1016/j.xcrp.2024.102057
Chicago author-date
Delcorps, Juliette, Kuber Singh Rawat, Mathilde Wells, Emna Ben Ayed, Bruno Grignard, Christophe Detrembleur, Bertrand Blankert, Pascal Gerbaux, Veronique Van Speybroeck, and Olivier Coulembier. 2024. “Turning Carbon Dioxide into Dialkyl Carbonates through Guanidinium-Assisted SN2 N2 Ion-Pair Process.” CELL REPORTS PHYSICAL SCIENCE 5 (7). https://doi.org/10.1016/j.xcrp.2024.102057.
Chicago author-date (all authors)
Delcorps, Juliette, Kuber Singh Rawat, Mathilde Wells, Emna Ben Ayed, Bruno Grignard, Christophe Detrembleur, Bertrand Blankert, Pascal Gerbaux, Veronique Van Speybroeck, and Olivier Coulembier. 2024. “Turning Carbon Dioxide into Dialkyl Carbonates through Guanidinium-Assisted SN2 N2 Ion-Pair Process.” CELL REPORTS PHYSICAL SCIENCE 5 (7). doi:10.1016/j.xcrp.2024.102057.
Vancouver
1.
Delcorps J, Singh Rawat K, Wells M, Ben Ayed E, Grignard B, Detrembleur C, et al. Turning carbon dioxide into dialkyl carbonates through guanidinium-assisted SN2 N2 ion-pair process. CELL REPORTS PHYSICAL SCIENCE. 2024;5(7).
IEEE
[1]
J. Delcorps et al., “Turning carbon dioxide into dialkyl carbonates through guanidinium-assisted SN2 N2 ion-pair process,” CELL REPORTS PHYSICAL SCIENCE, vol. 5, no. 7, 2024.
@article{01J5X1R47TQE5ACTC71XNMADSW,
  abstract     = {{The synthesis of dialkyl carbonates, versatile compounds with applications in organic synthesis, pharmaceuticals, and polymers, has attracted considerable attention due to their environmentally benign nature. Here, we describe the selective bimolecular nucleophilic substitution (SN2) N 2) reaction between primary and secondary alkyl iodides with 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD)-based carbon dioxide-binding organic liquids. We show that TBD is a great candidate for bulk carbon dioxide and alcohol binding at 100 degrees C. degrees C. TBDbased carbonate salts are selective for SN2 N 2 processes, allowing them to work with highly reactive alkyl iodide while eliminating unwanted base quaternization either in acetonitrile or in bulk at both 21 degrees C degrees C and 65 degrees C. degrees C. The high reactivity of these TBD-based carbon dioxide-binding organic liquids toward backside SN2 N 2 processes at low temperature is explained by the presence of the TBD.H+ + guanidinium, revealing a unique metal-free cation-assisted SN2 N 2 ion-pair process.}},
  articleno    = {{102057}},
  author       = {{Delcorps, Juliette and Singh Rawat, Kuber and  Wells, Mathilde and  Ben Ayed, Emna and  Grignard, Bruno and  Detrembleur, Christophe and  Blankert, Bertrand and  Gerbaux, Pascal and Van Speybroeck, Veronique and  Coulembier, Olivier}},
  issn         = {{2666-3864}},
  journal      = {{CELL REPORTS PHYSICAL SCIENCE}},
  keywords     = {{METAL-FREE SYNTHESIS,DIMETHYL CARBONATE,ORGANIC CARBONATES,S(N)2 REACTIONS,CO2,AMINOLYSIS,CATALYSTS,LIQUIDS,TEMPERATURE,SOLUBILITY}},
  language     = {{eng}},
  number       = {{7}},
  pages        = {{22}},
  title        = {{Turning carbon dioxide into dialkyl carbonates through guanidinium-assisted SN2 N2 ion-pair process}},
  url          = {{http://doi.org/10.1016/j.xcrp.2024.102057}},
  volume       = {{5}},
  year         = {{2024}},
}

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