4
views
0
recommends
+1 Recommend
0 collections
    0
    shares
      • Record: found
      • Abstract: found
      • Article: not found

      DFT investigation of the reaction mechanism for the guanidine catalysed ring-opening of cyclic carbonates by aromatic and alkyl-amines

      Read this article at

      ScienceOpenPublisher
      Bookmark
          There is no author summary for this article yet. Authors can add summaries to their articles on ScienceOpen to make them more accessible to a non-specialist audience.

          Abstract

          The bifunctional activity (base/H-bond donor) of TBD allows understanding its higher efficiency compared to its methyl counterpart (MTBD) for the aminolysis of cyclic carbonates by amines.

          Abstract

          The guanidine catalysed aminolysis of propylene carbonate has been investigated using density functional theory (DFT) and highlights that different reaction pathways are involved, depending on the aromatic or aliphatic nature of the amine. The structural ability of 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) to simultaneously give and receive protons was demonstrated by a detailed mechanistic investigation. The bifunctional activity (base/H-bond donor) of TBD significantly reduces the Gibbs energy of the reaction and allows understanding of its higher efficiency compared to its methyl counterpart (MTBD).

          Related collections

          Most cited references39

          • Record: found
          • Abstract: found
          • Article: not found

          Sustainable conversion of carbon dioxide: the advent of organocatalysis

          The conversion of carbon dioxide (CO 2 ), an abundant renewable carbon reagent, into chemicals of academic and industrial interest is of imminent importance to create a higher degree of sustainability in chemical processing and production. The conversion of carbon dioxide (CO 2 ), an abundant renewable carbon reagent, into chemicals of academic and industrial interest is of imminent importance to create a higher degree of sustainability in chemical processing and production. Recent progress in this field is characterised by a plethora of organic molecules able to mediate the conversion of suitable substrates in the presence of CO 2 into a variety of value-added commodities with advantageous features combining cost-effectiveness, metal-free transformations and general substrate activation profiles. In this review, the latest developments in the field of CO 2 catalysis are discussed with a focus on organo-mediated conversions and their increasing importance in serving as practicable alternatives for metal-based processes. Also a critical assessment of the state-of-the-art methods is presented with attention to those features that need further development to increase the usefulness of organocatalysis in the production of organic molecules of potential commercial interest.
            Bookmark
            • Record: found
            • Abstract: found
            • Article: not found

            Advanced Corrections of Hydrogen Bonding and Dispersion for Semiempirical Quantum Mechanical Methods.

            Semiempirical quantum mechanical methods with corrections for noncovalent interactions, namely dispersion and hydrogen bonds, reach an accuracy comparable to much more expensive methods while being applicable to very large systems (up to 10 000 atoms). These corrections have been successfully applied in computer-assisted drug design, where they significantly improve the correlation with the experimental data. Despite these successes, there are still several unresolved issues that limit the applicability of these methods. We introduce a new generation of both hydrogen-bonding and dispersion corrections that address these problems, make the method more robust, and improve its accuracy. The hydrogen-bonding correction has been completely redesigned and for the first time can be used for geometry optimization and molecular-dynamics simulations without any limitations, as it and its derivatives have a smooth potential energy surface. The form of this correction is simpler than its predecessors, while the accuracy has been improved. For the dispersion correction, we adopt the latest developments in DFT-D, using the D3 formalism by Grimme. The new corrections have been parametrized on a large set of benchmark data including nonequilibrium geometries, the S66x8 data set. As a result, the newly developed D3H4 correction can accurately describe a wider range of interactions. We have parametrized this correction for the PM6, RM1, OM3, PM3, AM1, and SCC-DFTB methods.
              Bookmark
              • Record: found
              • Abstract: not found
              • Article: not found

              Recent progress in catalytic conversions of carbon dioxide

                Bookmark

                Author and article information

                Journal
                RSCACL
                RSC Advances
                RSC Adv.
                Royal Society of Chemistry (RSC)
                2046-2069
                2017
                2017
                : 7
                : 31
                : 18993-19001
                Affiliations
                [1 ]Institut des Sciences Moléculaires
                [2 ]UMR 5255 CNRS Université Bordeaux
                [3 ]F-33405 Talence Cedex
                [4 ]France
                [5 ]Center for Education and Research on Macromolecules
                [6 ]CESAM Research Unit
                [7 ]Université de Liège
                [8 ]B-4000 LIEGE
                [9 ]Belgium
                Article
                10.1039/C7RA00220C
                5977d284-dbda-439a-a111-7132fbacd51c
                © 2017
                History

                Comments

                Comment on this article