Basically, nucleophilicity matters little: towards unravelling the supramolecular driving forces in enzyme-like CO2 conversion
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Show full item recordcomunitat-uji-handle:10234/9
comunitat-uji-handle2:10234/7053
comunitat-uji-handle3:10234/8639
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Title
Basically, nucleophilicity matters little: towards unravelling the supramolecular driving forces in enzyme-like CO2 conversionDate
2022-08-03Publisher
Royal Society of ChemistryISSN
1477-0520; 1477-0539Bibliographic citation
Esteve, F., Altava, B., Luis, S. V., & García-Verdugo, E. (2022). Basically, nucleophilicity matters little: towards unravelling the supramolecular driving forces in enzyme-like CO 2 conversion. Organic & Biomolecular Chemistry, 20(33), 6637-6645.Type
info:eu-repo/semantics/articleVersion
info:eu-repo/semantics/acceptedVersionAbstract
The reaction mechanism for the cycloaddition of CO2 to styrene oxide in the presence of macrocyclic pseudopeptides has been studied using DFT methods. Computational calculations indicate that the unprecedented catalytic ... [+]
The reaction mechanism for the cycloaddition of CO2 to styrene oxide in the presence of macrocyclic pseudopeptides has been studied using DFT methods. Computational calculations indicate that the unprecedented catalytic behaviour previously observed experimentally, in which the most reactive species was not the most nucleophilic but the most basic one, can be associated to the tight cooperativity between several supramolecular interactions promoted by simple peptidomimetics able to display a synzymatic behaviour. This bizarre catalytic performance afforded remarkable conversions of a sluggish substrate like styrene oxide into the desired cyclic carbonate, even under relatively mild reaction conditions, opening the way for the practical use of CO2 as a raw material in the preparation of valuable chemicals. Furthermore, the remote modification of essential structural features of the macrocycle (synzyme engineering) permitted the driving forces of the synzymatic system to be analyzed, stressing the crucial synergic effect between an elegantly preorganized oxyanion hole and additional aromatic interactions. [-]
Is part of
Organic & Biomolecular Chemistry, Issue 33 (2022)Funder Name
Universitat Jaume I | Generalitat Valenciana | Ministerio de Ciencia e Innovación - Agencia estatal de Investigación / FEDER
Project code
UJI-B2021-31 | AICO/2021/139 | RTI2018-098233-B-C22
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info:eu-repo/semantics/openAccess
info:eu-repo/semantics/openAccess
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