pKa Modulation of Pyrrolidine-Based Catalytic Polymers Used for the Preparation of Glycosyl Hydrazides at Physiological pH and Temperature
Inspired by the ability of enzymes to use the surrounding hydrophobic and/or polarizable groups to modulate the pK of a given amino acid, we designed a series of soluble polymers able to decrease the basicity of pyrrolidine (from 11.2 to 8.6 pK units), which clearly increases its aminocatalytic acti...
| Autores: | , , , , , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 2020 |
| País: | España |
| Institución: | Consejo Superior de Investigaciones Científicas (CSIC) |
| Repositorio: | DIGITAL.CSIC. Repositorio Institucional del CSIC |
| OAI Identifier: | oai:digital.csic.es:10261/217563 |
| Acceso en línea: | http://hdl.handle.net/10261/217563 |
| Access Level: | acceso abierto |
| Palabra clave: | Enzyme-like organocatalysis Iminium activation Pyrrolidine pKa modulation Polymers Hydrazones |
| Sumario: | Inspired by the ability of enzymes to use the surrounding hydrophobic and/or polarizable groups to modulate the pK of a given amino acid, we designed a series of soluble polymers able to decrease the basicity of pyrrolidine (from 11.2 to 8.6 pK units), which clearly increases its aminocatalytic activity at physiological pH in C═N bond formation reactions via ion iminium activation. Other parameters such as charge density, hydrophobic/hydrophilic balance, and aggregation state have been studied as important factors in the catalytic activity of the polymers for a given substrate. To demonstrate the utility of our approach, an optimal pyrrolidine-based catalytic polymer has been used for the formation of C-N bonds between hydrazides and free sugars as the model system for the preparation of glycoconjugates. |
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