Síntesis y reactividad de sulfamidatos cíclicos derivados de aminoácidos
This PhD Thesis is focused on obtaining a library of α- and β-amino acids by opening different cyclic sulfamidates in a stereospecific and regioselective manner. Thus, an study of the synthesis and reactivity of different amino acid-derived cyclic sulfamidates against nucleophiles of different nat...
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| Formato: | text (thesis) |
| Lenguaje: | spa |
| Publicado: |
Universidad de La Rioja (España)
2021
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| Acceso en línea: | https://dialnet.unirioja.es/servlet/oaites?codigo=297366 |
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| Sumario: | This PhD Thesis is focused on obtaining a library of α- and β-amino acids by opening different cyclic sulfamidates in a stereospecific and
regioselective manner. Thus, an study of the synthesis and reactivity of different amino acid-derived cyclic sulfamidates against nucleophiles of
different nature has been carried out.
Firstly, in chapter 3 a library of cyclic sulfamidates derived from amino acids and protected in different ways is presented, to be used as starting
products in other chapters. For this purpose, already published methods are replicated or modified to scale them up, simplify them or obtain new
sulfamidates.
In chapter 4, the reactivity of several cyclic sulfamidates derived from different amino acids towards O-carbohydrates is studied. In this way, their
reactivity is compared depending on their structure, obtaining good results in the openings of a cyclic sulfamidate derived from α-methylserine. In
addition, an analogue of the TN antigen, present in cancer-related processes, is synthesized.
In Chapter 5, the opening of cyclic sulfamidates with peptides is carried out. First, the behavior of serine-derived sulfamidates in nucleophilic
openings with peptides in the presence of base is evaluated. On the other hand, in collaboration with Dr. De Luca's group, a methodology based
on the use of molecular sieve is used to avoid undesired elimination reactions. This methodology allows obtaining a library of peptides containing
different lanthionines in their structure.
In order to broaden the applications of cyclic sulfamidates towards obtaining new β2,2-amino acids, throughout chapter 6, a new methodology to
obtain different α-alkylisoserines is developed. For this purpose, the synthesis and alkylation of bicyclic N,O-acetals derived from isoserine, which
allow after their hydrolysis the obtaining of several enantiomerically pure (R)- and (S)-alkylisoserines, is studied theoretically and experimentally.
Finally, from (R)-α-benzylisoserine, in Chapter 7, a new cyclic sulfamidate is obtained from which, by means of its nucleophilic opening with
nucleophiles of different nature, new β2,2-amino acids are obtained. |
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