Sterically‐Controlled Self‐Immolation in Phosphoramidate Linkers Triggered by Light
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F20%3A00519381" target="_blank" >RIV/61388963:_____/20:00519381 - isvavai.cz</a>
Alternative codes found
RIV/00216208:11310/20:10414587
Result on the web
<a href="https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/ejoc.201901882" target="_blank" >https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/ejoc.201901882</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1002/ejoc.201901882" target="_blank" >10.1002/ejoc.201901882</a>
Alternative languages
Result language
angličtina
Original language name
Sterically‐Controlled Self‐Immolation in Phosphoramidate Linkers Triggered by Light
Original language description
Phosphoramidate prodrugs stand out for their applications as drug delivery systems. However, information on their activation remains limited to prodrug half‐live and metabolite structure, which hinders their development. Considering the lack of data on phosphoramidate self‐immolation, we studied light‐triggered self‐immolation of phosphoramidate‐based linkers bearing various amino acid arms by NMR spectroscopy with in situ irradiation, complemented with mathematical fitting, and by optical methods. By changing the alanine arm, we were able to systematically fine‐tune, slow down or speed up the cyclization rate. The cyclization rate of branched amino acid arms increased with the steric demands of their α‐substituents according to the Thorpe‐Ingold effect. The cyclization of β‐alanine and proline was very slow or did not proceed at all, but lactate may be a good alternative for the alanine arm because lactate exhibits a significantly slower cyclization rate than alanine (ca. 60 times). Overall, our study demonstrates that phosphoramidate self‐immolation strongly depends on the structure of the amino acid arm and on the conditions used (solvent, concentration and temperature), thereby providing a solid foundation for the rational design of new self‐immolative phosphoramidate systems with desired properties.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10401 - Organic chemistry
Result continuities
Project
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Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2020
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
European Journal of Organic Chemistry
ISSN
1434-193X
e-ISSN
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Volume of the periodical
2020
Issue of the periodical within the volume
7
Country of publishing house
DE - GERMANY
Number of pages
10
Pages from-to
897-906
UT code for WoS article
000512726900001
EID of the result in the Scopus database
2-s2.0-85079463446