Metal Ion-Induced Large Fragment Deactivation: A Different Strategy for Site-Selectivity in a Complex Molecule.
Large Fragment Deactivation
Molecular Blocking
Radical Fluorination
Scattershot Reaction
Site-Selectivity
Journal
Angewandte Chemie (International ed. in English)
ISSN: 1521-3773
Titre abrégé: Angew Chem Int Ed Engl
Pays: Germany
ID NLM: 0370543
Informations de publication
Date de publication:
22 Mar 2024
22 Mar 2024
Historique:
received:
09
11
2023
medline:
8
12
2023
pubmed:
8
12
2023
entrez:
8
12
2023
Statut:
ppublish
Résumé
Complex natural product functionalizations generally involve the use of highly engineered reagents, catalysts, or enzymes to react exclusively at a desired site through lowering of a select transition state energy. In this communication, we report a new, complementary strategy in which all transition states representing undesirable sites in a complex ionophore substrate are simultaneously energetically increased through the chelation of a metal ion to the large fragment we wish to neutralize. In the case of an electrophilic, radical based fluorination reaction, charge repulsion (electric field effects), induced steric effects, and electron withdrawal provide the necessary deactivation and proof of principle to afford a highly desirable natural product derivative. We envisage that many other electrophilic or charge based synthetic methods may be amenable to this approach as well.
Identifiants
pubmed: 38063469
doi: 10.1002/anie.202317070
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
e202317070Subventions
Organisme : National Science Foundation
ID : CHE 2102116
Organisme : Natural Sciences and Engineering Research Council of Canada
ID : RGPIN-2019-04205
Informations de copyright
© 2023 Wiley-VCH GmbH.
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