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Research Article Open access CC BY 4.0

Controlling Site Selectivity in the Phosphorylation of Amphiphilic Diols: Aminopyridine Organocatalysts vs. Stoichiometric Amine Bases

Shai Ben Sasson, Noa Naama, Mikhail Kozlov, Ibrahim Amer, Moshe Portnoy

Organics · pp. 25–25 · Published 11 Jun 2026

10.3390/org7020025

Abstract

Our recent studies demonstrated that dialkylaminopyridine organocatalysts featuring an extensive secondary sphere preferentially phosphorylate the alcohol at the apolar domain of a model amphiphilic diol. In the present study, this site-selective behavior was corroborated across a broader range of amphiphilic diols. Furthermore, we found that the site selectivity can be inverted by applying certain saturated aliphatic amine bases in stoichiometric amounts. Screening identified cis-2,6-dimethylpiperidine as the most selective promoter, consistently inducing phosphorylation at the polar domain across all tested diols. Remarkably, despite being a secondary amine, this base did not produce any detectable phosphoramidate byproduct.

Amphiphile Chemistry Phosphoramidate Selectivity Amine gas treating Stoichiometry Phosphorylation Combinatorial chemistry

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