Work

Ring-Opening of Aziridines Using Tethered Hemiketals

Year: 2026

Type: article

Abstract: We present the first examples of aziridine ring-opening reactions by pendant hemiketal tethers. The reactions proceed smoothly at room temperature with catalytic quantities of the Lewis acid triphenylcarbenium tetrafluoroborate. The hemiketal tether is derived from the reaction solvent, acetone, in most cases. Other ketone solvents, including cyclopentanone and cyclobutanone, are also compatible. We hypothesize that the Lewis acid catalyzes the addition of the solvent to the alcohol of the aziridine substrate, forming a hemiketal tether, which then attacks the aziridine in an S N 2 manner. Given that mixtures of products are formed in many cases, an alternate mechanism involving an intermolecular attack by the carbonyl solvent followed by ketalization may also be operative. A variety of functional groups are compatible, and the products are useful for further transformations.

Source: The Journal of Organic Chemistry

DOI: 10.1021/acs.joc.5c02746

Authors: Raju Silver, Abhijit Manna, Steven P. Kelley, Shyam Sathyamoorthi

Institutions: University of Kansas, University of Missouri

Language: English

Topic: Synthesis and Catalytic Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: National Institutes of Health, National Institute of General Medical Sciences

Awards: G4233733361, G5036224426, Chemical Biology of Infectious Disease, Tethered aza-Wacker Technology for Complex Antibiotic Assembly