Monodentate Halogen Bond Activation of Aziridines in Formal [3+2] Cycloadditions

12 May 2025, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

The ring opening of aziridines to produce various N-heterocycles traditionally requires strong Lewis acids or transition metal catalysts, with non-covalent organocatalytic approaches remaining largely unexplored. Herein, we demonstrate that N-heterocyclic iodonium salts can effectively catalyze [3+2] cycloadditions of aziridines through a monodentate halogen bond (XB) activation. Using 1-5 mol% of the iodolium catalyst, a wide range of aziridines undergo an efficient cycloaddition with a variety of dipolarophiles (carbonyls, alkynes, and alkenes) to furnish oxazolidines, pyrrolines, and pyrrolidines. DFT calculations revealed a previously underexplored N-activation mode, with detailed non-covalent interaction analysis showing that the N-heterocyclic iodonium salt's exceptional performance stems from combined I-N and I-π interactions.

Keywords

halogen bonding
organocatalysis
hypervalent iodine
aziridines
iodonium salts

Supplementary materials

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Supporting Information
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Experimental procedures and spectroscopic characterization of discussed compounds.
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