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Heterocyclic Group Transfer Reactions with I(III) N-HVI Reagents: Access to N-Alkyl (Heteroaryl)onium Salts via Olefin Aminolactonization

submitted on 09.09.2020, 19:54 and posted on 10.09.2020, 08:08 by Anthony F. Tierno, Jennifer C. Walters, Andres Vazquez-Lopez, Xiao Xiao, Sarah Wengryniuk

Pyridinium and related N-alkyl (heteroaryl)onium salts are versatile synthetic intermediates in organic chemistry, with applications ranging from ring functionalizations to provide diverse piperidine scaffolds to their recent emergence as radical precursors in deaminative cross couplings. Despite their ever-expanding applications, methods for their synthesis have seen little innovation, continuing to rely on a limited set of decades old transforms. Herein, we leverage (bis)cationic nitrogen-ligated I(III) hypervalent iodine reagents, or N-HVIs, as “heterocyclic group transfer reagents” to provide access to a broad scope of (heteroaryl)onium salts via the aminolactonization of alkenoic acids. The reactions proceed in excellent yields, under mild conditions, and are capable of incorporating a broad scope of sterically and electronically diverse aromatic heterocycles. The N-HVI reagents can be generated in situ, the products isolated via simple trituration, and subsequent derivatizations demonstrate the power of this platform for diversity-oriented synthesis of 6-membered nitrogen heterocycles. Mechanistic studies indicate the reaction proceeds via initial olefin activation followed by lactonization and subsequent intermolecular nucleophilic displacement of an (alkyl)(aryl)iodonium salt hypernucleofuge.


CAREER: Novel Synthetic Applications of Poly(cationic) lambda-3 Iodanes

Directorate for Mathematical & Physical Sciences

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National Institutes of Health R01 GM123098


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Temple University


United States

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