FCCC LOGO Faculty Publications
Tierno AF , Walters JC , Vazquez-Lopez A , Xiao X , Wengryniuk SE
Heterocyclic group transfer reactions with I(iii) N-HVI reagents: access to N-alkyl(heteroaryl)onium salts via olefin aminolactonization
Chem Sci. 2021 Apr 12;12(18) :6385-6392
PMID: 34084438    PMCID: PMC8115303    URL: https://www.ncbi.nlm.nih.gov/pubmed/34084438
Back to previous list
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 transformations and a limited subset of coupling partners. 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 N-alkyl(heteroaryl)onium salts via the aminolactonization of alkenoic acids, the first example of engaging an olefin to directly generate these salts. 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.
2041-6539 Tierno, Anthony F Walters, Jennifer C Vazquez-Lopez, Andres Xiao, Xiao Wengryniuk, Sarah E Orcid: 0000-0002-4797-0181 Journal Article Chem Sci. 2021 Apr 12;12(18):6385-6392. doi: 10.1039/d1sc00187f.