Design concept for α-hydrogen-substituted nitroxides

Michal Amar, Sukanta Bar, Mark A. Iron, Hila Toledo, Boris Tumanskii, Linda J.W. Shimon, Mark Botoshansky, Natalia Fridman and Alex M. Szpilman ()
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Michal Amar: Schulich Faculty of Chemistry, Technion-Israel Institute of Technology
Sukanta Bar: Schulich Faculty of Chemistry, Technion-Israel Institute of Technology
Mark A. Iron: Weizmann Institute of Science
Hila Toledo: Schulich Faculty of Chemistry, Technion-Israel Institute of Technology
Boris Tumanskii: Schulich Faculty of Chemistry, Technion-Israel Institute of Technology
Linda J.W. Shimon: Weizmann Institute of Science
Mark Botoshansky: Schulich Faculty of Chemistry, Technion-Israel Institute of Technology
Natalia Fridman: Schulich Faculty of Chemistry, Technion-Israel Institute of Technology
Alex M. Szpilman: Schulich Faculty of Chemistry, Technion-Israel Institute of Technology

Nature Communications, 2015, vol. 6, issue 1, 1-9

Abstract: Abstract Stable nitroxides (nitroxyl radicals) have many essential and unique applications in chemistry, biology and medicine. However, the factors influencing their stability are still under investigation, and this hinders the design and development of new nitroxides. Nitroxides with tertiary alkyl groups are generally stable but obviously highly encumbered. In contrast, α-hydrogen-substituted nitroxides are generally inherently unstable and rapidly decompose. Herein, a novel, concept for the design of stable cyclic α-hydrogen nitroxides is described, and a proof-of-concept in the form of the facile synthesis and characterization of two diverse series of stable α-hydrogen nitroxides is presented. The stability of these unique α-hydrogen nitroxides is attributed to a combination of steric and stereoelectronic effects by which disproportionation is kinetically precluded. These stabilizing effects are achieved by the use of a nitroxide co-planar substituent in the γ-position of the backbone of the nitroxide. This premise is supported by a computational study, which provides insight into the disproportionation pathways of α-hydrogen nitroxides.

Date: 2015
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DOI: 10.1038/ncomms7070

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