Synthesis of 2,5-Bis(spirocyclohexane)-Substituted Nitroxides of Pyrroline and Pyrrolidine Series, Including Thiol-Specific Spin Label: An Analogue of MTSSL with Long Relaxation Time

• Published in: Journal of organic chemistry 2012-09, Vol.77 (18), p.8016-8027
• Main Authors: Kirilyuk, Igor A, Polienko, Yuliya F, Krumkacheva, Olesya A, Strizhakov, Rodion K, Gatilov, Yurii V, Grigor’ev, Igor A, Bagryanskaya, Elena G
• Format: Article
• Language: English
• Subjects: Cyclic N-Oxides - chemical synthesis; Cyclic N-Oxides - chemistry; Electron Spin Resonance Spectroscopy; Mesylates - chemical synthesis; Mesylates - chemistry; Molecular Structure; Nitric Oxide - chemical synthesis; Nitric Oxide - chemistry; Pyrroles - chemical synthesis; Pyrroles - chemistry; Pyrrolidines - chemical synthesis; Pyrrolidines - chemistry; Spin Labels; Spiro Compounds - chemical synthesis; Spiro Compounds - chemistry; Sulfhydryl Compounds - chemical synthesis; Sulfhydryl Compounds - chemistry
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo301235j

The nitroxides of 7-azadispiro[5.1.5.2]pentadecane and 7-azadispiro[5.1.5.2]pentadeca-14-ene series have been prepared, including thiol-specific methane thiosulfonate spin label for site-directed spin labeling. The effect of spirocyclohexane moieties on chemical and spectral properties has been studied. The obtained temperature dependencies of electron spin relaxation parameters demonstrate that new nitroxides may be suitable for PELDOR distance measurements at 80–120 K. Moreover, the new nitroxides demonstrated much higher stability toward reduction by ascorbate than spirocyclohexane-substituted nitroxides of piperidine series and showed 1.3–3.14 times lower reduction rates compared to corresponding 2,2,5,5-tetramethyl nitroxides.