Abstract
3,5-Dimethylidene-1,2,2,6,6-pentamethyl-4-oxopiperidine was shown by the kinetic method to be less reactive than 3,5-dimethylidene-2,2,6,6-tetramethyl-4-oxopiperidin-1-oxyl in the nucleophilic addition of secondary amines and Diels—Alder dimerization. According to the quantum-chemical AM1 calculations, this is due to the difference in the structures of the activated complexes (in the reactions with amines) and to the “press” effect created by theN-methyl group that impedes the necessary cycle flattening (in the Diels—Alder reaction).
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Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1698–1702, October, 2000.
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Shapiro, A.B., Borbulevich, O.Y., Koroteev, S.V. et al. The reactivity of 3,5-dimethylidene-2,2,6,6-tetramethyl-4-oxopiperidin-1-oxyl and its diamagneticN-methyl analog in nucleophilic addition of amines and diels—Alder dimerization. Russ Chem Bull 49, 1682–1686 (2000). https://doi.org/10.1007/BF02496333
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DOI: https://doi.org/10.1007/BF02496333