Abstract
Tautomers of N-allyl- and N-propargyl-substituted trifluoromethanesulfonimides (CF3SO2)2NR (R = CH2CH=CH2, Z/E-CH=CHMe, CH2C≡CH, CH=CH=CH2, C≡CCH2) were calculated by the DFT (B3LYP, wB97XD, PBE1PBE), MP2, and CBS-QB3 methods. The results were compared with the theoretical data for the corresponding amines and amides NHRR1 (R1 = H, CF3SO2). It was shown that there is no conjugation between the nitrogen atom and C=C bond and that conjugation exists with the C≡C bond with electron density displacement toward the nitrogen atom. The calculations of anions derived from N-allyl- and N-propargyl-trifluoromethanesulfonimides revealed the possibility of their rearrangement with elimination of trifluoromethanesulfinate anion and formation of its H-complex with N-(prop-2-en-1-ylidene)trifluoromethanesulfonamide or N-(prop-2-yn-1-ylidene)trifluoromethanesulfonamide.
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Original Russian Text © A.V. Kuzmin, B.A. Shainyan, 2017, published in Zhurnal Organicheskoi Khimii, 2017, Vol. 53, No. 10, pp. 1479–1482.
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Kuzmin, A.V., Shainyan, B.A. N-allyl and N-propargyl trifluoromethanesulfonimides. Theoretical analysis. Russ J Org Chem 53, 1505–1509 (2017). https://doi.org/10.1134/S1070428017100037
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DOI: https://doi.org/10.1134/S1070428017100037