Abstract
In this work we present mechanism of the base-catalyzed 2-azaallylic rearrangement in homogeneous media. Detailed 2-azaallylic rearrangement studies have shown that tautomerism of derivatives of benzylidenebenzhydrylamines and N-fluorenylidenebenzylamines is not adequately encomposed by the Hammet equation and the equilibrium constant in the case of studied derivatives depends on the electronic as well as steric factors of the azaallylic system substituents. The presence of steric interactions which influence the equilibrium state has been additionally confirmed by means of crystallographic and molecular mechanics data as well as NOE studies.
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References
S. Ramakrishan, M.B. Sukhaswami, K.M. Patil and C. Eswaram, J. Biomol. Struct. Dyn. 15 (1998) 605.
T. Tanaka, T. Enoki, A.Y. Grosberg, S. Masamune, T. Oya, Y. Takaoka, K. Tanaka, Ch. Wang and G. Wang, Ber. Bunsenges. Phys. Chem. 102(11) (1998) 1529.
M.S. Madhusudhan and S. Vishveshwara, J. Biomol. Struct. Dyn. 16 (1998) 715.
R. Russel and D. Herschlag, RNA-A Publication of a RNA Society 5 (1999) 158.
E.E. Snell, in: Chemical and Biological Aspects of Pyridoxal Catalysis, eds. P.M. Fasella, A.E. Braunstein and A. Rossi-Fanelli (Macmillan, New York, 1963) pp. 1–12.
E.E. Snell, A.E. Braunstein, E.S. Severin, Yu.M. Torchinsky, eds., Pyridoxal Catalysis: Enzymes and Model Systems (Interscience, New York, 1968).
D.E. Metzier, M. Ikara and E.E. Severin and Yu.M. Torchinsky, eds., Pyridoxal Catalysis: Enzymes and Model Systems (Interscience, New York, 1968).
C.K. Ingold and C.W. Shoppee, J. Chem. Soc. (1929) 1199.
Shoppee, J. Chem. Soc. (1931) 1225.
D.J. Cram and R.D. Guthrie, J. Am. Chem. Soc. (1966) 5760.
D.J. Cram and R.D. Guthrie, J. Am. Chem. Soc. 87 (1965) 397.
A. Echevarria, J. Miller and M.G. Nascimento, Org. Magn. Reson. 23 (1985) 809.
W.B. Jennings, V.E. Boyd and P.B. Coulter, Org. Magn. Reson. 21 (1983) 279.
P. Smidt and Van Dang, J. Org. Chem. 41 (1976) 2013.
Weissberg, Organic Solvents. Physical Properties and Methods of Purification, 2nd Ed. (New York, 1955) p. 552.
M.J. O'Donnell, J. Am. Chem. Soc. 110 (1988) 8520.
J.K. Badenhoop and F. Wienhold, Int. J. Quantum Chem. 72 (1999) 269.
M.J. O'Donnel, J. Am. Chem. Soc. 110 (1988) 8520.
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Rogman, A., Gancarz, R., Domagalska, B.W. et al. 2-azaallylic rearrangement in homogeneous systems. Topics in Catalysis 11, 451–460 (2000). https://doi.org/10.1023/A:1027271124759
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DOI: https://doi.org/10.1023/A:1027271124759