Tetrahedron p. 2151 - 2159 (1984)
Update date:2022-08-04
Topics:
Shustov, G. V.
Zolotoi, A. B.
Zaichenko, N. L.
Dyachenko, O. A.
Atovmyan, L. O.
Kostyanovsky, R. G.
A second-kind asymmetric transformation involving N-atom inversion has been observed at 20o for 1(S)-α-carboxyethyl-3,3-bis(trifluoromethyl)diaziridine 1 and its methyl ester 2.X-Ray data for the diastereomer (1S, 2S, α-S), 1A (which is termodynamically preferred in the crystalline phase), 1H NMR spectra of ethyl ester 3-15N(1) and 3-15N(2), CD spectra of 1A,B, 2A,B, potassium salt 4A,B, and semiempirical calculations (MINDO/3 and INDO) for 1A, show that the stereospecificity of crystallization of the diastereomer A is due to the higher energy of the crystal lattice of the diastereomer (1R, 2R, α-S), 1B because of hindered charge compensation as well as to the hindrance by the CF3 groups to intermolecular H-bonds.According to semiempirical calculations, the stability of 3,3-bis(trifluoromethyl)-diaziridines (TFD) to the action of electrophiles is due to the lowering of the n- and w-orbital energies and depolarization of the C-N bonds due to hyperconjugation and the inductive effect of the CF3-groups.The steric effect of these groups is the reason of the low configurational stability of TFD compared with the 3,3-dimethyl analogues.
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Doi:10.1021/jo00195a053
(1984)Doi:10.1021/acs.orglett.7b01107
(2017)Doi:10.1039/c5cc03134f
(2015)Doi:10.1021/jo01032a018
(1964)Doi:10.1021/jm00335a027
(1964)Doi:10.1016/0040-4020(68)88054-8
(1968)