title: Role of negative hyperconjugation and anomeric effects in the stabilization of the intermediate in SNV reactions.
abstract: The role of negative hyperconjugation and anomeric and polar effects in stabilizing the XZHCbetaCalphaYY'- intermediates in SNV reactions was studied computationally by DFT methods. Destabilizing steric effects are also discussed. The following ions were studied: X = CH3O, CH3S, CF3CH2O and Y = Y' = Z = H (7b-7d), Y = Y' = H, Z = CH3O, CH3S, CF3CH2O (7e-7i), YY' = Meldrum's acid-like moiety (Mu), Z = H, (8b-8d), and YY' = Mu, Z = CH3O, CH3S, CF3CH2O (8e-8i). The electron-withdrawing Mu substituent at Calpha stabilizes considerably the intermediates and allows their accumulation. The hyperconjugation ability (HCA) (i.e., the stabilization due to 2p(Calpha) --> sigma*(Cbeta-X) interaction) in 8b-8d follows the order (for X, kcal/mol) CH3S (8.5) > CF3CH2O (7.6) approximately CH3O (7.5). The HCA in 8b-8d is significantly smaller than that in 7b-7d due to charge delocalization in Mu in the former. The calculated solvent (1:1 DMSO/H2O) effect is small. The stability of disubstituted ions (7e-7i and 8e-8i) is larger than that of monosubstituted ions due to additional stabilization by negative hyperconjugation and an anomeric effect. However, steric repulsion between the geminal Cbeta substituents destabilizes these ions. The steric effects are larger when one or both substituents are CH3S. The anomeric stabilization (the energy difference between the anti,anti and gauche,gauche conformers) in the disubstituted anions contributes only a small fraction to their total stabilization. Its order (for the following X/Z pairs, kcal/mol) is CF3CH2O/CH3S (8i, 4.9) > CF3CH2O/CH3O (8h, 3.9) > CH3O/CH3S (8g, 3.3) > CH3S/CH3S (8f, 2.9) > CH3O/CH3O (8e, 2.4). Significantly larger anomeric effects of ca. 8-9 kcal/mol are calculated for the corresponding conjugate acids.
authors: Schulich Faculty of Chemistry and The Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa 32000, Israel. chrmiri@tx.technion.ac.il
authors: Miriam
authors: M
authors: Karni
authors: Claude F
authors: CF
authors: Bernasconi
authors: Zvi
authors: Z
authors: Rappoport