B3LYP functionals nucleophilic substitutions

Nucleophilic vinylic substitutions of 4//-pyran-4-onc and 2,6-dimethyl-4//-pyran-4-one with a hydroxide ion in aqueous solution were calculated by the density functional theory (B3LYP) and ab initio (MP2) methods using the 6-31+G(d) and 6-31G (d) basis sets. The aqueous solution was modelled by a supermolecular approach, where 11 water molecules were involved in the reaction system. The calculations confirmed a different addition-elimination mechanism of the reaction compared with that in the gas phase or non-polar solution. Addition of OH- at the C(2) vinylic carbon of the pyranone ring with an activation barrier of 10-11 kcalmol-1 (B3LYP) has been identified as the rate-determining step, in good quantitative and qualitative agreement with experimental kinetics. Solvent effects increase the activation barrier of the addition step and, conversely, decrease the barrier of the elimination step.138... 

Investigation of the electron distribution in 3-aryl(hetaryl)substituted 2-methoxy-and 2-methylthiopropenals ArCH=C(XMeX3H=0 (X = O, S) using DFT calculations at B3LYP/6-311+G and M06/6-311+G levels, together with natural bond orbital (NBO) analysis, resulted in the prediction of possible electrophilic (Markovnikov-type) or nucleophilic (Michael-type) addition reactions as a function of the donor and acceptor effects of the substituents. ... 

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