Regioselectivity of the intramolecular nucleophilic attack in [R[sbnd]CH−[sbnd]N[dbnd]CH[sbnd]C6H4[sbnd]Y]: A mass spectrometric and computational study

Abstract

The investigation into the intramolecular nucleophilic attack in carbanion [RCH −NCHC6H4Y] in the gas phase has been carried out by mass spectrometry and density functional theory (DFT). The main results of the present work are as follows: the regioselectivity of the intramolecular attack depends on the substituent on the para-position of the benzene ring. NO2 favors C3-attack to form spiro-σ-adduct and it also contributes to the loss of HCN, while other substituents (H, OMe, NMe2 and Cl) favor C4-attack to yield bicyclo-σ-adduct and in this condition, HCN cannot be lost. In the meantime, DFT calculations also demonstrate that the loss of HCN from the spiro-σ-adduct is both thermodynamically and kinetically beneficial, while that from the bicyclo-σ-adduct is disadvantageous either in kinetics or thermodynamics.