Kinetics and mechanism of benzylamine additions to ethyl α-acetyl-β-phenylacrylates in acetonitrile
Abstract
Kinetic studies of the addition of benzylamines to a noncyclic dicarbonyl group activated
The kinetic isotope effects (kH/kD > 1.0) measured with deuterated benzylamines (XC6H4CH2ND2) increase with a stronger electron acceptor substituent (δσX > 0) which is the same trend as those found for other dicarbonyl group activated series ( 1–4), but is in contrast to those for other ( noncarbonyl) group activated series (5–9). For the dicarbonyl series, the reactivity-selectivity principle (RSP) holds, but for others the anti-RSP applies. These are interpreted to indicate an insignificant imbalance for the former, but substantial lag in the resonance delocalization in the transition state for the latter series.