Nucleophilic Addition of Amino-groups to an Activated Carbon–Carbon Double Bond

Abstract

The review presents data on the effect of structural and steric factors, catalysts, and solvents on the mode and rate of condensation of activated olefins with amines, which indicate that the mechanisms of such condensations are to some extent general. The considerable importance of the steric inhibition of the reactions is evidence in favour of the hypothesis of a polar transition state characterised by a rigid structure. Proton transfer involving a proton donor and (or) acceptor or, more rarely, the ejection of a negative ion (see the reactions of β-halogeno-olefins) plays a significant role in the stabilisation of the transition state. The sequence of relative activities of the olefins CH 2 = CHX is affected both by the polarising effect of the group X and the possibility of the delocalisation of the charges in the activated complex. Nevertheless the problems of the catalytic effect of proton-donating, alkaline, and particularly peroxidic additives are still not completely clear and require further study. The bibliography includes 266 references. CONTENTS

Synthesis and antifungal and antibacterial bioactivity of cyclic diamines containing boronate esters

“…Compound 1 is presumably generated in this reaction via initial aldimine formation at one of the amine groups followed by an intramolecular hydroamination of the activated double bond with the other amine. 49 To test this hypothesis, we prepared the aldimine derived from addition of propylamine to 2-HC(O)C 6 H 4 Bpin. Although 11 B NMR data suggested that the imine nitrogen was coordinated to the boron atom, attempts to carry out an intermolecular hydroamination on this imine with various primary amines proved unsuccessful.…”

Haloalkenes activated by geminal groups in reactions with N-nucleophiles

“…In terms of their activating capacity, these groups can be arranged in the sequence CN 4 COOR 5 < C(O)R 5 CHO, 10 which shows a good correlation with the activity series of unsaturated compounds of the CH 2 =CH ± EWG type in the Michael reaction with amines. 11 II. Reactions of haloalkenes activated by geminal groups with N-nucleophiles…”

A New Class of Polymers: Starburst-Dendritic Macromolecules

“…A methanolic medium was preferred for exhaustive Michael addition reactions. 8 Attempts to conduct the addition reactions either neat or in non-protic medium invariable led to limited alkylation products. For example, neat alkylation of EDA gave predominately the tri-and tetra-adduct in a ratio of -70: 30, whereas, in methanol tetra-adduct formation was…”