Synthesis and Properties of Polyfunctional Cyclic β‐Alkoxy‐α,β‐Unsaturated Ketones Based on 4‐Methylene‐1,3‐dioxolanes

• Published in: European journal of organic chemistry 2018-08, Vol.2018 (27-28), p.3853-3861
• Main Authors: Gerus, Igor I., Balabon, Olga A., Pazenok, Sergiy V., Lui, Norbert, Kondratov, Ivan S., Tarasenko, Karen V., Shaitanova, Elena N., Ivasyshyn, Viktor E., Kukhar, Valery P.
• Format: Article
• Language: English
• Subjects: Acylation; Aliphatic compounds; Amination; Amines; Ammonia; Aromatic compounds; Chemical synthesis; Enaminones; Enones; Fluorinated compounds; Fluorination; Heterocyclic compounds; Isomers; Ketones; Methylene; Organic chemistry
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.201800786

New CCl3‐ and CF3‐substituted enones, bearing additional hidden hydroxymethyl functions, were prepared by acylation of 4‐methylene 1,3‐dioxolanes. The synthesized enones are interesting building blocks for agrochemical and medicinal chemistry research. The reactivity of synthesized enones with various amines was studied, and enaminones 13 and 14 were obtained under NH3 interaction; the reaction with aliphatic primary amines afforded enaminones 17 in high yields as equilibrium mixtures of E and Z isomers. The reaction of fluorinated enone 9c with anilines afforded a mixture of products, including non‐aromatic heterocyclic compounds 25 and 26 bearing the CF3 group as well as furan 27 with CF3 and amino functions at positions 5 and 3, respectively. The hydrolysis of enone 9c afforded cyclic compound 11. The synthesis of new polyfunctional cyclic β‐alkoxy‐α,β‐unsaturated ketones, bearing trifluoromethyl and trichloromethyl groups, was developed. The reactions of amination and hydrolysis of these enones were investigated.