Domino Reactions Based on Combinatorial Bond Transformations in Electron-Deficient Tertiary Enamines

Abstract

Electron-deficient enamines such as enaminones and enaminoesters are moieties showing widespread application in organic synthesis. Among the various available electron-deficient enamines, the N,N-disubstituted amino-functionalized ones (tertiary enamines) represent a class of special enamines with distinct properties and important applications. Based on our longstanding interest in exploring novel synthetic methods using electron-deficient tertiary enamines, we present herein the research advances in organic synthesis via domino reactions making use of the combinatorial C-N, C=C, C-H, and other bond transformations of electron-deficient tertiary enamines.

Recent Advances in Transition Metal Catalyzed Synthesis of β‐Enaminones and β‐Enaminoesters

“…Owing to the amine‐alkene‐carbonyl conjugated structural features, they combine nucleophilicity of enamines with electrophilicity of enones or enesters (Figure 1). They have been served as versatile building blocks in organic synthesis for aromatic compounds, heterocyclic and fused heterocyclic compounds as well as non‐cyclic compounds under appropriate reaction conditions [1–7] . On the other hand, β ‐enaminones and β ‐enaminoesters substructures are common structural motifs in a large number of biologically active molecules and pharmaceutical substances [8] .…”

“…They have been served as versatile building blocks in organic synthesis for aromatic compounds, heterocyclic and fused heterocyclic compounds as well as non-cyclic compounds under appropriate reaction conditions. [1][2][3][4][5][6][7] On the other hand, β-enaminones and βenaminoesters substructures are common structural motifs in a large number of biologically active molecules and pharmaceutical substances. [8] Therefore, the development of convenient and efficient methods for the construction of β-enaminones and β-enaminoesters have received increasing attention.…”

Mannich Reaction with Enaminones: Convenient Synthesis of Functionalized Tetrahydro‐pyrimidines, Dihydro‐1,3‐oxazines, and Dihydro‐1,2,4‐triazepines

“…On the other hand, the chemistry of enaminones has been the subject of wide and increasing interest because of their importance as versatile synthetic intermediates for construction and modification of heterocyclic systems, natural products, and drug design . Although the utility of tertiary enaminones as intermediates in synthesis of a variety of heterocycles was reported , the use of secondary enaminones as synthetic intermediates was less widely recognized and had seen limited use . In particular, Mannich reaction with secondary enaminones, derived from 1,3‐indandione or dimedone , has been reported as a route to fused tetrahydropyrimidines, dihydro‐1,3‐oxazines, and benzodiazepines.…”

in situ Formation of RSCl/ArSeCl and Their Oxidative Coupling with Enaminone Derivatives Under Transition‐metal Free Conditions

“…[1] On the other hand, there has been long-standing interest in the construction of CÀ S/Se bonds because of their important applications in organic synthesis [2] and the broad biological properties associated with S or Se-containing compounds. [1] On the other hand, there has been long-standing interest in the construction of CÀ S/Se bonds because of their important applications in organic synthesis [2] and the broad biological properties associated with S or Se-containing compounds.…”

“…Enaminones and their analogues play important roles in numerous organic transformations due to the fact that this class of compounds possess both electrophilic and nucleophilic reactive sites in their structures, which enables the construction of various molecules with enriched structural diversity. [1] On the other hand, there has been long-standing interest in the construction of CÀ S/Se bonds because of their important applications in organic synthesis [2] and the broad biological properties associated with S or Se-containing compounds. [3] As a result, α-chalcogenylenaminone compounds and their analogues, known as significant and useful polyfunctionalized olefins, have attracted considerable attention from organic chemists to explore their synthetic method and application.…”