Synthesis and Reactivity of Electron-Deficient 3-Vinylchromones

Abstract

The reported methods and data for the synthesis and reactivity of electron-deficient 3-vinylchromones containing electron-withdrawing­ groups at the exo-cyclic double bond are summarized and systematized for the first time. The main methods for obtaining these compounds are Knoevenagel condensation, Wittig reaction, and palladium-catalyzed cross-couplings. The most important chemical properties are transformations under the action of mono- and dinucleophiles, ambiphilic cyclizations, and cycloaddition reactions. The cross-conjugated and polyelectrophilic dienone system in 3-vinylchromones provides their high reactivity and makes these compounds valuable building blocks for the preparation of more complex heterocyclic systems. Chemical transformations of 3-vinylchromones usually begin with an attack of the C-2 atom and are accompanied by the opening of the pyrone ring followed by recyclization, in which the carbonyl group of chromone, an exo-double bond or a substituent on it can take part. The mechanisms of the reactions are discussed, the conditions for their implementation are described, and the yields of the resulting products are given. This review focuses on an analysis and generalization of the knowledge that has accumulated on the chemistry of electron-deficient 3-vinylchromones, mostly over the past 15 years. 1 Introduction 2 Synthesis of 3-Vinylchromones 3 Reactions with Mononucleophiles 4 Reactions with Dinucleophiles 5 Ambiphilic Cyclization 6 Cycloaddition Reactions 7 Other Reactions 8 Conclusion

Keywords

• 3-vinylchromones
• nucleophilic reactions
• ambiphilic cyclizations­
• cycloaddition reactions
• heterocycles