α-Haloenamides: Synthesis and Subsequent Transformations

Abstract

The aim of this Short Review is to give an updated overview of the synthesis of α-haloenamides, which constitute a versatile subclass of enamides. α-Haloenamides can be prepared from ynamides, acetamides, or gem-dibromoalkenes in the presence of N-nucleophiles and easily converted into more elaborated structures through halogen-metal exchange and transition-metal-catalyzed cross-coupling reactions.

1 Introduction

2 α-Haloenamide Synthesis

2.1 Hydrohalogenation of Ynamides

2.1.1 cis-Hydrohalogenation of Ynamides

2.1.2 trans-Hydrohalogenation of Ynamides

2.2 α,β-Dihalogenation

2.2.1 lodochlorination and Iodobromination of Ynamides

2.2.2 Iodofluorination of Ynamides

2.3 Chloroselenation of Ynamides

2.4 Carbohalogenation of Ynamides

2.4.1 Carboiodination

2.4.2 Chloroallylation

2.4.3 Chloro-benzhydrylation

2.4.4 Chloro-γ-hydroxylation

2.5 Vilsmeier–Haack Reactions

2.6 Cross-Coupling Reaction of gem-Dibromoalkenes in the Presence of N-Nucleophiles

3 Transformations of α-Haloenamides

3.1 Suzuki and Sonogashira Reactions

3.2 Heck Reaction

3.3 Stille Reaction

3.4 Miscellaneous Applications

3.4 Carbonylation

3.4.2 Reduction

3.4.3 Synthesis of α-Fluoroimides

3.4.4 Palladium-Catalyzed Intramolecular Cyclization

4 Conclusion

Key words

α-haloenamides - synthesis - ynamides - halogenation - cross-coupling reactions

Publication History

Received: 26 July 2022

Accepted after revision: 09 August 2022

Accepted Manuscript online:
09 August 2022

Article published online:
26 October 2022

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