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Synlett 2024; 35(02): 145-154
DOI: 10.1055/a-2127-1086
DOI: 10.1055/a-2127-1086
synpacts
Enamine N-Oxides: Design, Synthesis, and Function in Bioorthogonal Reactions
This research was supported by the National Institute of Environmental Health Sciences (NIH NIEHS; 1DP2ES030448) and the Claudia Adams Barr Program for Innovative Cancer Research.
Abstract
Enamine N-oxides act as a chemical linchpin bridging two bioorthogonal associative and dissociative reactions. This article describes the design of enamine N-oxides, their synthesis through the retro-Cope elimination reaction, the use of solvent, hyperconjugation, strain, and rehybridization effects to achieve bioorthogonal reactivity, and their rapid reductive cleavage with diboron reagents. The coordinated assembly and disassembly of the enamine N-oxide motif constitutes a powerful chemical operation that enables the attachment and detachment of small molecules from biomacromolecules in a biological setting.
1 Introduction
2 Background
3 General Access to Linear Enamine N-Oxides
4 Strain-Promoted Hydroamination Reaction
5 Electronically Activated Alkynes
6 Chemically Revertible Reactions
7 Conclusion
Key words
bioorthogonal chemistry - enamine N-oxides - ligation reaction - cleavage reaction - strain-promoted reaction - rehybridization effect - diboronPublication History
Received: 25 May 2023
Accepted after revision: 11 July 2023
Accepted Manuscript online:
11 July 2023
Article published online:
04 September 2023
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