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Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions
Published on: July 17, 2020
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Azide-to-Diazo Transformation Facilitated by Michael Addition via Phosphazide Formation
Tomoki Mano1, Takahiro Yasuda1, Gaku Orimoto1
1Department of Biological Science and Technology, Faculty of Advanced Engineering, Tokyo University of Science, Tokyo, Japan.
Angewandte Chemie (International Ed. in English)
|April 21, 2026
Summary
A novel Michael addition reaction involving thiols and amines to 2-azidoacrylic acid esters was discovered. This transformation utilizes an azide-to-diazo conversion, yielding versatile organonitrogen compounds.
Area of Science:
- Organic Chemistry
- Synthetic Chemistry
Background:
- Michael addition reactions are fundamental in organic synthesis.
- Azidoacrylates are versatile building blocks but their transformations can be challenging.
Purpose of the Study:
- To disclose a new synthetic route for Michael addition to 2-azidoacrylic acid esters.
- To explore the utility of azide-to-diazo conversion in this context.
Main Methods:
- Reaction of 2-azidoacrylic acid esters with thiols and amines.
- In situ generation of phosphazide intermediates using (4-dimethylaminophenyl)di(tert-butyl)phosphine (Amphos).
- Utilizing azide-to-diazo conversion and N-N bond cleavage.
Main Results:
- A novel 1,4-addition pathway was established.
- The reaction proceeds through phosphazide intermediates.
- Versatile Michael adducts were synthesized efficiently under practical conditions.
Conclusions:
- The developed method provides a new pathway for synthesizing functionalized organonitrogen compounds.
- The reaction's versatility allows for the creation of diverse molecular structures.
- This work expands the synthetic utility of azidoacrylates.
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