Citation: Quoc Hoang Pham, Ivan Sliusarevskyi, Argha Saha, Lennard Kloene, Nico J. Linnartz, Claire Empel, Iris M. Oppel, Debabrata Maiti, Rene M. Koenigs. A metal-catalyzed triplet relay strategy for aza-Pauson-Khand reactions[J]. Chinese Chemical Letters, ;2026, 37(10): 112306. doi: 10.1016/j.cclet.2025.112306 shu

A metal-catalyzed triplet relay strategy for aza-Pauson-Khand reactions

a.
RWTH Aachen University, Institute of Organic Chemistry, Aachen 52074, Germany
b.
Indian Institute of Technology Bombay, Department of Chemistry, Powai, Mumbai 400076, India
c.
University of Bayreuth, Bayreuth 95447, Germany
d.
RWTH Aachen University, Institute of Inorganic Chemistry, Aachen 52074, Germany

dmaiti@iitb.ac.in

rene.koenigs@uni-bayreuth.de

Received Date: 4 September 2025
Revised Date: 5 December 2025
Accepted Date: 21 December 2025
Available Online: 22 December 2025

Figures(6)

The reactivity of metal-catalyzed nitrene transfer reaction is typically governed by (2 + 1) cycloaddition reaction chemistry to forge aziridine heterocycles. Herein, we describe a strategy to overcome this classic reactivity using mixed-valency diruthenium(Ⅱ,Ⅲ) paddlewheel complexes or silver(I) catalysts. These metal complexes allow the efficient relay of the diradical nature of triplet nitrene reagents in catalytic fashion and enable (2 + 2 + 1) cycloaddition reactions of 1,6-dienes with nitrenes as an N₁ unit. We have exemplified this concept in a broad substrate scope, including the functionalization of drug molecules and describe applications of the reaction products in the synthesis of drug analogues. This catalytic (2 + 2 + 1) cycloaddition now opens up new concepts and strategies in leveraging catalytic nitrene transfer reactions beyond classic aziridination chemistry.
- Nitrene,
- Cycloaddition,
- Triplet reactivity radical chemistry,
- Computational studies
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1.
沈阳化工大学材料科学与工程学院沈阳 110142