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![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
Oxy-pyridinium Ylides Mediated 1,4-Pyridyl/Aryl Translocation
Yaping Tang1, Meirong Huang2, Zichun Yan1
1Jiangsu Key Laboratory of Advanced Catalytic Materials & Technology, School of Petrochemical Engineering, Changzhou University, Changzhou, Jiangsu 213164, People's Republic of China.
Abstract:
Molecular rearrangement via carbene transfer is a powerful tool to access molecular diversity. Herein, we describe an efficient approach to selective pyridyl/aryl relocation via a rhodium-catalyzed aminoarylation of diazo compounds, providing a promising strategy to access ortho-pyridyl N-alkylated pyridone scaffolds in a single operation. This reaction features the novel reactivity of oxy-pyridinium ylide, rhodium-associated five-membered transition state, and 1,4-pyridyl/aryl relocation. A computational study discloses the initial oxy-pyridinium ylide formation, keto-enol tautomerization, and 1,4-pyridyl migration to complete the whole rearrangement.
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