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Aerobic oxidation/metal-free cyclization cascades of nitrosoarenes and allenynes with TEMPO/O2: a switch of diradical to single radical intermediates
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Aerobic oxidation/metal-free cyclization cascades of nitrosoarenes and allenynes with TEMPO/O2: a switch of diradical to single radical intermediates

Chandrima Maitra, Debashis Barik, Yeu-Shiuan Ho, Mu-Jeng ChengRai-Shung Liu
Organic Chemistry Frontiers
2023

摘要

Organic Chemistry
New cascade oxidative cyclizations between nitrosoarenes and allenynes in the presence of TEMPO/O 2 mixtures afford new indanones fused with an aziridine ring. These four-component reactions are catalyst- and additive-free, yielding no byproducts with nearly 100% atom economy. Our DFT calculations indicate that the nitrosoarene/allenyne mixtures generate diradical intermediates that are intercepted by a TEMPO radical to form a single nitroxy radical to take up one O 2 molecule. This reaction model can also rationalize new chemoselectivity for nitrosoarenes bearing para-alkyl substituents.

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