One-Pot Synthesis of Quinoxaline N-Oxides via Radical-Mediated Cyclization of Ketene N,S-Acetals

Abstract

A facile and efficient one-pot synthesis of bench-stable quinoxaline N-oxides has been realized using α-oxoketene N,S-acetals and tert-butyl nitrite (TBN) in open air via cascade annulation. The double functionalization of N,S-acetals proceeds through an unanticipated (Csp²)–H nitrosation by NO radical (generated in situ by TBN) and subsequent intramolecular N-arylation leading to quinoxaline, which undergoes oxidation to quinoxaline N-oxides harboring three variegated substituents on their framework. Notably, two new C–N bonds are formed with the same N-oxide nitrogen. This protocol features short reaction time, good functional group tolerance and mild conditions, and does not require the use of either catalyst or external additive.

Key words

ketene N,S-acetals - tert-butyl nitrite (TBN) - radical coupling - quinoxaline N-oxides

Publication History

Received: 09 June 2023

Accepted after revision: 13 July 2023

Accepted Manuscript online:
13 July 2023

Article published online:
06 September 2023

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