Phosphine-Mediated Redox Cyclization of 1-(2-Nitroaryl)prop-2-ynones to 3-Hydroxyquinolin-4-ones: Formal Intramolecular Oxyamination of α,β-Ynones

3-Hydroxyquinoline-4(1H)-ones (3HQs) are privileged structural motifs. The current methods for their synthesis necessitate strongly acidic or basic conditions, which hamper the generality and practicality. Here, we describe phosphine-mediated redox transformation of easily accessible 1-(2nitroaryl)prop-2-ynones to 3HQs. Besides establishing a new entry to the synthesis of 3HQs under neutral conditions, this method is the first formal intramolecular oxyamination of alpha,beta-ynones. The synthetic utility of this method is demonstrated in the total synthesis of japonine, its analogs, and rare quinoline derivatives.

Automated summary

This study describes a new method for the synthesis of 3HQs under neutral conditions, which also represents the first intramolecular oxyamination of α,β-ynones. The synthetic utility of this method is demonstrated by successfully synthesizing japonine, its analogs, and rare quinoline derivatives.