Iridium-Catalyzed Intramolecular Asymmetric Allylation of Vinyl Benzoxazinones for the Synthesis of Chiral 4H-3,1-Benzoxazines via Kinetic Resolution

Chiral benzoxazinones and 4H-3,1-benzoxazines as important motifs are widely found in abundant pharmaceuticals and biological molecules. We herein successfully developed the first kinetic resolution (KR) process of racemic benzoxazinones through Ircatalyzed asymmetric intramolecular allylation, furnishing a wide range of chiral benzoxazinones and 4H-3,1-benzoxazines with excellent results via outstanding KR performances (with the s factor up to 170). This protocol exhibited broad substrate scope generality and good functional group tolerance, and the chiral 4H-3,1-benzoxazine products could be readily transformed to other useful optically active heterocycles.

Automated summary

Chiral benzoxazinones and 4H-3,1-benzoxazines are important motifs found in pharmaceuticals and biological molecules. This study successfully developed a kinetic resolution process for racemic benzoxazinones through iridium-catalyzed asymmetric intramolecular allylation, providing a wide range of chiral benzoxazinones and 4H-3,1-benzoxazines with excellent results. The protocol demonstrated broad substrate scope and good functional group tolerance, and the chiral 4H-3,1-benzoxazine products could be easily transformed into other useful optically active heterocycles.