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Abstract A catalytic atroposelective cycloaddition reaction between thioureas and ynals is developed. This reaction features the first NHC‐catalyzed addition of thioureas to acetylenic acylazolium intermediates to eventually set up C−N axial chirality with excellent optical purities. The obtained axially chiral thiazine derivative products bear multiple functional groups and are feasible for further transformations.
Li et al. (Thu,) studied this question.