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Summary: Atropisomers beyond the C-C axis have become important additions to the field of axially chiral compounds. Previously considered challenging, these atropisomers characterized by C-N, C-O, C-B, or N-N bonds have been found to possess stable axially chiral frameworks due to their shorter bond lengths and electron-repelling effects. Recent years have seen rapid progress in this emerging area, with various catalytic approaches being reported for their efficient synthesis. These X-Y axially chiral compounds are valuable molecules that can be utilized as ligands or catalysts in asymmetric catalysis or evaluated for their potential biological activities. The chemistry of atropisomers beyond C-C axial chirality is believed to hold an important position in organic chemistry and beyond.
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