This study presents an efficient and direct catalytic synthesis of N–N axially chiral pyrroles and indoles with vicinal central chirality through oxidative N-heterocyclic carbene (NHC) catalyzed (3 + 3) cycloaddition. The method involves the formation of 5,6-dihydropyrimidin-4-ones from isothioureas and enals, followed by conversion to N–N atropisomers. This approach allows for the synthesis of structurally diverse N–N axially chiral pyrroles and indoles with moderate to good yields and excellent enantioselectivities. The reaction mechanism and enantioselectivity are explored using DFT calculations, revealing the importance of non-covalent interactions between the isothiourea and NHC catalyst. The study also demonstrates the potential applications of these axially chiral compounds in synthetic transformations, such as functionalization and chiral ligand development.This study presents an efficient and direct catalytic synthesis of N–N axially chiral pyrroles and indoles with vicinal central chirality through oxidative N-heterocyclic carbene (NHC) catalyzed (3 + 3) cycloaddition. The method involves the formation of 5,6-dihydropyrimidin-4-ones from isothioureas and enals, followed by conversion to N–N atropisomers. This approach allows for the synthesis of structurally diverse N–N axially chiral pyrroles and indoles with moderate to good yields and excellent enantioselectivities. The reaction mechanism and enantioselectivity are explored using DFT calculations, revealing the importance of non-covalent interactions between the isothiourea and NHC catalyst. The study also demonstrates the potential applications of these axially chiral compounds in synthetic transformations, such as functionalization and chiral ligand development.