An organocatalytic atroposelective strategy for accessing enantioenriched axially chiral IAN analogues was developed for the first time. A class of novel atropisomeric C2arylquinoline skeletons were synthesized with high enantiocontrol via chiral phosphoric-acid-catalyzed heteroannulation of in situ generated vinylidene ortho-quinone methide (VQM) intermediates with ortho-aminophenones. The strategy tolerated a broad substrate scope, providing a facile organocatalytic approach to IAN analogues in good yields and excellent enantioselectivities under mild reaction conditions. Moreover, the synthetic utility of this methodology was illustrated through further transformations into IAN-type ligand and axially chiral thiourea. Research on axially chiral biaryls has developed rapidly and gained considerable momentum in recent years because of their widespread appearance in natural products, [1] bioactive molecules, [2] and privileged chiral ligands and catalysts. [3] In sharp contrast, the asymmetric construction of axially chiral heterobiaryls was still underdeveloped, [4] even though it is scientifically important and of great significance in practical application. [5] For instance, the effective approaches to access axially chiral 2-arylpyridines (isoquinolines) are especially scanty, while they have emerged as essential backbone of numerous chiral catalysts and ligands in asymmetric catalysis (Figure 1). [6] This type of heteroaryl atropisomers ordinarily formed a chelate ring with metal atom through the coordination of nitrogen and other donor atoms, such as phosphorus, nitrogen, oxygen, and sulfur, providing the asymmetric induction in various metal-catalyzed enantioselective transformations (Figure 2 a). [7] Conventionally, synthetic approaches for enantioenriched 2-arylpyridine/isoquinoline skeletons depend mainly on transition-metal mediated patterns, such as cross-coupling, [6i,r] (dynamic) kinetic resolution/ transformation, [6a,g,h,j-q,s] and de novo construction of a (hetero)aromatic ring.