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An efficient approach for asymmetric synthesis of planar‐chiral macrocycles (paracyclophanes) has been disclosed through enantioselective electrophilic aromatic aminations with azodicarboxylates enabled by chiral phosphoric acid catalysis. A wide range of chiral macrocycles bearing varied ring sizes (16 to 23‐membered) and functional group‐containing ansa chains were readily afforded using this method, with excellent yields and high enantioselectivities (23 examples, up to 99.5 : 0.5 er). Experimental studies and DFT calculations were performed to elucidate the mechanism and origin of stereoselectivities of these reactions. Preliminary utilization of the planar‐chiral macrocycle as chiral organocatalyst showcased the potential applications of these novel chiral skeletons. [ABSTRACT FROM AUTHOR]

An efficient kinetic resolution of N-aryl β-amino alcohols has been developed via asymmetric para-aminations of anilines with azodicarboxylates enabled by chiral phosphoric acid catalysis. Broad substrate scope and high kinetic resolution performances were afforded with this method. Control experiments supported the critical roles of the NH and OH group in these reactions. [ABSTRACT FROM AUTHOR]

The first kinetic resolution of hydroquinoline derivatives with α,α‐disubstitution has been achieved through asymmetric remote aminations with azodicarboxylates enabled by chiral phosphoric acid catalysis. Mechanistic studies suggest a monomeric catalyst pathway proceeding through rate‐ and enantio‐determining electrophilic attack promoted by a network of attractive non‐covalent interactions between the substrate and catalyst. Facile subsequent removal and transformations of the newly introduced hydrazine moiety enable these protocols to serve as powerful tools for asymmetric synthesis of N‐heterocycles with α,α‐disubstitution. [ABSTRACT FROM AUTHOR]

A series of cyclohexyl‐fused SPINOL‐derived phosphoric acids (Cy‐SPA) have been developed to catalyze the kinetic resolution of 2‐N‐acylamido tertiary allylic alcohols, providing access to chiral oxazolines bearing C‐2 alkyl substituents with high enantioselectivities (with s‐factors up to 153). Gram‐scale reaction with 1 mol% catalyst loading and transformations of the chiral products demonstrates the value of these methods. [ABSTRACT FROM AUTHOR]

Asymmetric functionalizations of α‐sulfanyl cyclic ketones were realized via chiral phosphoric acid catalyzed enantioselective addition reactions with aldimines, azodicarboxylates and allenamides. A series of chiral organosulfur compounds possessing sulfur‐containing tetrasubstituted stereocenters were accessed via these methods, with excellent regioselectivities and high stereoselectivities. [ABSTRACT FROM AUTHOR]