Guanidine-catalyzed enantioselective desymmetrization of meso-aziridines.

Organocatalyzed enantioselective desymmetrization of aziridines and epoxides

Enantioselective desymmetrization of meso-aziridines and meso-epoxides with various nucleophiles by organocatalysis has emerged as a cutting-edge approach in recent years. This review summarizes the origin and recent developments of enantioselective desymmetrization of meso-aziridines and meso-epoxides in the presence of organocatalysts.

The Ti-BINOLate-catalyzed, enantioselective ring-opening of meso-aziridines with amines.

The titanium-BINOLate-catalyzed, highly enantioselective ring-opening reaction of meso-aziridines has been developed which furnishes trans-1,2-diamines in typically good yields and excellent enantioselectivities. N-Aryl aziridines attached to a 5- or 6-membered carbocyclic ring are among the best substrates for this process providing the products in up to >99% ee. The chiral catalyst is easily ...

Lithium BINOL Phosphate Catalyzed Desymmetrization of meso-Epoxides with Aromatic Thiols

A highly enantioselective method for desymmetrization of meso-epoxides using thiols is reported. This is the first example of epoxide activation achieved using metal BINOL phosphates. The reaction has a broad scope in terms of epoxide substrates and aromatic thiol nucleophiles. The resulting β-hydroxyl sulfides are obtained in excellent yield and enantioselectivity.

Palladium-Catalyzed, Enantioselective Heine Reaction

Aziridines are important synthetic intermediates for the generation of nitrogen-containing molecules. N-Acylaziridines undergo rearrangement by ring expansion to produce oxazolines, a process known as the Heine reaction. The first catalytic, enantioselective Heine reaction is reported for meso-N-acylaziridines where a palladium(II)-diphosphine complex is employed. The highly enantioenriched oxa...

Vanadium-catalyzed enantioselective desymmetrization of meso secondary allylic alcohols and homoallylic alcohols.