Axially chiral enamides bearing a N-C axis have been recently studied and were proposed to be valuable chiral building blocks, but a stereoselective synthesis has not been achieved. Here, we...

Axially chiral styrenes are of great interest since they may serve as a class of novel chiral ligands in asymmetric synthesis. However, only recently have strategies been developed for their enantioselective preparation. Thus, the development of novel and efficient methodologies is highly desirable. Herein, we reported the first tandem iridium catalysis as a general strategy for the synthesis of axially chiral styrenes enabled by Asymmetric Allylic Substitution-Isomerization (AASI) using cinnamyl carbonate analogues as electrophiles and naphthols as nucleophiles. In this approach, axially chiral styrenes were generated through two independent iridium-catalytic cycles: iridium-catalyzed asymmetric allylic substitution and in situ isomerization via stereospecific 1,3-hydride transfer catalyzed by the same iridium catalyst. Both experimental and computational studies demonstrated that the isomerization proceeded by iridium-catalyzed benzylic C–H bond oxidative addition, followed by terminal C–H reductive elimination. Amid the central-to-axial chirality transfer, the hydroxyl of naphthol plays a crucial role in ensuring the stereospecificity by coordinating with the Ir­(I) center. The process accommodated broad functional group compatibility. The products were generated in excellent yields with excellent to high enantioselectivities, which could be transformed to various axially chiral molecules.

We highlighted the recent advances in the field of central-to-axial chirality transfer for the synthesis of axially chiral molecules.

All-carbon quaternary stereocenters are versatile building blocks, and their asymmetric construction has attracted much attention. Herein, we disclose an axial-to-central chirality transfer strategy for the synthesis of chiral quaternary stereocenters via dearomatization of (S)-BINOLs. The reaction proceeded smoothly with a wide range of propargyl carbonates to afford chiral spiro-compounds in high yields with excellent enantioselectivities. In addition, the strategy was extended to kinetic resolution of rac-BINOLs albeit with moderate s value.

An efficient tandem cycloisomerization–amination reaction catalyzed by silver is described. This rapid and atom-economic reaction delivered 1-amino-2H-quinolizin-2-one scaffolds in high yields under mild conditions. The reaction could be extended to an asymmetric version albeit with moderate enantioselective excess of the products. In addition, the products can be easily reduced into various azabicycles containing 4-pyridones, which are important building blocks in organic synthesis.