N-Heterocyclic carbene-catalyzed enantioselective (dynamic) kinetic resolution for the assembly of inherently chiral macrocycles

Abstract

Heterocalixaromatics play a significant role in supramolecular chemistry and material sciences. However, the absence of robust enantioselective synthetic methods has constrained their broader applications. On the other hand, the construction of inherently chiral macrocycles via N-heterocyclic carbene (NHC) still remains underexplored to date. We herein report an NHC-catalyzed approach for the rapid assembly of inherently chiral macrocycles. This transformation proceeds via a dynamic kinetic resolution (DKR) or kinetic resolution (KR) process, enabling the conversion of racemic substrates into inherently chiral heterocalixaromatics with good to high yields, and high to excellent enantioselectivities. DFT calculations were carried out to clarify the chirality control in the related DKR process.