Aug 2026· ACS Catalysis· 1 citation· 88 references
Abstract
Heterohelicenes combine helical chirality with tunable electronic properties, making them attractive for applications in chiral materials and optoelectronics. However, their enantioselective synthesis, particularly for five-membered heterohelicenes, remains a long-standing challenge owing to the inherent synthetic difficulties and the lack of efficient catalytic strategies. Herein, we report a copper-catalyzed [3 + 2] annulation of propargylic esters followed by acid-promoted aromatization, thereby enabling a furan ring extension strategy for the convergent synthesis of heterohelicenes. A chiral N,N,P-ligand bearing a long alkyl chain provides effective stereocontrol, enabling the efficient construction of heterohelicene frameworks with high enantioselectivity. Mechanistic studies support a plausible catalytic cycle underlying the transformation. This strategy provides efficient access to enantioenriched, configurationally stable oxa[5]helicenes, aza[5]helicenes, and diheterohelicenes, establishes the synthetic potential of copper−allenylidene chemistry for helicene synthesis, and expands the toolbox for the development of chiral functional materials.
The enantioselective catalytic construction of structurally sophisticated helicenes integrating both helical and central chirality remains a formidable challenge, and organocatalytic strategies for helicene synthesis are still severely underexplored compared with transition-metal catalysis. Benefiting from the inhere...
Helicenes are a class of structurally fascinating polycyclic aromatic molecules composed of ortho-fused aromatic rings, which adopt a screwed shape and exhibit helical chirality due to the steric repulsion between the two terminal rings. However, the catalytic enantioselective synthesis of helicenes, especially those...
Wansen Xie, Tianren Qin, Yuheng Ma et al.· ACS Catalysis· 0 citations
Semisaturated heterocycles are privileged scaffolds in natural products and pharmaceuticals, yet a general and versatile catalytic strategy to access these chiral architectures remains a formidable challenge. Herein, we report a unified synthetic platform utilizing the earth-abundant cobalt coupled with a chiral N,N'-d...
Inherently chiral molecules generated by the curvature of planar frameworks represent an emerging class of three-dimensional chiral architectures, yet their catalytic asymmetric synthesis remains highly challenging. Herein, we report a Pd-catalyzed asymmetric Suzuki-Miyaura coupling for the efficient construction of in...
The enantioselective construction of boron-centered chirality remains a challenging topic in asymmetric catalysis. Although notable progress has been made in recent years, most existing strategies still rely on transition-metal catalysis, whereas organocatalytic approaches remain relatively scarce. Herein, we report...
Qing Yang, Jia-Hong Wu, Jingyu Ma et al.· ACS Catalysis· 0 citations
The development of general methods for the enantioselective synthesis of axially chiral molecules remains a longstanding challenge in organic synthesis. Among these, allenes represent a particularly important class of motifs due to their unique structural and electronic properties, yet their catalytic enantioselective...
