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 an amide-based bisphosphonium salt-catalyzed asymmetric SNAr reaction that enables desymmetrically enantioselective C−O bond formation between prochiral α,α-dichloro BODIPY and phenolic nucleophiles, providing efficient access to boron-stereogenic BODIPY scaffolds. The strategy shows broad substrate scope and high stereocontrol (37 examples, up to 99% yield and >99% ee). Photophysical studies reveal that the resulting BODIPY derivatives display tunable optical properties and pronounced chiroptical activity. Mechanistic investigations indicate that cooperative hydrogen-bonding and ion-pair interactions between the catalyst and substrates generate a semienclosed chiral microenvironment, thereby enabling effective control over the stereoselectivity of the reaction. Our strategy transforms chiral BODIPYs from simple materials into highly diversifiable platform molecules bearing two synthetically valuable reactive sites, thereby unlocking synthetic versatility.
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...
ABSTRACT The efficient construction of boron stereogenic centers alongside axial chirality remains a significant synthetic challenge, particularly under one‐pot conditions. Herein, we report a cobalt/Salox‐catalyzed enantioselective annulation strategy that enables the simultaneous formation of B‐stereogenic frameworks...
Subramani Kumaran, Harihara Subramanian Ravi Sankar, Pritam Maity et al.· Advancement of science· 0 citations
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 di...
The construction of structurally complex, stereochemically rich spirocyclic frameworks remains a formidable challenge in organic synthesis, particularly when multiple stereoelements installed with precision in a single operation. Herein, we disclose a cobalt/Salicyloxazoline (Salox) catalyzed (4 + 1) spiroannulation...
Subramani Kumaran, Abir Das, J. R. Premkumar et al.· Communications Chemistry· 0 citations
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...
