biostudies-literatureCai YNational Natural Science Foundation of ChinaFundamental Research Funds for the Central Uviersitye2102310118https://www.ebi.ac.uk/biostudies/studies/S-EPMC8488665biostudies-literatureUnknown118(39)Electrophilic aromatic substitution (EAS) reactions are widely regarded as characteristic reactions of aromatic species, but no comparable reaction has been reported for molecules with Craig-Möbius aromaticity. Here, we demonstrate successful EAS reactions of Craig-Möbius aromatics, osmapentalenes, and fused osmapentalenes. The highly reactive nature of osmapentalene makes it susceptible to electrophilic attack by halogens, thus osmapentalene, osmafuran-fused osmapentalene, and osmabenzene-fused osmapentalene can undergo typical EAS reactions. In addition, the selective formation of a series of halogen substituted metalla-aromatics via EAS reactions has revealed an unprecedented approach to otherwise elusive compounds such as the unsaturated cyclic chlorirenium ions. Density functional theory calculations were conducted to study the electronic effect on the regioselectivity of the EAS reactions.Proceedings of the National Academy of Sciences of the United States of AmericaElectrophilic aromatic substitution reactions of compounds with Craig-Mobius aromaticity.PMC848866521871225U17052542072019004221931002Hua YXia HChen ZLan QLu ZZhang HCai YLin ZFei JfalseElectrophilic aromatic substitution reactions of compounds with Craig-Mobius aromaticity.Electrophilic aromatic substitution (EAS) reactions are widely regarded as characteristic reactions of aromatic species, but no comparable reaction has been reported for molecules with Craig-Möbius aromaticity. Here, we demonstrate successful EAS reactions of Craig-Möbius aromatics, osmapentalenes, and fused osmapentalenes. The highly reactive nature of osmapentalene makes it susceptible to electrophilic attack by halogens, thus osmapentalene, osmafuran-fused osmapentalene, and osmabenzene-fused osmapentalene can undergo typical EAS reactions. In addition, the selective formation of a series of halogen substituted metalla-aromatics via EAS reactions has revealed an unprecedented approach to otherwise elusive compounds such as the unsaturated cyclic chlorirenium ions. Density functional theory calculations were conducted to study the electronic effect on the regioselectivity of the EAS reactions.2021-01-01T00:00:00Z2021 Sep2025-04-22T09:56:32.809Z2025-04-05T23:22:58.965ZS-EPMC84886653454485910.1073/pnas.2102310118