biostudies-literatureBloch JMDivision of ChemistryNational Cancer InstituteNational Institute of General Medical SciencesNIGMS NIH HHSNational Institute on Aging30146-30153https://www.ebi.ac.uk/biostudies/studies/S-EPMC12371869biostudies-literatureUnknown147(33)The Diels-Alder reaction of benzenes remains a significant synthetic challenge, owing to their highly stabilized aromatic cores. In this work, the dearomatization agent {WTp(NO)(PMe₃)} is used to promote Diels-Alder reactions of dihapto-coordinated (η²) benzenes with alkynes. The resulting η²-barrelene complexes can be oxidized to liberate intact barrelenes. Alternatively, mild pyrolysis leads to the extraction of the corresponding tungsten-acetylene complex and concomitant formation of new arenes possessing substituents originating from the acetylene dienophiles.Journal of the American Chemical SocietyTungsten-Enabled Diels-Alder Cycloaddition and Cycloreversion of Arenes and Alkynes: Divergent Synthesis of Highly Functionalized Barrelenes and Arenes.PMC12371869R21AG07699CHE-2215062R35 GM152065CHE-2018870R35GM152065P30CA044579Bloch JMEricson MNTepe JJSavelson EMeng AQDickie DAHarman WDPatel IUfalseTungsten-Enabled Diels-Alder Cycloaddition and Cycloreversion of Arenes and Alkynes: Divergent Synthesis of Highly Functionalized Barrelenes and Arenes.The Diels-Alder reaction of benzenes remains a significant synthetic challenge, owing to their highly stabilized aromatic cores. In this work, the dearomatization agent {WTp(NO)(PMe₃)} is used to promote Diels-Alder reactions of dihapto-coordinated (η²) benzenes with alkynes. The resulting η²-barrelene complexes can be oxidized to liberate intact barrelenes. Alternatively, mild pyrolysis leads to the extraction of the corresponding tungsten-acetylene complex and concomitant formation of new arenes possessing substituents originating from the acetylene dienophiles.2025-01-01T00:00:00Z2025 Aug2026-05-08T10:50:37.592Z2026-05-03T03:05:53.924ZS-EPMC123718694077931710.1021/jacs.5c08320