biostudies-literatureLee DUniversity of MinnesotaNational Cancer InstituteNCI NIH HHSNational Institutes of HealthNIH HHSNational Science Foundation2527-2537https://www.ebi.ac.uk/biostudies/studies/S-EPMC8797013biostudies-literatureUnknown7(9)Polycyclic, highly fused and, perforce, highly conjugated aromatic organic compounds (PACs) have been of interest to chemists since the discovery of naphthalene in 1821. In modern decades these have attracted ever-growing attention because of their architectures, properties, and wide-ranging practical applications (cf. The Bigger Picture). Given the unabated interest in such molecules, the development of new methods and strategies for the practical synthesis of PACs having new structural motifs is important. Here we describe one-pot, purely thermal cyclizations of substrates containing sets of independent triynes, each arrayed upon a common core structure. This produces topologically unique products through sequential generation/trapping of a series of benzyne intermediates. More specificaChemRadial hexadehydro-Diels-Alder reactions.PMC8797013CHE-1665389S10 OD011952P30 CA077598CA-77598S10OD011952Ross SPXiao XHoye TRLee DfalseRadial hexadehydro-Diels-Alder reactions.Polycyclic, highly fused and, perforce, highly conjugated aromatic organic compounds (PACs) have been of interest to chemists since the discovery of naphthalene in 1821. In modern decades these have attracted ever-growing attention because of their architectures, properties, and wide-ranging practical applications (cf. The Bigger Picture). Given the unabated interest in such molecules, the development of new methods and strategies for the practical synthesis of PACs having new structural motifs is important. Here we describe one-pot, purely thermal cyclizations of substrates containing sets of independent triynes, each arrayed upon a common core structure. This produces topologically unique products through sequential generation/trapping of a series of benzyne intermediates. More specifica2021-01-01T00:00:00Z2021 Sep2025-04-05T16:11:47.277Z2025-04-05T16:11:47.277ZS-EPMC87970133509723810.1016/j.chempr.2021.08.010