Pozo Míguez, IagoCobas Martínez, AgustínPeña Gil, DiegoGuitián Rivera, EnriquePérez Meirás, María Dolores2022-08-092022-08-092021Org. Lett. 2021, 23, 7376−7380. https://doi.org/10.1021/acs.orglett.1c025521523-7060http://hdl.handle.net/10347/29041The reaction of 2-(trimethylsilyl)thiophen-3-yl triflate with CsF in the presence of 2,3,4,5-tetraphenylcyclopentadienone affords 4,5,6,7-tetraphenylbenzo[b]thiophene, as it would be expected from the hypothesized generation and trapping of 2-thiophyne. However, a detailed experimental and computational study discards the intermediacy of this elusive 5-membered hetaryne. Instead, a complex mechanism involving the generation of an intermediate ketocarbene, which adds to the cyclopentadienone to give an isolable tricyclic intermediate, followed by thermal rearrangements, is proposedeng© 2021 The Authors. Published by American Chemical Society. This work is licenced under a Creative Commons Attribution 4.0 International licence (https://creativecommons.org/licenses/by/4.0/legalcode)Atribución 4.0 Internacionalhttp://creativecommons.org/licenses/by/4.0/AdductsCentral nervous systemChemical reactionsPrecursorsRearrangementjournal article10.1021/acs.orglett.1c02552open access