RT Journal Article
T1 Toward 2-Thiophyne: ketocarbene versus hetaryne intermediates from 2-(Trimethylsilyl)thiophen-3-yl Triflate
A1 Pozo Míguez, Iago
A1 Cobas Martínez, Agustín
A1 Peña Gil, Diego
A1 Guitián Rivera, Enrique
A1 Pérez Meirás, María Dolores
K1 Adducts
K1 Central nervous system
K1 Chemical reactions
K1 Precursors
K1 Rearrangement
AB The 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 proposed
PB ACS Publications
SN 1523-7060
YR 2021
FD 2021
LK http://hdl.handle.net/10347/29041
UL http://hdl.handle.net/10347/29041
LA eng
NO Org. Lett. 2021, 23, 7376−7380. https://doi.org/10.1021/acs.orglett.1c02552
NO Financial support from the Spanish Agencia Estatal de Investigación (Nos. PID2019-110037GB-I00 and PCI2019-111933-2), the European Union’s Horizon 2020 (FET-Open project, Grant No. 863098), the Xunta de Galicia (No. ED431C 2020/22 and Centro Singular de Investigación de Galicia accreditation 2019-2022, ED431G 2019/03) and the European Union (European Regional Development Fund-ERDF, is gratefully acknowledged. The authors thank the Centro de Supercomputación de Galicia (CESGA) for generous allocation of computer time. I.P. thanks Xunta de Galicia and the European Union (European Social Fund, ESF) for the award of a predoctoral fellowship
DS Minerva
RD 24 abr 2026