RT Journal Article
T1 Aryne‐Based Synthesis of Cyclobutadiene‐Containing Oligoacenes and Related Extended Biphenylene Derivatives
A1 Álvarez Pérez, Berta
A1 Janeiro, Jesús
A1 Cobas Martínez, Agustín
A1 Ortuño Maqueda, Manuel Ángel
A1 Peña Gil, Diego
A1 Guitián Rivera, Enrique
A1 Pérez Meirás, María Dolores
K1 Polycyclic conjugated hydrocarbons
K1 Arynes
K1 Cycloaddition reactions
K1 Biphenylene
K1 Cyclobutadiene containing oligoacenes
AB A previously undescribed aryne derived from a π-extended biphenylene, 2,3-didehydrobenzo[b]biphenylene, has been developed. The participation of this new aryne building block in [4+2] and palladium-catalyzed [2+2+2] cycloaddition reactions has been applied to the synthesis of a variety of polycyclic conjugated hydrocarbons (PCHs) with appealing structures which combine (aromatic) benzene and (antiaromatic) cyclobutadiene (CBD) rings. Among them, a family of unsubstituted (or barely substituted) CBD-oligoacenes has been accessed by iterative Diels-Alder reactions of the new aryne with furans and/or isobenzofurans, followed by deoxygenative aromatization of the resulting epoxy-derivatives. The experimental and computational studies of the newly synthesized PCHs suggest an important degree of electron delocalization along the polycyclic skeleton, more pronounced in the linearly fused derivatives. The computed ACID plots reveal clockwise current density vectors at the peripheral bonds, originating from the σ contributions of the antiaromatic cyclobutadiene rings.
PB Wiley
SN 1615-4150
YR 2024
FD 2024
LK http://hdl.handle.net/10347/33648
UL http://hdl.handle.net/10347/33648
LA eng
NO B. Álvarez, J. Janeiro, A. Cobas, M. A. Ortuño, D. Peña, E. Guitián, D. Pérez, Adv. Synth. Catal. 2024, 366, 961. https://doi.org/10.1002/adsc.202301264
NO Financial support from grants PID2019-110037GB-I00, PID2022-140845OB-C62 and PID2022-139933NB-I00, funded by MCIN/AEI/10.13039/501100011033, the European Union’s Horizon 2020 (FET-Open project SPRING, Grant No. 863098), and ERC Synergy Grant MOLDAM (951519), the Xunta de Galicia (ED431C 2020/22, ED431H 2020/21 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. BA and JJ thank the Agencia Estatal de Investigación for the award of pre-doctoral fellowships (BES-2017-079748 and PRE2020-092897, respectively)
DS Minerva
RD 30 abr 2026