RT Journal Article
T1 K+ -Mediated vs Pd-Catalyzed Cyclotrimerization of 9,10-Didehydrotribenzo[8]annulene (TribenzoCOTyne): Stereodivergent Access to (α,α,α)- and (α,α,β)-Fragments of Cubic Graphite
A1 Bello García, Jesús
A1 Varela Carrete, Jesús Ángel
A1 Saá Rodríguez, Carlos
K1 Benzo[8]annulenes
K1 COT conformers
K1 COTynes (didehydro[8]annulenes
K1 Cubic graphite
K1 Cyclotrimerizations
AB A remarkable stereodivergent cyclotrimeriza-tion of 9,10-didehydrotribenzo[8]annulene (tribenzoCO-Tyne) to the corresponding (α,α,α)- and (α,α,β)-benzo-fused derivatives has been developed by controlling the reaction conditions. While the K+ -mediated cyclotrime-rization afforded the (α,α,α) stereoisomer, using Pd as a catalyst resulted in the (α,α,β)-derivative. Both stereo-isomers were evidenced by spectroscopic data and crystal X-Ray analysis. The (α,α,α) stereoisomer is a fragment of cubic graphite (CG), an elusive 3D carbon allotrope that contains carbon cages, since all of its sixty carbons are part of the structure of CG, and 36 constitute a part of the C48 molecular cage of CG. Experimental and computational mechanistic studies revealed that the potassium ion would play a key role as a template to favor the formation of the (α,α,α) stereo-isome
PB Wiley
SN 1433-7851
YR 2024
FD 2024
LK https://hdl.handle.net/10347/38245
UL https://hdl.handle.net/10347/38245
LA eng
NO Bello-García, J., Varela, J. A., Saá, C. (2024). K+‐Mediated vs Pd‐Catalyzed Cyclotrimerization of 9,10‐Didehydrotribenzo[8]annulene (TribenzoCOTyne): Stereodivergent Access to (α,α,α)‐ and (α,α,β)‐Fragments of Cubic Graphite. "Angewandte Chemie International Edition", vol. 63, e202414017
NO We acknowledge financial support from MICIN (projects PID2020-118048GB􀀀 I00/AEI/10.13039/501100011033, PID2023-151279NB􀀀 I00 and ORFEO-CINQA network RED2022-134287-T), the Xunta de Galicia (project ED431 C 2022/27 and Centro singular de investigación deGalicia accreditation 2023–2027, ED431G 2023/03) and the European Union (European Regional Development Fund – ERDF). We are also grateful to the CESGA (Xunta de Galicia) for computational time. J. B􀀀 G. thanks MICIN for a predoctoral contract
DS Minerva
RD 27 abr 2026