Gold-catalyzed regiospecific annulation of unsymmetrically substituted 1,5-diynes for the precise synthesis of bispentalenes

• Verfasst von: Tavakkolifard, Sara [VerfasserIn]
• Verfasst von: Sekine, Kohei [VerfasserIn]
• Verfasst von: Museridze, Ketevan [VerfasserIn]
• Verfasst von: Michel, Elena [VerfasserIn]
• Verfasst von: Rominger, Frank [VerfasserIn]
• Verfasst von: Rudolph, Matthias [VerfasserIn]
• Verfasst von: Hashmi, A. Stephen K. [VerfasserIn]
• Titel: Gold-catalyzed regiospecific annulation of unsymmetrically substituted 1,5-diynes for the precise synthesis of bispentalenes
• Verf.angabe: Sara Tavakkolifard, Kohei Sekine, Lisa Reichert, Mina Ebrahimi, Ketevan Museridz, Elena Michel, Frank Rominger, Rasool Babaahmadi, Alireza Ariafard, Brian F. Yates, Matthias Rudolph, and A. Stephen K. Hashmi
• E-Jahr: 2019
• Jahr: July 16, 2019
• Umfang: 7 S.
• Fussnoten: Version of record online: August 28, 2019 ; Gesehen am 07.11.2019
• Titel Quelle: Enthalten in: Chemistry - a European journal
• Ort Quelle: Weinheim : Wiley-VCH, 1995
• Jahr Quelle: 2019
• Band/Heft Quelle: 25(2019), 52, Seite 12180-12186
• ISSN Quelle: 1521-3765
• DOI: doi:10.1002/chem.201902381
• Datenträger: Online-Ressource
• Sprache: eng
• Sach-SW: gold
• Sach-SW: homogeneous catalysis
• Sach-SW: pentalenes
• Sach-SW: polycyclic aromatic hydrocarbons
• Sach-SW: regiospecific
• K10plus-PPN: 1681392569
• K10plus-PPN:
  Universitätsbibliothek
• Lokale URL UB: Zum Volltext

Abstract

Precise control of the selectivity in organic synthesis is important to access the desired molecules. We demonstrate a regiospecific annulation of unsymmetrically substituted 1,2-di(arylethynyl)benzene derivatives for a geometry-controlled synthesis of linear bispentalenes, which is one of the promising structures for material science. A gold-catalyzed annulation of unsymmetrically substituted 1,2-di(arylethynyl)benzene could produce two isomeric pentalenes, but both electronic and steric effects on the aromatics at the terminal position of the alkyne prove to be crucial for the selectivity; especially a regiospecific annulation was achieved with sterically blocked substituents; namely, 2,4,6-trimetyl benzene or 2,4-dimethyl benzene. This approach enables the geometrically controlled synthesis of linear bispentalenes from 1,2,4,5-tetraethynylbenzene or 2,3,6,7-tetraethynylnaphthalene. Moreover, the annulation of a series of tetraynes with a different substitution pattern regioselectively provided the bispentalene scaffolds. A computational study revealed that this is the result of a kinetic control induced by the bulky NHC ligands.