Gold-Catalyzed Regiospecific Annulation of Unsymmetrically Substituted 1,5-Diynes for the Precise Synthesis of Bispentalenes

Sara Tavakkolifard, Kohei Sekine, Lisa Reichert, Mina Ebrahimi, Ketevan Museridz, Elena Michel, Frank Rominger, Rasool Babaahmadi, Alireza Ariafard, Brian F. Yates, Matthias Rudolph, A. Stephen K. Hashmi

Research output: Contribution to journalArticle

3 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)12180-12186
Number of pages7
JournalChemistry - A European Journal
Volume25
Issue number52
DOIs
Publication statusPublished - Sep 18 2019

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

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    Tavakkolifard, S., Sekine, K., Reichert, L., Ebrahimi, M., Museridz, K., Michel, E., Rominger, F., Babaahmadi, R., Ariafard, A., Yates, B. F., Rudolph, M., & Hashmi, A. S. K. (2019). Gold-Catalyzed Regiospecific Annulation of Unsymmetrically Substituted 1,5-Diynes for the Precise Synthesis of Bispentalenes. Chemistry - A European Journal, 25(52), 12180-12186. https://doi.org/10.1002/chem.201902381