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

Citation

Tavakkolifard, S and Sekine, K and Reichert, L and Ebrahimi, M and Museridz, K and Michel, E and Rominger, F and Babaahmadi, R and Ariafard, A and Yates, BF and Rudolph, M and Hashmi, ASK, Gold-catalyzed regiospecific annulation of unsymmetrically substituted 1,5-diynes for the precise synthesis of bispentalenes, Chemistry: A European Journal, 25, (52) pp. 12180-12186. ISSN 0947-6539 (2019) [Refereed Article]


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Copyright 2019 the authors. Licensed under Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0) https://creativecommons.org/licenses/by-nc-nd/4.0/

DOI: doi:10.1002/chem.201902381

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.

Item Details

Item Type:Refereed Article
Keywords:gold catalysis, mechanistic study, Density Functional Theory, 1,5-diynes
Research Division:Chemical Sciences
Research Group:Organic chemistry
Research Field:Physical organic chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding knowledge
Objective Field:Expanding knowledge in the chemical sciences
UTAS Author:Babaahmadi, R (Mr Rasool Babaahmadi)
UTAS Author:Ariafard, A (Associate Professor Alireza Ariafard)
UTAS Author:Yates, BF (Professor Brian Yates)
ID Code:137658
Year Published:2019
Funding Support:Australian Research Council (DP180100904)
Web of Science® Times Cited:13
Deposited By:Chemistry
Deposited On:2020-02-25
Last Modified:2021-05-13
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