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

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Tavakkolifard, S, Sekine, K, Reichert, L, Ebrahimi, M, Museridz, K, Michel, E, Rominger, F, Babaahmadi, R, Ariafard, A ORCID: 0000-0003-2383-6380, Yates, BF ORCID: 0000-0001-9663-3301, Rudolph, M and Hashmi, ASK 2019 , 'Gold-catalyzed regiospecific annulation of unsymmetrically substituted 1,5-diynes for the precise synthesis of bispentalenes' , Chemistry: A European Journal, vol. 25, no. 52 , pp. 12180-12186 , doi: 10.1002/chem.201902381.

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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 Type: Article
Authors/Creators: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
Keywords: gold catalysis, mechanistic study, Density Functional Theory, 1,5-diynes
Journal or Publication Title: Chemistry: A European Journal
Publisher: Wiley-V C H Verlag Gmbh
ISSN: 0947-6539
DOI / ID Number: 10.1002/chem.201902381
Copyright Information:

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/

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