APEX Strategy Represented by Diels–Alder Cycloadditions—New Opportunities for the Syntheses of Functionalised PAHs |
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Authors: | Aneta Kurpanik Dr Marek Matussek Dr Gra?yna Szafraniec-Gorol Dr Micha? Filapek Prof Piotr Lodowski Beata Marcol-Szumilas Witold Ignasiak Jan Grzegorz Ma?ecki Prof Barbara Machura Magdalena Ma?ecka Prof Witold Danikiewicz Prof Sebastian Pawlus Prof Stanis?aw Krompiec |
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Institution: | 1. Institute of Chemistry, Faculty of Science and Technology, University of Silesia, Bankowa 14, 40-007 Katowice, Poland;2. Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland;3. August Che?kowski Institute of Physics &, Silesian Centre for Education and Interdisciplinary Studies, Faculty of Science and Technology, University of Silesia, 75. Pu?ku Piechoty 1A, 41-500 Chorzów, Poland |
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Abstract: | Diels–Alder cycloaddition of various dienophiles to the bay region of polycyclic aromatic hydrocarbons (PAHs) is a particularly effective and useful tool for the modification of the structure of PAHs and thereby their final properties. The Diels–Alder cycloaddition belongs to the single-step annulative π-extension (APEX) reactions and represents the maximum in synthetic efficiency for the constructions of π-extended PAHs including functionalised ones, nanographenes, and π-extended fused heteroarenes. Herein we report new applications of the APEX strategy for the synthesis of derivatives of 1,2-diarylbenzoghi]perylene, 1,2-diarylbenzoghi]perylenebisimide and 1,2-disubstituted-benzoj]coronene. Namely, the so far unknown cycloaddition of 1,2-diarylacetylenes into the perylene and perylenebisimide bay regions was used. 1,2-Disubstituted-benzoj]coronenes were obtained via cycloaddition of benzyne into 1,2-diarylbenzoghi]perylenes by using a new highly effective system for benzyne generation and/or high pressure conditions. Moreover, we report an unprecedented Diels–Alder cycloaddition–cycloaromatisation domino-type reaction between 1,4-(9,9-dialkylfluoren-3-yl)-1,3-butadiynes and perylene. The obtained diaryl-substituted core-extended PAHs were characterised by DFT calculation as well as electrochemical and spectroscopic measurements. |
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Keywords: | APEX cycloaddition cycloaromatization Diel–Alder reaction PAHs perylenes |
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