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APEX Strategy Represented by Diels–Alder Cycloadditions—New Opportunities for the Syntheses of Functionalised PAHs
Author(s) -
Kurpanik Aneta,
Matussek Marek,
SzafraniecGorol Grażyna,
Filapek Michał,
Lodowski Piotr,
MarcolSzumilas Beata,
Ignasiak Witold,
Małecki Jan Grzegorz,
Machura Barbara,
Małecka Magdalena,
Danikiewicz Witold,
Pawlus Sebastian,
Krompiec Stanisław
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202001327
Subject(s) - cycloaddition , aryne , perylene , chemistry , coronene , diels–alder reaction , computational chemistry , combinatorial chemistry , photochemistry , organic chemistry , molecule , catalysis
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‐diarylbenzo[ghi]perylene, 1,2‐diarylbenzo[ghi]perylenebisimide and 1,2‐disubstituted‐benzo[j]coronene. Namely, the so far unknown cycloaddition of 1,2‐diarylacetylenes into the perylene and perylenebisimide bay regions was used. 1,2‐Disubstituted‐benzo[j]coronenes were obtained via cycloaddition of benzyne into 1,2‐diarylbenzo[ghi]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.