Diels-Alder Reactivity of Triisopropylsilyl Ethynyl Substituted Acenes.

Autor: Jester F; Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany., Kaczun T; Interdisciplinary Center for Scientific Computing, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 205, 69120, Heidelberg, Germany., Maier S; Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany., Meiners P; Interdisciplinary Center for Scientific Computing, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 205, 69120, Heidelberg, Germany., Weigold S; Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany., Rominger F; Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany., Dreuw A; Interdisciplinary Center for Scientific Computing, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 205, 69120, Heidelberg, Germany., Freudenberg J; Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany., Bunz UHF; Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2024 Oct 17, pp. e202403522. Date of Electronic Publication: 2024 Oct 17.
DOI: 10.1002/chem.202403522
Abstrakt: We investigated the Diels-Alder reaction of 6,13-bis(triisopropylsilylethynyl)pentacene (1) with small dienophiles such as (bridged) dihydronaphthalenes/cyclohexenes that yielded adducts at the central ring, the other dienophiles predominantly or exclusively attacked the unsubstituted off-center ring. The difference in regioselectivity was investigated by DFT calculations. Apart from dispersion interactions, it is due to the steric demand of the dienophiles, which need to fit in between the silylethynyl substituents to react at the central ring. Epoxynaphthalene adducts of 1 as well as its anthracene and tetracene congeners were deoxygenated, easily furnishing triarenobarrelenes with TIPS-ethynyl substituents at the bridgeheads, attractive building blocks for porous solids and higher acene-based trimers.
(© 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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