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The Effect of Benzannulation on the Structures, Reactivity and Molecular Dynamics of Indenes, Pentalenes, Azulenes and Related Molecules
The stabilising effect of benzannulation on isoindenes formed in the course of sigmatropic shifts of (C(5)H(5))Fe(CO)(2) or of organo-silyl groups, and on exocyclic allyl intermediates in the course of haptotropic shifts of organometallic fragments over polycyclic skeletons (fluorene, cyclopenta[def...
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Formato: | Online Artículo Texto |
Lenguaje: | English |
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MDPI
2022
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9229948/ https://www.ncbi.nlm.nih.gov/pubmed/35745005 http://dx.doi.org/10.3390/molecules27123882 |
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author | McGlinchey, Michael J. |
author_facet | McGlinchey, Michael J. |
author_sort | McGlinchey, Michael J. |
collection | PubMed |
description | The stabilising effect of benzannulation on isoindenes formed in the course of sigmatropic shifts of (C(5)H(5))Fe(CO)(2) or of organo-silyl groups, and on exocyclic allyl intermediates in the course of haptotropic shifts of organometallic fragments over polycyclic skeletons (fluorene, cyclopenta[def]phenanthrene, syn and anti dibenzpentalenes) is exemplified. This approach led to the development of the first organometallic molecular brake. Benzyne cycloadditions to anthracenes to form triptycenes also led to unexpected or multiple adducts that were characterised by X-ray crystallography. Synthetic routes to the previously elusive benz[cd]azulene system are presented. Finally, the complete mechanism of the stepwise assembly of dispiro- and diindenyltetracenes from fluorenylallenes is presented, whereby every intermediate has been unambiguously structurally characterised. |
format | Online Article Text |
id | pubmed-9229948 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-92299482022-06-25 The Effect of Benzannulation on the Structures, Reactivity and Molecular Dynamics of Indenes, Pentalenes, Azulenes and Related Molecules McGlinchey, Michael J. Molecules Review The stabilising effect of benzannulation on isoindenes formed in the course of sigmatropic shifts of (C(5)H(5))Fe(CO)(2) or of organo-silyl groups, and on exocyclic allyl intermediates in the course of haptotropic shifts of organometallic fragments over polycyclic skeletons (fluorene, cyclopenta[def]phenanthrene, syn and anti dibenzpentalenes) is exemplified. This approach led to the development of the first organometallic molecular brake. Benzyne cycloadditions to anthracenes to form triptycenes also led to unexpected or multiple adducts that were characterised by X-ray crystallography. Synthetic routes to the previously elusive benz[cd]azulene system are presented. Finally, the complete mechanism of the stepwise assembly of dispiro- and diindenyltetracenes from fluorenylallenes is presented, whereby every intermediate has been unambiguously structurally characterised. MDPI 2022-06-17 /pmc/articles/PMC9229948/ /pubmed/35745005 http://dx.doi.org/10.3390/molecules27123882 Text en © 2022 by the author. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Review McGlinchey, Michael J. The Effect of Benzannulation on the Structures, Reactivity and Molecular Dynamics of Indenes, Pentalenes, Azulenes and Related Molecules |
title | The Effect of Benzannulation on the Structures, Reactivity and Molecular Dynamics of Indenes, Pentalenes, Azulenes and Related Molecules |
title_full | The Effect of Benzannulation on the Structures, Reactivity and Molecular Dynamics of Indenes, Pentalenes, Azulenes and Related Molecules |
title_fullStr | The Effect of Benzannulation on the Structures, Reactivity and Molecular Dynamics of Indenes, Pentalenes, Azulenes and Related Molecules |
title_full_unstemmed | The Effect of Benzannulation on the Structures, Reactivity and Molecular Dynamics of Indenes, Pentalenes, Azulenes and Related Molecules |
title_short | The Effect of Benzannulation on the Structures, Reactivity and Molecular Dynamics of Indenes, Pentalenes, Azulenes and Related Molecules |
title_sort | effect of benzannulation on the structures, reactivity and molecular dynamics of indenes, pentalenes, azulenes and related molecules |
topic | Review |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9229948/ https://www.ncbi.nlm.nih.gov/pubmed/35745005 http://dx.doi.org/10.3390/molecules27123882 |
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