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Trityl-Containing Alcohols—An Efficient Chirality Transmission Process from Inductor to the Stereodynamic Propeller and their Solid-State Structural Diversity
The cascade process of a dynamic chirality transmission from the permanent chirality center to the stereodynamic triphenylmethyl group has been studied for series of optically active trityl derivatives. The structural analysis, carried out with the use of complementary methods, enabled us to determi...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7036902/ https://www.ncbi.nlm.nih.gov/pubmed/32041345 http://dx.doi.org/10.3390/molecules25030707 |
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author | Górczyńska, Sylwia Brzdonkiewicz, Aleksandra Jelecki, Maciej Czapik, Agnieszka Stasiak, Bartosz Kwit, Marcin |
author_facet | Górczyńska, Sylwia Brzdonkiewicz, Aleksandra Jelecki, Maciej Czapik, Agnieszka Stasiak, Bartosz Kwit, Marcin |
author_sort | Górczyńska, Sylwia |
collection | PubMed |
description | The cascade process of a dynamic chirality transmission from the permanent chirality center to the stereodynamic triphenylmethyl group has been studied for series of optically active trityl derivatives. The structural analysis, carried out with the use of complementary methods, enabled us to determine the mechanism of chirality transfer. The process of chirality transmission involves a set of weak but complementary electrostatic interactions. The induction of helicity in a trityl propeller is revealed by rising non-zero cotton effects in the area of trityl UV-absorption. The presence of an additional stereogenic center in close proximity to the trityl-containing stereogenic center significantly affects the sign and, to a lesser extent, magnitude of the respective cotton effects. Despite the bulkiness of the trityl, in the crystalline phase, the molecules under study strictly fill the space. In the crystal, molecules form aggregates stabilized by OH•••O hydrogen bonds. However, the presence of two trityl groups precludes formation of OH•••O hydrogen bonding. Additionally, the trityl group seems to be responsible for the formation of the solid solutions by e.g., racemates of trans- and cis-2-tritylcyclohexanol. Therefore, the trityl group acts as a supramolecular protective group, which in turn can be used in the crystal engineering. |
format | Online Article Text |
id | pubmed-7036902 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-70369022020-03-11 Trityl-Containing Alcohols—An Efficient Chirality Transmission Process from Inductor to the Stereodynamic Propeller and their Solid-State Structural Diversity Górczyńska, Sylwia Brzdonkiewicz, Aleksandra Jelecki, Maciej Czapik, Agnieszka Stasiak, Bartosz Kwit, Marcin Molecules Article The cascade process of a dynamic chirality transmission from the permanent chirality center to the stereodynamic triphenylmethyl group has been studied for series of optically active trityl derivatives. The structural analysis, carried out with the use of complementary methods, enabled us to determine the mechanism of chirality transfer. The process of chirality transmission involves a set of weak but complementary electrostatic interactions. The induction of helicity in a trityl propeller is revealed by rising non-zero cotton effects in the area of trityl UV-absorption. The presence of an additional stereogenic center in close proximity to the trityl-containing stereogenic center significantly affects the sign and, to a lesser extent, magnitude of the respective cotton effects. Despite the bulkiness of the trityl, in the crystalline phase, the molecules under study strictly fill the space. In the crystal, molecules form aggregates stabilized by OH•••O hydrogen bonds. However, the presence of two trityl groups precludes formation of OH•••O hydrogen bonding. Additionally, the trityl group seems to be responsible for the formation of the solid solutions by e.g., racemates of trans- and cis-2-tritylcyclohexanol. Therefore, the trityl group acts as a supramolecular protective group, which in turn can be used in the crystal engineering. MDPI 2020-02-06 /pmc/articles/PMC7036902/ /pubmed/32041345 http://dx.doi.org/10.3390/molecules25030707 Text en © 2020 by the authors. 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 (http://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Article Górczyńska, Sylwia Brzdonkiewicz, Aleksandra Jelecki, Maciej Czapik, Agnieszka Stasiak, Bartosz Kwit, Marcin Trityl-Containing Alcohols—An Efficient Chirality Transmission Process from Inductor to the Stereodynamic Propeller and their Solid-State Structural Diversity |
title | Trityl-Containing Alcohols—An Efficient Chirality Transmission Process from Inductor to the Stereodynamic Propeller and their Solid-State Structural Diversity |
title_full | Trityl-Containing Alcohols—An Efficient Chirality Transmission Process from Inductor to the Stereodynamic Propeller and their Solid-State Structural Diversity |
title_fullStr | Trityl-Containing Alcohols—An Efficient Chirality Transmission Process from Inductor to the Stereodynamic Propeller and their Solid-State Structural Diversity |
title_full_unstemmed | Trityl-Containing Alcohols—An Efficient Chirality Transmission Process from Inductor to the Stereodynamic Propeller and their Solid-State Structural Diversity |
title_short | Trityl-Containing Alcohols—An Efficient Chirality Transmission Process from Inductor to the Stereodynamic Propeller and their Solid-State Structural Diversity |
title_sort | trityl-containing alcohols—an efficient chirality transmission process from inductor to the stereodynamic propeller and their solid-state structural diversity |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7036902/ https://www.ncbi.nlm.nih.gov/pubmed/32041345 http://dx.doi.org/10.3390/molecules25030707 |
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