Computational Insight into the Rope-Skipping Isomerization of Diarylether Cyclophanes

The restricted rotation of chemical bonds may lead to the formation of stable, conformationally chiral molecules. While the asymmetry in chiral molecules is generally observed in the presence of one or more stereocenters, asymmetry exhibited by conformational chirality in compounds lacking stereocen...

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Autores principales:	Thomas J. Summers, Hrishikesh Tupkar, Tyler M. Ozvat, Zoë Tregillus, Kenneth A. Miller, Nathan J. DeYonker
Formato:	article
Lenguaje:	EN
Publicado:	MDPI AG 2021
Materias:	isomerization computational diarylether cyclophanes atropisomerism Mathematics QA1-939
Acceso en línea:	https://doaj.org/article/ed1c3dfcaf4d4f67872771aa4e5c9164
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spelling	oai:doaj.org-article:ed1c3dfcaf4d4f67872771aa4e5c91642021-11-25T19:06:57ZComputational Insight into the Rope-Skipping Isomerization of Diarylether Cyclophanes10.3390/sym131121272073-8994https://doaj.org/article/ed1c3dfcaf4d4f67872771aa4e5c91642021-11-01T00:00:00Zhttps://www.mdpi.com/2073-8994/13/11/2127https://doaj.org/toc/2073-8994The restricted rotation of chemical bonds may lead to the formation of stable, conformationally chiral molecules. While the asymmetry in chiral molecules is generally observed in the presence of one or more stereocenters, asymmetry exhibited by conformational chirality in compounds lacking stereocenters, called atropisomerism, depends on structural and temperature factors that are still not fully understood. This atropisomerism is observed in natural diarylether heptanoids where the length of the intramolecular tether constrains the compounds to isolable enantiomers at room temperature. In this work, we examine the impact tether length has on the activation free energies to isomerization of a diarylether cyclophane substructure with a tether ranging from 6 to 14 carbons. Racemization activation energies are observed to decay from 48 kcal/mol for a 7-carbon tether to 9.2 kcal/mol for a 14-carbon tether. Synthetic efforts to experimentally test these constraints are also presented. This work will likely guide the design and synthesis of novel asymmetric cyclophanes that will be of interest in the catalysis community given the importance of atropisomeric ligands in the field of asymmetric catalysis.Thomas J. SummersHrishikesh TupkarTyler M. OzvatZoë TregillusKenneth A. MillerNathan J. DeYonkerMDPI AGarticleisomerizationcomputationaldiarylether cyclophanesatropisomerismMathematicsQA1-939ENSymmetry, Vol 13, Iss 2127, p 2127 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	isomerization computational diarylether cyclophanes atropisomerism Mathematics QA1-939
spellingShingle	isomerization computational diarylether cyclophanes atropisomerism Mathematics QA1-939 Thomas J. Summers Hrishikesh Tupkar Tyler M. Ozvat Zoë Tregillus Kenneth A. Miller Nathan J. DeYonker Computational Insight into the Rope-Skipping Isomerization of Diarylether Cyclophanes
description	The restricted rotation of chemical bonds may lead to the formation of stable, conformationally chiral molecules. While the asymmetry in chiral molecules is generally observed in the presence of one or more stereocenters, asymmetry exhibited by conformational chirality in compounds lacking stereocenters, called atropisomerism, depends on structural and temperature factors that are still not fully understood. This atropisomerism is observed in natural diarylether heptanoids where the length of the intramolecular tether constrains the compounds to isolable enantiomers at room temperature. In this work, we examine the impact tether length has on the activation free energies to isomerization of a diarylether cyclophane substructure with a tether ranging from 6 to 14 carbons. Racemization activation energies are observed to decay from 48 kcal/mol for a 7-carbon tether to 9.2 kcal/mol for a 14-carbon tether. Synthetic efforts to experimentally test these constraints are also presented. This work will likely guide the design and synthesis of novel asymmetric cyclophanes that will be of interest in the catalysis community given the importance of atropisomeric ligands in the field of asymmetric catalysis.
format	article
author	Thomas J. Summers Hrishikesh Tupkar Tyler M. Ozvat Zoë Tregillus Kenneth A. Miller Nathan J. DeYonker
author_facet	Thomas J. Summers Hrishikesh Tupkar Tyler M. Ozvat Zoë Tregillus Kenneth A. Miller Nathan J. DeYonker
author_sort	Thomas J. Summers
title	Computational Insight into the Rope-Skipping Isomerization of Diarylether Cyclophanes
title_short	Computational Insight into the Rope-Skipping Isomerization of Diarylether Cyclophanes
title_full	Computational Insight into the Rope-Skipping Isomerization of Diarylether Cyclophanes
title_fullStr	Computational Insight into the Rope-Skipping Isomerization of Diarylether Cyclophanes
title_full_unstemmed	Computational Insight into the Rope-Skipping Isomerization of Diarylether Cyclophanes
title_sort	computational insight into the rope-skipping isomerization of diarylether cyclophanes
publisher	MDPI AG
publishDate	2021
url	https://doaj.org/article/ed1c3dfcaf4d4f67872771aa4e5c9164
work_keys_str_mv	AT thomasjsummers computationalinsightintotheropeskippingisomerizationofdiarylethercyclophanes AT hrishikeshtupkar computationalinsightintotheropeskippingisomerizationofdiarylethercyclophanes AT tylermozvat computationalinsightintotheropeskippingisomerizationofdiarylethercyclophanes AT zoetregillus computationalinsightintotheropeskippingisomerizationofdiarylethercyclophanes AT kennethamiller computationalinsightintotheropeskippingisomerizationofdiarylethercyclophanes AT nathanjdeyonker computationalinsightintotheropeskippingisomerizationofdiarylethercyclophanes
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Computational Insight into the Rope-Skipping Isomerization of Diarylether Cyclophanes

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