A new fundamental type of conformational isomerism

Canfield, PJ; Blake, IM; Cai, ZL; Luck, IJ; Krausz, E; Kobayashi, R; Reimers, JR; Crossley, MJ

A new fundamental type of conformational isomerism

Canfield, PJ Blake, IM Cai, ZL Luck, IJ Krausz, E Kobayashi, R Reimers, JR

Crossley, MJ

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Publication Type:: Journal Article
Citation:: Nature Chemistry, 2018, 10 (6), pp. 615 - 624
Issue Date:: 2018-06-01

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Field	Value	Language
dc.contributor.author	Canfield, PJ	en_US
dc.contributor.author	Blake, IM	en_US
dc.contributor.author	Cai, ZL	en_US
dc.contributor.author	Luck, IJ	en_US
dc.contributor.author	Krausz, E	en_US
dc.contributor.author	Kobayashi, R	en_US
dc.contributor.author	Reimers, JR https://orcid.org/0000-0001-5157-7422	en_US
dc.contributor.author	Crossley, MJ	en_US
dc.date.available	2020-05-25T19:07:32Z
dc.date.issued	2018-06-01	en_US
dc.identifier.citation	Nature Chemistry, 2018, 10 (6), pp. 615 - 624	en_US
dc.identifier.issn	1755-4330	en_US
dc.identifier.uri	http://hdl.handle.net/10453/125589
dc.description.abstract	© 2018 The Author(s). Isomerism is a fundamental chemical concept, reflecting the fact that the arrangement of atoms in a molecular entity has a profound influence on its chemical and physical properties. Here we describe a previously unclassified fundamental form of conformational isomerism through four resolved stereoisomers of a transoid (BF)O(BF)-quinoxalinoporphyrin. These comprise two pairs of enantiomers that manifest structural relationships not describable within existing IUPAC nomenclature and terminology. They undergo thermal diastereomeric interconversion over a barrier of 104 ± 2 kJ mol-1, which we term 'akamptisomerization'. Feasible interconversion processes between conceivable synthesis products and reaction intermediates were mapped out by density functional theory calculations, identifying bond-angle inversion (BAI) at a singly bonded atom as the reaction mechanism. We also introduce the necessary BAI stereodescriptors parvo and amplo. Based on an extended polytope formalism of molecular structure and stereoisomerization, BAI-driven akamptisomerization is shown to be the final fundamental type of conformational isomerization.	en_US
dc.relation	http://purl.org/au-research/grants/arc/DP150103137
dc.relation.ispartof	Nature Chemistry	en_US
dc.relation.isbasedon	10.1038/s41557-018-0043-6	en_US
dc.subject.classification	Organic Chemistry	en_US
dc.title	A new fundamental type of conformational isomerism	en_US
dc.type	Journal Article
utslib.citation.volume	6	en_US
utslib.citation.volume	10	en_US
utslib.for	0306 Physical Chemistry (incl. Structural)	en_US
utslib.for	03 Chemical Sciences	en_US
pubs.embargo.period	Not known	en_US
pubs.organisational-group	/University of Technology Sydney
pubs.organisational-group	/University of Technology Sydney/Faculty of Science
pubs.organisational-group	/University of Technology Sydney/Faculty of Science/School of Mathematical and Physical Sciences
utslib.copyright.status	open_access
pubs.issue	6	en_US
pubs.publication-status	Published	en_US
pubs.volume	10	en_US

Abstract:

© 2018 The Author(s). Isomerism is a fundamental chemical concept, reflecting the fact that the arrangement of atoms in a molecular entity has a profound influence on its chemical and physical properties. Here we describe a previously unclassified fundamental form of conformational isomerism through four resolved stereoisomers of a transoid (BF)O(BF)-quinoxalinoporphyrin. These comprise two pairs of enantiomers that manifest structural relationships not describable within existing IUPAC nomenclature and terminology. They undergo thermal diastereomeric interconversion over a barrier of 104 ± 2 kJ mol-1, which we term 'akamptisomerization'. Feasible interconversion processes between conceivable synthesis products and reaction intermediates were mapped out by density functional theory calculations, identifying bond-angle inversion (BAI) at a singly bonded atom as the reaction mechanism. We also introduce the necessary BAI stereodescriptors parvo and amplo. Based on an extended polytope formalism of molecular structure and stereoisomerization, BAI-driven akamptisomerization is shown to be the final fundamental type of conformational isomerization.

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http://hdl.handle.net/10453/125589