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Hypervalent Iodine(III) Compounds as Biaxial Halogen Bond Donors

[Image: see text] “Hypervalent” iodine(III) derivatives have been established as powerful reagents in organic transformations, but so far only a handful of studies have addressed their potential use as halogen-bonding noncovalent Lewis acids. In contrast to “classical” halogen-bond donors based on i...

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Autores principales: Heinen, Flemming, Engelage, Elric, Cramer, Christopher J., Huber, Stefan M.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2020
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7252947/
https://www.ncbi.nlm.nih.gov/pubmed/32286829
http://dx.doi.org/10.1021/jacs.9b13309
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author Heinen, Flemming
Engelage, Elric
Cramer, Christopher J.
Huber, Stefan M.
author_facet Heinen, Flemming
Engelage, Elric
Cramer, Christopher J.
Huber, Stefan M.
author_sort Heinen, Flemming
collection PubMed
description [Image: see text] “Hypervalent” iodine(III) derivatives have been established as powerful reagents in organic transformations, but so far only a handful of studies have addressed their potential use as halogen-bonding noncovalent Lewis acids. In contrast to “classical” halogen-bond donors based on iodine(I) compounds, iodine(III) salts feature two directional electrophilic axes perpendicular to each other. Herein we present the first systematic investigation on biaxial binding to such Lewis acids in solution. To this end, hindered and unhindered iodolium species were titrated with various substrates, including diesters and diamides, via (1)H NMR spectroscopy and isothermal titration calorimetry. Clear evidence for biaxial binding was obtained in two model systems, and the association strengths increased by 2 orders of magnitude. These findings were corroborated by density functional theory calculations (which reproduced the trend well but underestimated the absolute binding constants) and a cocrystal featuring biaxial coordination of a diamide to the unhindered iodolium compound.
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spelling pubmed-72529472020-05-29 Hypervalent Iodine(III) Compounds as Biaxial Halogen Bond Donors Heinen, Flemming Engelage, Elric Cramer, Christopher J. Huber, Stefan M. J Am Chem Soc [Image: see text] “Hypervalent” iodine(III) derivatives have been established as powerful reagents in organic transformations, but so far only a handful of studies have addressed their potential use as halogen-bonding noncovalent Lewis acids. In contrast to “classical” halogen-bond donors based on iodine(I) compounds, iodine(III) salts feature two directional electrophilic axes perpendicular to each other. Herein we present the first systematic investigation on biaxial binding to such Lewis acids in solution. To this end, hindered and unhindered iodolium species were titrated with various substrates, including diesters and diamides, via (1)H NMR spectroscopy and isothermal titration calorimetry. Clear evidence for biaxial binding was obtained in two model systems, and the association strengths increased by 2 orders of magnitude. These findings were corroborated by density functional theory calculations (which reproduced the trend well but underestimated the absolute binding constants) and a cocrystal featuring biaxial coordination of a diamide to the unhindered iodolium compound. American Chemical Society 2020-04-14 2020-05-13 /pmc/articles/PMC7252947/ /pubmed/32286829 http://dx.doi.org/10.1021/jacs.9b13309 Text en Copyright © 2020 American Chemical Society This is an open access article published under a Creative Commons Non-Commercial No Derivative Works (CC-BY-NC-ND) Attribution License (http://pubs.acs.org/page/policy/authorchoice_ccbyncnd_termsofuse.html) , which permits copying and redistribution of the article, and creation of adaptations, all for non-commercial purposes.
spellingShingle Heinen, Flemming
Engelage, Elric
Cramer, Christopher J.
Huber, Stefan M.
Hypervalent Iodine(III) Compounds as Biaxial Halogen Bond Donors
title Hypervalent Iodine(III) Compounds as Biaxial Halogen Bond Donors
title_full Hypervalent Iodine(III) Compounds as Biaxial Halogen Bond Donors
title_fullStr Hypervalent Iodine(III) Compounds as Biaxial Halogen Bond Donors
title_full_unstemmed Hypervalent Iodine(III) Compounds as Biaxial Halogen Bond Donors
title_short Hypervalent Iodine(III) Compounds as Biaxial Halogen Bond Donors
title_sort hypervalent iodine(iii) compounds as biaxial halogen bond donors
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7252947/
https://www.ncbi.nlm.nih.gov/pubmed/32286829
http://dx.doi.org/10.1021/jacs.9b13309
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