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Optical Resolution of Carboxylic Acid Derivatives of Homoleptic Cyclometalated Iridium(III) Complexes via Diastereomers Formed with Chiral Auxiliaries
[Image: see text] We report on a facile method for the optical resolution of cyclometalated iridium(III) (Ir(III)) complexes via diastereomers formed with chiral auxiliaries. The racemic carboxylic acids of Ir(III) complexes (fac-4 (fac-Ir(ppyCO(2)H)(3) (ppy: 2-phenylpyridine)), fac-6 (fac-Ir(tpyCO(...
Autores principales: | , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2023
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10369494/ https://www.ncbi.nlm.nih.gov/pubmed/37432912 http://dx.doi.org/10.1021/acs.inorgchem.3c00685 |
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author | Kanbe, Azusa Yokoi, Kenta Yamada, Yasuyuki Tsurui, Makoto Kitagawa, Yuichi Hasegawa, Yasuchika Ogata, Daiji Yuasa, Junpei Aoki, Shin |
author_facet | Kanbe, Azusa Yokoi, Kenta Yamada, Yasuyuki Tsurui, Makoto Kitagawa, Yuichi Hasegawa, Yasuchika Ogata, Daiji Yuasa, Junpei Aoki, Shin |
author_sort | Kanbe, Azusa |
collection | PubMed |
description | [Image: see text] We report on a facile method for the optical resolution of cyclometalated iridium(III) (Ir(III)) complexes via diastereomers formed with chiral auxiliaries. The racemic carboxylic acids of Ir(III) complexes (fac-4 (fac-Ir(ppyCO(2)H)(3) (ppy: 2-phenylpyridine)), fac-6 (fac-Ir(tpyCO(2)H)(3) (tpy: 2-(4′-tolyl)pyridine)), and fac-13 (fac-Ir(mpiqCO(2)H)(3) (mpiq: 1-(4′-methylphenyl)isoquinoline))) were converted into the diastereomers, Δ- and Λ-forms of fac-9 (from fac-6), fac-10 (from fac-4), fac-11 (from fac-6), and fac-14 (from fac-13), respectively, by the condensation with (1R,2R)-1,2-diaminocyclohexane or (1R,2R)-2-aminocyclohexanol. The resulting diastereomers were separated by HPLC (with a nonchiral column) or silica gel column chromatography, and their absolute stereochemistry was determined by X-ray single-crystal structure analysis and CD (circular dichroism) spectra. Spectra of all diastereomers of the Ir(III) complexes are reported. Hydrolysis of the ester moieties of Δ- and Λ-forms of fac-10, fac-11, and fac-14 gave both enantiomers of the corresponding carboxylic acid derivatives in the optically pure forms, Δ-fac and Λ-fac-4, -6, and -13, respectively. |
format | Online Article Text |
id | pubmed-10369494 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-103694942023-07-27 Optical Resolution of Carboxylic Acid Derivatives of Homoleptic Cyclometalated Iridium(III) Complexes via Diastereomers Formed with Chiral Auxiliaries Kanbe, Azusa Yokoi, Kenta Yamada, Yasuyuki Tsurui, Makoto Kitagawa, Yuichi Hasegawa, Yasuchika Ogata, Daiji Yuasa, Junpei Aoki, Shin Inorg Chem [Image: see text] We report on a facile method for the optical resolution of cyclometalated iridium(III) (Ir(III)) complexes via diastereomers formed with chiral auxiliaries. The racemic carboxylic acids of Ir(III) complexes (fac-4 (fac-Ir(ppyCO(2)H)(3) (ppy: 2-phenylpyridine)), fac-6 (fac-Ir(tpyCO(2)H)(3) (tpy: 2-(4′-tolyl)pyridine)), and fac-13 (fac-Ir(mpiqCO(2)H)(3) (mpiq: 1-(4′-methylphenyl)isoquinoline))) were converted into the diastereomers, Δ- and Λ-forms of fac-9 (from fac-6), fac-10 (from fac-4), fac-11 (from fac-6), and fac-14 (from fac-13), respectively, by the condensation with (1R,2R)-1,2-diaminocyclohexane or (1R,2R)-2-aminocyclohexanol. The resulting diastereomers were separated by HPLC (with a nonchiral column) or silica gel column chromatography, and their absolute stereochemistry was determined by X-ray single-crystal structure analysis and CD (circular dichroism) spectra. Spectra of all diastereomers of the Ir(III) complexes are reported. Hydrolysis of the ester moieties of Δ- and Λ-forms of fac-10, fac-11, and fac-14 gave both enantiomers of the corresponding carboxylic acid derivatives in the optically pure forms, Δ-fac and Λ-fac-4, -6, and -13, respectively. American Chemical Society 2023-07-11 /pmc/articles/PMC10369494/ /pubmed/37432912 http://dx.doi.org/10.1021/acs.inorgchem.3c00685 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Kanbe, Azusa Yokoi, Kenta Yamada, Yasuyuki Tsurui, Makoto Kitagawa, Yuichi Hasegawa, Yasuchika Ogata, Daiji Yuasa, Junpei Aoki, Shin Optical Resolution of Carboxylic Acid Derivatives of Homoleptic Cyclometalated Iridium(III) Complexes via Diastereomers Formed with Chiral Auxiliaries |
title | Optical Resolution
of Carboxylic Acid Derivatives
of Homoleptic Cyclometalated Iridium(III) Complexes via Diastereomers
Formed with Chiral Auxiliaries |
title_full | Optical Resolution
of Carboxylic Acid Derivatives
of Homoleptic Cyclometalated Iridium(III) Complexes via Diastereomers
Formed with Chiral Auxiliaries |
title_fullStr | Optical Resolution
of Carboxylic Acid Derivatives
of Homoleptic Cyclometalated Iridium(III) Complexes via Diastereomers
Formed with Chiral Auxiliaries |
title_full_unstemmed | Optical Resolution
of Carboxylic Acid Derivatives
of Homoleptic Cyclometalated Iridium(III) Complexes via Diastereomers
Formed with Chiral Auxiliaries |
title_short | Optical Resolution
of Carboxylic Acid Derivatives
of Homoleptic Cyclometalated Iridium(III) Complexes via Diastereomers
Formed with Chiral Auxiliaries |
title_sort | optical resolution
of carboxylic acid derivatives
of homoleptic cyclometalated iridium(iii) complexes via diastereomers
formed with chiral auxiliaries |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10369494/ https://www.ncbi.nlm.nih.gov/pubmed/37432912 http://dx.doi.org/10.1021/acs.inorgchem.3c00685 |
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