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Mild complexation protocol for chiral Cp(x)Rh and Ir complexes suitable for in situ catalysis
A practical complexation method for chiral cyclopentadienyl (Cp(x)) iridium and rhodium complexes is described. The procedure uses the free Cp(x)H with stable and commercially available rhodium(i) and iridium(i) salts without base or additive. The conditions are mild and do not require the exclusion...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Royal Society of Chemistry
2018
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6346397/ https://www.ncbi.nlm.nih.gov/pubmed/30774871 http://dx.doi.org/10.1039/c8sc04385j |
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author | Audic, B. Wodrich, M. D. Cramer, N. |
author_facet | Audic, B. Wodrich, M. D. Cramer, N. |
author_sort | Audic, B. |
collection | PubMed |
description | A practical complexation method for chiral cyclopentadienyl (Cp(x)) iridium and rhodium complexes is described. The procedure uses the free Cp(x)H with stable and commercially available rhodium(i) and iridium(i) salts without base or additive. The conditions are mild and do not require the exclusion of air and moisture. A salient feature is the suitability for in situ complexations enhancing the user-friendliness of Cp(x) ligands in asymmetric catalysis. DFT-calculations confirm an intramolecular proton abstraction pathway by either the bound acetate or methoxide. Furthermore, the superior facial selectivity of the proton abstraction step enabled the development of TMS-containing trisubstituted Cp(x) ligands which display improved enantioselectivities for the benchmarking dihydroisoquinolone synthesis. |
format | Online Article Text |
id | pubmed-6346397 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2018 |
publisher | Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-63463972019-02-15 Mild complexation protocol for chiral Cp(x)Rh and Ir complexes suitable for in situ catalysis Audic, B. Wodrich, M. D. Cramer, N. Chem Sci Chemistry A practical complexation method for chiral cyclopentadienyl (Cp(x)) iridium and rhodium complexes is described. The procedure uses the free Cp(x)H with stable and commercially available rhodium(i) and iridium(i) salts without base or additive. The conditions are mild and do not require the exclusion of air and moisture. A salient feature is the suitability for in situ complexations enhancing the user-friendliness of Cp(x) ligands in asymmetric catalysis. DFT-calculations confirm an intramolecular proton abstraction pathway by either the bound acetate or methoxide. Furthermore, the superior facial selectivity of the proton abstraction step enabled the development of TMS-containing trisubstituted Cp(x) ligands which display improved enantioselectivities for the benchmarking dihydroisoquinolone synthesis. Royal Society of Chemistry 2018-10-31 /pmc/articles/PMC6346397/ /pubmed/30774871 http://dx.doi.org/10.1039/c8sc04385j Text en This journal is © The Royal Society of Chemistry 2019 http://creativecommons.org/licenses/by-nc/3.0/ This article is freely available. This article is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported Licence (CC BY-NC 3.0) |
spellingShingle | Chemistry Audic, B. Wodrich, M. D. Cramer, N. Mild complexation protocol for chiral Cp(x)Rh and Ir complexes suitable for in situ catalysis |
title | Mild complexation protocol for chiral Cp(x)Rh and Ir complexes suitable for in situ catalysis
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title_full | Mild complexation protocol for chiral Cp(x)Rh and Ir complexes suitable for in situ catalysis
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title_fullStr | Mild complexation protocol for chiral Cp(x)Rh and Ir complexes suitable for in situ catalysis
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title_full_unstemmed | Mild complexation protocol for chiral Cp(x)Rh and Ir complexes suitable for in situ catalysis
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title_short | Mild complexation protocol for chiral Cp(x)Rh and Ir complexes suitable for in situ catalysis
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title_sort | mild complexation protocol for chiral cp(x)rh and ir complexes suitable for in situ catalysis |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6346397/ https://www.ncbi.nlm.nih.gov/pubmed/30774871 http://dx.doi.org/10.1039/c8sc04385j |
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