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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...

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Autores principales: Audic, B., Wodrich, M. D., Cramer, N.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2018
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.
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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
title_full Mild complexation protocol for chiral Cp(x)Rh and Ir complexes suitable for in situ catalysis
title_fullStr Mild complexation protocol for chiral Cp(x)Rh and Ir complexes suitable for in situ catalysis
title_full_unstemmed Mild complexation protocol for chiral Cp(x)Rh and Ir complexes suitable for in situ catalysis
title_short Mild complexation protocol for chiral Cp(x)Rh and Ir complexes suitable for in situ catalysis
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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