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The First Crystal Structure of a Reactive Dirhodium Carbene Complex and a Versatile Method for the Preparation of Gold Carbenes by Rhodium‐to‐Gold Transmetalation
The dirhodium carbene derived from bis(4‐methoxyphenyl)diazomethane and [Rh(tpa)(4)]⋅CH(2)Cl(2) (tpa=triphenylacetate) was characterized by UV, IR, and NMR spectroscopy, HRMS, as well as by X‐ray diffraction. The isolated complex exhibits prototypical rhodium carbene reactivity in that it cyclopropa...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
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WILEY‐VCH Verlag
2015
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4832834/ https://www.ncbi.nlm.nih.gov/pubmed/26534892 http://dx.doi.org/10.1002/anie.201506902 |
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author | Werlé, Christophe Goddard, Richard Fürstner, Alois |
author_facet | Werlé, Christophe Goddard, Richard Fürstner, Alois |
author_sort | Werlé, Christophe |
collection | PubMed |
description | The dirhodium carbene derived from bis(4‐methoxyphenyl)diazomethane and [Rh(tpa)(4)]⋅CH(2)Cl(2) (tpa=triphenylacetate) was characterized by UV, IR, and NMR spectroscopy, HRMS, as well as by X‐ray diffraction. The isolated complex exhibits prototypical rhodium carbene reactivity in that it cyclopropanates 4‐methoxystyrene at low temperature. Experimental structural information on this important type of reactive intermediate is extremely scarce and thus serves as a reference point for mechanistic discussions of rhodium catalysis in general. Moreover, dirhodium carbenes are shown to undergo remarkably facile carbene transfer on treatment with [LAuNTf(2)] (L=phosphine). This formal transmetalation opens a valuable new entry into gold carbene complexes that cannot easily be made otherwise; three fully characterized representatives illustrate this aspect. |
format | Online Article Text |
id | pubmed-4832834 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2015 |
publisher | WILEY‐VCH Verlag |
record_format | MEDLINE/PubMed |
spelling | pubmed-48328342016-04-27 The First Crystal Structure of a Reactive Dirhodium Carbene Complex and a Versatile Method for the Preparation of Gold Carbenes by Rhodium‐to‐Gold Transmetalation Werlé, Christophe Goddard, Richard Fürstner, Alois Angew Chem Int Ed Engl Communications The dirhodium carbene derived from bis(4‐methoxyphenyl)diazomethane and [Rh(tpa)(4)]⋅CH(2)Cl(2) (tpa=triphenylacetate) was characterized by UV, IR, and NMR spectroscopy, HRMS, as well as by X‐ray diffraction. The isolated complex exhibits prototypical rhodium carbene reactivity in that it cyclopropanates 4‐methoxystyrene at low temperature. Experimental structural information on this important type of reactive intermediate is extremely scarce and thus serves as a reference point for mechanistic discussions of rhodium catalysis in general. Moreover, dirhodium carbenes are shown to undergo remarkably facile carbene transfer on treatment with [LAuNTf(2)] (L=phosphine). This formal transmetalation opens a valuable new entry into gold carbene complexes that cannot easily be made otherwise; three fully characterized representatives illustrate this aspect. WILEY‐VCH Verlag 2015-11-04 2015-12-14 /pmc/articles/PMC4832834/ /pubmed/26534892 http://dx.doi.org/10.1002/anie.201506902 Text en © 2015 The Authors. Published by Wiley‐VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution Non‐Commercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes. Open access. |
spellingShingle | Communications Werlé, Christophe Goddard, Richard Fürstner, Alois The First Crystal Structure of a Reactive Dirhodium Carbene Complex and a Versatile Method for the Preparation of Gold Carbenes by Rhodium‐to‐Gold Transmetalation |
title | The First Crystal Structure of a Reactive Dirhodium Carbene Complex and a Versatile Method for the Preparation of Gold Carbenes by Rhodium‐to‐Gold Transmetalation |
title_full | The First Crystal Structure of a Reactive Dirhodium Carbene Complex and a Versatile Method for the Preparation of Gold Carbenes by Rhodium‐to‐Gold Transmetalation |
title_fullStr | The First Crystal Structure of a Reactive Dirhodium Carbene Complex and a Versatile Method for the Preparation of Gold Carbenes by Rhodium‐to‐Gold Transmetalation |
title_full_unstemmed | The First Crystal Structure of a Reactive Dirhodium Carbene Complex and a Versatile Method for the Preparation of Gold Carbenes by Rhodium‐to‐Gold Transmetalation |
title_short | The First Crystal Structure of a Reactive Dirhodium Carbene Complex and a Versatile Method for the Preparation of Gold Carbenes by Rhodium‐to‐Gold Transmetalation |
title_sort | first crystal structure of a reactive dirhodium carbene complex and a versatile method for the preparation of gold carbenes by rhodium‐to‐gold transmetalation |
topic | Communications |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4832834/ https://www.ncbi.nlm.nih.gov/pubmed/26534892 http://dx.doi.org/10.1002/anie.201506902 |
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