Direct Observation of Aryl Gold(I) Carbenes that Undergo Cyclopropanation, C−H Insertion, and Dimerization Reactions

Mesityl gold(I) carbenes lacking heteroatom stabilization or shielding ancillary ligands have been generated and spectroscopically characterized from chloro(mesityl)methylgold(I) carbenoids bearing JohnPhos‐type ligands by chloride abstraction with GaCl(3). The aryl carbenes react with PPh(3) and al...

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Autores principales: García‐Morales, Cristina, Pei, Xiao‐Li, Sarria Toro, Juan M., Echavarren, Antonio M.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2019
Materias:
Communications
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6593763/
https://www.ncbi.nlm.nih.gov/pubmed/30644625
http://dx.doi.org/10.1002/anie.201814577
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author García‐Morales, Cristina
Pei, Xiao‐Li
Sarria Toro, Juan M.
Echavarren, Antonio M.
author_facet García‐Morales, Cristina
Pei, Xiao‐Li
Sarria Toro, Juan M.
Echavarren, Antonio M.
author_sort García‐Morales, Cristina
collection PubMed
description Mesityl gold(I) carbenes lacking heteroatom stabilization or shielding ancillary ligands have been generated and spectroscopically characterized from chloro(mesityl)methylgold(I) carbenoids bearing JohnPhos‐type ligands by chloride abstraction with GaCl(3). The aryl carbenes react with PPh(3) and alkenes to give stable phosphonium ylides and cyclopropanes, respectively. Oxidation with pyridine N‐oxide and intermolecular C−H insertion to cyclohexane have also been observed. In the absence of nucleophiles, a bimolecular reaction, similar to that observed for other metal carbenes, leads to a symmetrical alkene.
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spelling pubmed-65937632019-07-10 Direct Observation of Aryl Gold(I) Carbenes that Undergo Cyclopropanation, C−H Insertion, and Dimerization Reactions García‐Morales, Cristina Pei, Xiao‐Li Sarria Toro, Juan M. Echavarren, Antonio M. Angew Chem Int Ed Engl Communications Mesityl gold(I) carbenes lacking heteroatom stabilization or shielding ancillary ligands have been generated and spectroscopically characterized from chloro(mesityl)methylgold(I) carbenoids bearing JohnPhos‐type ligands by chloride abstraction with GaCl(3). The aryl carbenes react with PPh(3) and alkenes to give stable phosphonium ylides and cyclopropanes, respectively. Oxidation with pyridine N‐oxide and intermolecular C−H insertion to cyclohexane have also been observed. In the absence of nucleophiles, a bimolecular reaction, similar to that observed for other metal carbenes, leads to a symmetrical alkene. John Wiley and Sons Inc. 2019-02-11 2019-03-18 /pmc/articles/PMC6593763/ /pubmed/30644625 http://dx.doi.org/10.1002/anie.201814577 Text en © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.
spellingShingle Communications
García‐Morales, Cristina
Pei, Xiao‐Li
Sarria Toro, Juan M.
Echavarren, Antonio M.
Direct Observation of Aryl Gold(I) Carbenes that Undergo Cyclopropanation, C−H Insertion, and Dimerization Reactions
title Direct Observation of Aryl Gold(I) Carbenes that Undergo Cyclopropanation, C−H Insertion, and Dimerization Reactions
title_full Direct Observation of Aryl Gold(I) Carbenes that Undergo Cyclopropanation, C−H Insertion, and Dimerization Reactions
title_fullStr Direct Observation of Aryl Gold(I) Carbenes that Undergo Cyclopropanation, C−H Insertion, and Dimerization Reactions
title_full_unstemmed Direct Observation of Aryl Gold(I) Carbenes that Undergo Cyclopropanation, C−H Insertion, and Dimerization Reactions
title_short Direct Observation of Aryl Gold(I) Carbenes that Undergo Cyclopropanation, C−H Insertion, and Dimerization Reactions
title_sort direct observation of aryl gold(i) carbenes that undergo cyclopropanation, c−h insertion, and dimerization reactions
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6593763/
https://www.ncbi.nlm.nih.gov/pubmed/30644625
http://dx.doi.org/10.1002/anie.201814577
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