Cargando…

Fast, greener and scalable direct coupling of organolithium compounds with no additional solvents

Although the use of catalytic rather than stoichiometric amounts of metal mediator in cross-coupling reactions between organic halides and organometallic counterparts improves significantly the atom economy and waste production, the use of solvents and stoichiometric generation of main-group byprodu...

Descripción completa

Detalles Bibliográficos
Autores principales: Pinxterhuis, Erik B., Giannerini, Massimo, Hornillos, Valentín, Feringa, Ben L.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group 2016
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4895725/
https://www.ncbi.nlm.nih.gov/pubmed/27251636
http://dx.doi.org/10.1038/ncomms11698
_version_ 1782435910095208448
author Pinxterhuis, Erik B.
Giannerini, Massimo
Hornillos, Valentín
Feringa, Ben L.
author_facet Pinxterhuis, Erik B.
Giannerini, Massimo
Hornillos, Valentín
Feringa, Ben L.
author_sort Pinxterhuis, Erik B.
collection PubMed
description Although the use of catalytic rather than stoichiometric amounts of metal mediator in cross-coupling reactions between organic halides and organometallic counterparts improves significantly the atom economy and waste production, the use of solvents and stoichiometric generation of main-group byproducts (B, Sn and Zn) hamper the ‘greenness' and industrial efficiency of these processes. Here we present a highly selective and green Pd-catalysed cross-coupling between organic halides and organolithium reagents proceeding without additional solvents and with short reaction times (10 min). This method bypasses a number of challenges previously encountered in Pd-catalysed cross-coupling with organolithium compounds such as strict exclusion of moisture, dilution and slow addition. Operational ease of this protocol combines the use of industrially viable catalysts loadings (down to 0.1 mol%), scalability of the process (tested up to 120 mmol) and exceptionally favourable environmental impact (E factors in several cases as low as 1).
format Online
Article
Text
id pubmed-4895725
institution National Center for Biotechnology Information
language English
publishDate 2016
publisher Nature Publishing Group
record_format MEDLINE/PubMed
spelling pubmed-48957252016-08-18 Fast, greener and scalable direct coupling of organolithium compounds with no additional solvents Pinxterhuis, Erik B. Giannerini, Massimo Hornillos, Valentín Feringa, Ben L. Nat Commun Article Although the use of catalytic rather than stoichiometric amounts of metal mediator in cross-coupling reactions between organic halides and organometallic counterparts improves significantly the atom economy and waste production, the use of solvents and stoichiometric generation of main-group byproducts (B, Sn and Zn) hamper the ‘greenness' and industrial efficiency of these processes. Here we present a highly selective and green Pd-catalysed cross-coupling between organic halides and organolithium reagents proceeding without additional solvents and with short reaction times (10 min). This method bypasses a number of challenges previously encountered in Pd-catalysed cross-coupling with organolithium compounds such as strict exclusion of moisture, dilution and slow addition. Operational ease of this protocol combines the use of industrially viable catalysts loadings (down to 0.1 mol%), scalability of the process (tested up to 120 mmol) and exceptionally favourable environmental impact (E factors in several cases as low as 1). Nature Publishing Group 2016-06-02 /pmc/articles/PMC4895725/ /pubmed/27251636 http://dx.doi.org/10.1038/ncomms11698 Text en Copyright © 2016, Nature Publishing Group, a division of Macmillan Publishers Limited. All Rights Reserved. http://creativecommons.org/licenses/by/4.0/ This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article's Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/
spellingShingle Article
Pinxterhuis, Erik B.
Giannerini, Massimo
Hornillos, Valentín
Feringa, Ben L.
Fast, greener and scalable direct coupling of organolithium compounds with no additional solvents
title Fast, greener and scalable direct coupling of organolithium compounds with no additional solvents
title_full Fast, greener and scalable direct coupling of organolithium compounds with no additional solvents
title_fullStr Fast, greener and scalable direct coupling of organolithium compounds with no additional solvents
title_full_unstemmed Fast, greener and scalable direct coupling of organolithium compounds with no additional solvents
title_short Fast, greener and scalable direct coupling of organolithium compounds with no additional solvents
title_sort fast, greener and scalable direct coupling of organolithium compounds with no additional solvents
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4895725/
https://www.ncbi.nlm.nih.gov/pubmed/27251636
http://dx.doi.org/10.1038/ncomms11698
work_keys_str_mv AT pinxterhuiserikb fastgreenerandscalabledirectcouplingoforganolithiumcompoundswithnoadditionalsolvents
AT giannerinimassimo fastgreenerandscalabledirectcouplingoforganolithiumcompoundswithnoadditionalsolvents
AT hornillosvalentin fastgreenerandscalabledirectcouplingoforganolithiumcompoundswithnoadditionalsolvents
AT feringabenl fastgreenerandscalabledirectcouplingoforganolithiumcompoundswithnoadditionalsolvents