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Sequential catalysis: exploiting a single rhodium(i) catalyst to promote an alkyne hydroacylation–aryl boronic acid conjugate addition sequence
We demonstrate that a single Rh(i) complex can promote two mechanistically distinct C–C bond-forming reactions – alkyne hydroacylation and aryl boronic acid conjugate addition – to deliver substituted ketone products from the controlled assembly of three readily available fragments. This is a rare e...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Royal Society of Chemistry
2017
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5351800/ https://www.ncbi.nlm.nih.gov/pubmed/28451201 http://dx.doi.org/10.1039/c6sc03066a |
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author | Fernández, Maitane Castaing, Matthias Willis, Michael C. |
author_facet | Fernández, Maitane Castaing, Matthias Willis, Michael C. |
author_sort | Fernández, Maitane |
collection | PubMed |
description | We demonstrate that a single Rh(i) complex can promote two mechanistically distinct C–C bond-forming reactions – alkyne hydroacylation and aryl boronic acid conjugate addition – to deliver substituted ketone products from the controlled assembly of three readily available fragments. This is a rare example of a Rh(i)/Rh(iii) cycle and a redox neutral Rh(i) cycle being promoted by a single catalyst. The process is broad in scope, allowing significant variation of all three reaction components. Incorporation of an enantiomerically pure bis-phosphine ligand renders the process enantioselective. Superior levels of enantioselectivity (up to >99% ee) can be achieved from using a two catalyst system, whereby two Rh(i) complexes, one incorporating an achiral bis-phosphine ligand and the second a chiral diene ligand, are introduced at the start of the reaction sequence. |
format | Online Article Text |
id | pubmed-5351800 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2017 |
publisher | Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-53518002017-04-27 Sequential catalysis: exploiting a single rhodium(i) catalyst to promote an alkyne hydroacylation–aryl boronic acid conjugate addition sequence Fernández, Maitane Castaing, Matthias Willis, Michael C. Chem Sci Chemistry We demonstrate that a single Rh(i) complex can promote two mechanistically distinct C–C bond-forming reactions – alkyne hydroacylation and aryl boronic acid conjugate addition – to deliver substituted ketone products from the controlled assembly of three readily available fragments. This is a rare example of a Rh(i)/Rh(iii) cycle and a redox neutral Rh(i) cycle being promoted by a single catalyst. The process is broad in scope, allowing significant variation of all three reaction components. Incorporation of an enantiomerically pure bis-phosphine ligand renders the process enantioselective. Superior levels of enantioselectivity (up to >99% ee) can be achieved from using a two catalyst system, whereby two Rh(i) complexes, one incorporating an achiral bis-phosphine ligand and the second a chiral diene ligand, are introduced at the start of the reaction sequence. Royal Society of Chemistry 2017-01-01 2016-09-09 /pmc/articles/PMC5351800/ /pubmed/28451201 http://dx.doi.org/10.1039/c6sc03066a Text en This journal is © The Royal Society of Chemistry 2016 http://creativecommons.org/licenses/by/3.0/ This is an Open Access article distributed under the terms of the Creative Commons Attribution 3.0 Unported License (http://creativecommons.org/licenses/by/3.0/) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. |
spellingShingle | Chemistry Fernández, Maitane Castaing, Matthias Willis, Michael C. Sequential catalysis: exploiting a single rhodium(i) catalyst to promote an alkyne hydroacylation–aryl boronic acid conjugate addition sequence |
title | Sequential catalysis: exploiting a single rhodium(i) catalyst to promote an alkyne hydroacylation–aryl boronic acid conjugate addition sequence
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title_full | Sequential catalysis: exploiting a single rhodium(i) catalyst to promote an alkyne hydroacylation–aryl boronic acid conjugate addition sequence
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title_fullStr | Sequential catalysis: exploiting a single rhodium(i) catalyst to promote an alkyne hydroacylation–aryl boronic acid conjugate addition sequence
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title_full_unstemmed | Sequential catalysis: exploiting a single rhodium(i) catalyst to promote an alkyne hydroacylation–aryl boronic acid conjugate addition sequence
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title_short | Sequential catalysis: exploiting a single rhodium(i) catalyst to promote an alkyne hydroacylation–aryl boronic acid conjugate addition sequence
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title_sort | sequential catalysis: exploiting a single rhodium(i) catalyst to promote an alkyne hydroacylation–aryl boronic acid conjugate addition sequence |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5351800/ https://www.ncbi.nlm.nih.gov/pubmed/28451201 http://dx.doi.org/10.1039/c6sc03066a |
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