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Magnesium-catalysed nitrile hydroboration
A β-diketiminato n-butylmagnesium complex is presented as a selective precatalyst for the reductive hydroboration of organic nitriles with pinacolborane (HBpin). Stoichiometric reactivity studies indicate that catalytic turnover ensues through the generation of magnesium aldimido, aldimidoborate and...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Royal Society of Chemistry
2016
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5952893/ https://www.ncbi.nlm.nih.gov/pubmed/29896350 http://dx.doi.org/10.1039/c5sc03114a |
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author | Weetman, Catherine Anker, Mathew D. Arrowsmith, Merle Hill, Michael S. Kociok-Köhn, Gabriele Liptrot, David J. Mahon, Mary F. |
author_facet | Weetman, Catherine Anker, Mathew D. Arrowsmith, Merle Hill, Michael S. Kociok-Köhn, Gabriele Liptrot, David J. Mahon, Mary F. |
author_sort | Weetman, Catherine |
collection | PubMed |
description | A β-diketiminato n-butylmagnesium complex is presented as a selective precatalyst for the reductive hydroboration of organic nitriles with pinacolborane (HBpin). Stoichiometric reactivity studies indicate that catalytic turnover ensues through the generation of magnesium aldimido, aldimidoborate and borylamido intermediates, which are formed in a sequence of intramolecular nitrile insertion and inter- and intramolecular B–H metathesis events. Kinetic studies highlight variations in mechanism for the catalytic dihydroboration of alkyl nitriles, aryl nitriles bearing electron withdrawing (Ar(EWG)CN) and aryl nitriles bearing electron donating (Ar(EDG)CN) substitution patterns. Kinetic isotope effects (KIEs) for catalysis performed with DBpin indicate that B–H bond breaking and C–H bond forming reactions are involved in the rate determining processes during the dihydroboration of alkyl nitriles and Ar(EDG)CN substrates, which display divergent first and second order rate dependences on [HBpin] respectively. In contrast, the hydroboration of Ar(EWG)CN substrates provides no KIE and HBpin is not implicated in the rate determining process during catalysis. Irrespective of these differences, a common mechanism is proposed in which the rate determining steps are deduced to vary through the establishment of several pre-equilibria, the relative positions of which are determined by the respective stabilities of the dimeric and monomeric magnesium aldimide and magnesium aldimidoborate intermediates as a result of adjustments to the basicity of the nitrile substrate. More generally, these observations indicate that homogeneous processes performed under heavier alkaline earth catalysis are likely to demonstrate previously unappreciated mechanistic diversity. |
format | Online Article Text |
id | pubmed-5952893 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2016 |
publisher | Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-59528932018-06-12 Magnesium-catalysed nitrile hydroboration Weetman, Catherine Anker, Mathew D. Arrowsmith, Merle Hill, Michael S. Kociok-Köhn, Gabriele Liptrot, David J. Mahon, Mary F. Chem Sci Chemistry A β-diketiminato n-butylmagnesium complex is presented as a selective precatalyst for the reductive hydroboration of organic nitriles with pinacolborane (HBpin). Stoichiometric reactivity studies indicate that catalytic turnover ensues through the generation of magnesium aldimido, aldimidoborate and borylamido intermediates, which are formed in a sequence of intramolecular nitrile insertion and inter- and intramolecular B–H metathesis events. Kinetic studies highlight variations in mechanism for the catalytic dihydroboration of alkyl nitriles, aryl nitriles bearing electron withdrawing (Ar(EWG)CN) and aryl nitriles bearing electron donating (Ar(EDG)CN) substitution patterns. Kinetic isotope effects (KIEs) for catalysis performed with DBpin indicate that B–H bond breaking and C–H bond forming reactions are involved in the rate determining processes during the dihydroboration of alkyl nitriles and Ar(EDG)CN substrates, which display divergent first and second order rate dependences on [HBpin] respectively. In contrast, the hydroboration of Ar(EWG)CN substrates provides no KIE and HBpin is not implicated in the rate determining process during catalysis. Irrespective of these differences, a common mechanism is proposed in which the rate determining steps are deduced to vary through the establishment of several pre-equilibria, the relative positions of which are determined by the respective stabilities of the dimeric and monomeric magnesium aldimide and magnesium aldimidoborate intermediates as a result of adjustments to the basicity of the nitrile substrate. More generally, these observations indicate that homogeneous processes performed under heavier alkaline earth catalysis are likely to demonstrate previously unappreciated mechanistic diversity. Royal Society of Chemistry 2016-01-01 2015-10-20 /pmc/articles/PMC5952893/ /pubmed/29896350 http://dx.doi.org/10.1039/c5sc03114a Text en This journal is © The Royal Society of Chemistry 2016 https://creativecommons.org/licenses/by/3.0/This article is freely available. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (CC BY 3.0) |
spellingShingle | Chemistry Weetman, Catherine Anker, Mathew D. Arrowsmith, Merle Hill, Michael S. Kociok-Köhn, Gabriele Liptrot, David J. Mahon, Mary F. Magnesium-catalysed nitrile hydroboration |
title | Magnesium-catalysed nitrile hydroboration
|
title_full | Magnesium-catalysed nitrile hydroboration
|
title_fullStr | Magnesium-catalysed nitrile hydroboration
|
title_full_unstemmed | Magnesium-catalysed nitrile hydroboration
|
title_short | Magnesium-catalysed nitrile hydroboration
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title_sort | magnesium-catalysed nitrile hydroboration |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5952893/ https://www.ncbi.nlm.nih.gov/pubmed/29896350 http://dx.doi.org/10.1039/c5sc03114a |
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