Single and double activation of acetone by isolobal B[triple bond, length as m-dash]N and B[triple bond, length as m-dash]B triple bonds

B[triple bond, length as m-dash]N and B[triple bond, length as m-dash]B triple bonds induce C–H activation of acetone to yield a (2-propenyloxy)aminoborane and an unsymmetrical 1-(2-propenyloxy)-2-hydrodiborene, respectively. DFT calculations showed that, despite their stark electronic differences,...

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Autores principales: Böhnke, Julian, Brückner, Tobias, Hermann, Alexander, González-Belman, Oscar F., Arrowsmith, Merle, Jiménez-Halla, J. Oscar C., Braunschweig, Holger
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2018
Materias:
Chemistry
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6009441/
https://www.ncbi.nlm.nih.gov/pubmed/30009006
http://dx.doi.org/10.1039/c8sc01249k
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author Böhnke, Julian
Brückner, Tobias
Hermann, Alexander
González-Belman, Oscar F.
Arrowsmith, Merle
Jiménez-Halla, J. Oscar C.
Braunschweig, Holger
author_facet Böhnke, Julian
Brückner, Tobias
Hermann, Alexander
González-Belman, Oscar F.
Arrowsmith, Merle
Jiménez-Halla, J. Oscar C.
Braunschweig, Holger
author_sort Böhnke, Julian
collection PubMed
description B[triple bond, length as m-dash]N and B[triple bond, length as m-dash]B triple bonds induce C–H activation of acetone to yield a (2-propenyloxy)aminoborane and an unsymmetrical 1-(2-propenyloxy)-2-hydrodiborene, respectively. DFT calculations showed that, despite their stark electronic differences, both the B[triple bond, length as m-dash]N and B[triple bond, length as m-dash]B triple bonds activate acetone via a similar coordination-deprotonation mechanism. In contrast, the reaction of acetone with a cAAC-supported diboracumulene yielded a unique 1,2,3-oxadiborole, which according to DFT calculations also proceeds via an unsymmetrical diborene, followed by intramolecular hydride migration and a second C–H activation of the enolate ligand.
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spelling pubmed-60094412018-07-13 Single and double activation of acetone by isolobal B[triple bond, length as m-dash]N and B[triple bond, length as m-dash]B triple bonds Böhnke, Julian Brückner, Tobias Hermann, Alexander González-Belman, Oscar F. Arrowsmith, Merle Jiménez-Halla, J. Oscar C. Braunschweig, Holger Chem Sci Chemistry B[triple bond, length as m-dash]N and B[triple bond, length as m-dash]B triple bonds induce C–H activation of acetone to yield a (2-propenyloxy)aminoborane and an unsymmetrical 1-(2-propenyloxy)-2-hydrodiborene, respectively. DFT calculations showed that, despite their stark electronic differences, both the B[triple bond, length as m-dash]N and B[triple bond, length as m-dash]B triple bonds activate acetone via a similar coordination-deprotonation mechanism. In contrast, the reaction of acetone with a cAAC-supported diboracumulene yielded a unique 1,2,3-oxadiborole, which according to DFT calculations also proceeds via an unsymmetrical diborene, followed by intramolecular hydride migration and a second C–H activation of the enolate ligand. Royal Society of Chemistry 2018-04-30 /pmc/articles/PMC6009441/ /pubmed/30009006 http://dx.doi.org/10.1039/c8sc01249k Text en This journal is © The Royal Society of Chemistry 2018 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
Böhnke, Julian
Brückner, Tobias
Hermann, Alexander
González-Belman, Oscar F.
Arrowsmith, Merle
Jiménez-Halla, J. Oscar C.
Braunschweig, Holger
Single and double activation of acetone by isolobal B[triple bond, length as m-dash]N and B[triple bond, length as m-dash]B triple bonds
title Single and double activation of acetone by isolobal B[triple bond, length as m-dash]N and B[triple bond, length as m-dash]B triple bonds
title_full Single and double activation of acetone by isolobal B[triple bond, length as m-dash]N and B[triple bond, length as m-dash]B triple bonds
title_fullStr Single and double activation of acetone by isolobal B[triple bond, length as m-dash]N and B[triple bond, length as m-dash]B triple bonds
title_full_unstemmed Single and double activation of acetone by isolobal B[triple bond, length as m-dash]N and B[triple bond, length as m-dash]B triple bonds
title_short Single and double activation of acetone by isolobal B[triple bond, length as m-dash]N and B[triple bond, length as m-dash]B triple bonds
title_sort single and double activation of acetone by isolobal b[triple bond, length as m-dash]n and b[triple bond, length as m-dash]b triple bonds
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6009441/
https://www.ncbi.nlm.nih.gov/pubmed/30009006
http://dx.doi.org/10.1039/c8sc01249k
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