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Alkynyl Moiety for Triggering 1,2‐Metallate Shifts: Enantiospecific sp(2)–sp(3) Coupling of Boronic Esters with p‐Arylacetylenes

The enantiospecific coupling of secondary and tertiary boronic esters to aromatics has been investigated. Using p‐lithiated phenylacetylenes and a range of boronic esters coupling has been achieved by the addition of N‐bromosuccinimide (NBS). The alkyne functionality of the intermediate boronate com...

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Autores principales: Ganesh, Venkataraman, Odachowski, Marcin, Aggarwal, Varinder K.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2017
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5577510/
https://www.ncbi.nlm.nih.gov/pubmed/28618129
http://dx.doi.org/10.1002/anie.201703894
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author Ganesh, Venkataraman
Odachowski, Marcin
Aggarwal, Varinder K.
author_facet Ganesh, Venkataraman
Odachowski, Marcin
Aggarwal, Varinder K.
author_sort Ganesh, Venkataraman
collection PubMed
description The enantiospecific coupling of secondary and tertiary boronic esters to aromatics has been investigated. Using p‐lithiated phenylacetylenes and a range of boronic esters coupling has been achieved by the addition of N‐bromosuccinimide (NBS). The alkyne functionality of the intermediate boronate complex reacts with NBS triggering the 1,2‐migration of the group on boron to carbon giving a dearomatized bromoallene intermediate. At this point elimination and rearomatization occurs with neopentyl boronic esters, giving the coupled products. However, using pinacol boronic esters, the boron moiety migrates to the adjacent carbon resulting in formation of ortho boron‐incorporated coupled products. The synthetic utility of the boron incorporated product has been demonstrated by orthogonal transformation of both the alkyne and boronic ester functionalities.
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spelling pubmed-55775102017-09-18 Alkynyl Moiety for Triggering 1,2‐Metallate Shifts: Enantiospecific sp(2)–sp(3) Coupling of Boronic Esters with p‐Arylacetylenes Ganesh, Venkataraman Odachowski, Marcin Aggarwal, Varinder K. Angew Chem Int Ed Engl Communications The enantiospecific coupling of secondary and tertiary boronic esters to aromatics has been investigated. Using p‐lithiated phenylacetylenes and a range of boronic esters coupling has been achieved by the addition of N‐bromosuccinimide (NBS). The alkyne functionality of the intermediate boronate complex reacts with NBS triggering the 1,2‐migration of the group on boron to carbon giving a dearomatized bromoallene intermediate. At this point elimination and rearomatization occurs with neopentyl boronic esters, giving the coupled products. However, using pinacol boronic esters, the boron moiety migrates to the adjacent carbon resulting in formation of ortho boron‐incorporated coupled products. The synthetic utility of the boron incorporated product has been demonstrated by orthogonal transformation of both the alkyne and boronic ester functionalities. John Wiley and Sons Inc. 2017-07-12 2017-08-07 /pmc/articles/PMC5577510/ /pubmed/28618129 http://dx.doi.org/10.1002/anie.201703894 Text en © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution (http://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Communications
Ganesh, Venkataraman
Odachowski, Marcin
Aggarwal, Varinder K.
Alkynyl Moiety for Triggering 1,2‐Metallate Shifts: Enantiospecific sp(2)–sp(3) Coupling of Boronic Esters with p‐Arylacetylenes
title Alkynyl Moiety for Triggering 1,2‐Metallate Shifts: Enantiospecific sp(2)–sp(3) Coupling of Boronic Esters with p‐Arylacetylenes
title_full Alkynyl Moiety for Triggering 1,2‐Metallate Shifts: Enantiospecific sp(2)–sp(3) Coupling of Boronic Esters with p‐Arylacetylenes
title_fullStr Alkynyl Moiety for Triggering 1,2‐Metallate Shifts: Enantiospecific sp(2)–sp(3) Coupling of Boronic Esters with p‐Arylacetylenes
title_full_unstemmed Alkynyl Moiety for Triggering 1,2‐Metallate Shifts: Enantiospecific sp(2)–sp(3) Coupling of Boronic Esters with p‐Arylacetylenes
title_short Alkynyl Moiety for Triggering 1,2‐Metallate Shifts: Enantiospecific sp(2)–sp(3) Coupling of Boronic Esters with p‐Arylacetylenes
title_sort alkynyl moiety for triggering 1,2‐metallate shifts: enantiospecific sp(2)–sp(3) coupling of boronic esters with p‐arylacetylenes
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5577510/
https://www.ncbi.nlm.nih.gov/pubmed/28618129
http://dx.doi.org/10.1002/anie.201703894
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