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The hexadehydro-Diels–Alder reaction

o-Benzynes (arynes) are among the most versatile of all reactive (short-lived) intermediates in organic chemistry. These species can be trapped to give products that are valuable from the perspective of both fine (pharmaceuticals) and commodity (agrochemicals, dyes, polymers, etc.) chemicals. Here w...

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Autores principales: Hoye, Thomas R., Baire, Beeraiah, Niu, Dawen, Willoughby, Patrick H., Woods, Brian P.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: 2012
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3538845/
https://www.ncbi.nlm.nih.gov/pubmed/23060191
http://dx.doi.org/10.1038/nature11518
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author Hoye, Thomas R.
Baire, Beeraiah
Niu, Dawen
Willoughby, Patrick H.
Woods, Brian P.
author_facet Hoye, Thomas R.
Baire, Beeraiah
Niu, Dawen
Willoughby, Patrick H.
Woods, Brian P.
author_sort Hoye, Thomas R.
collection PubMed
description o-Benzynes (arynes) are among the most versatile of all reactive (short-lived) intermediates in organic chemistry. These species can be trapped to give products that are valuable from the perspective of both fine (pharmaceuticals) and commodity (agrochemicals, dyes, polymers, etc.) chemicals. Here we show a fundamentally new strategy that unites a de novo generation of benzynes, through the title hexadehydro-Diels–Alder (HDDA) reaction, with their in situ elaboration into structurally complex benzenoid products. In the HDDA reaction a 1,3-diyne is engaged in a [4+2] cycloisomerization with a third (pendant) alkyne–the diynophile–to produce the highly reactive benzyne intermediate. The metal- and reagent-free reaction conditions for this simple, thermal transformation are notable. The subsequent and highly efficient trapping reactions increase the power of the overall process. Finally, we provide examples of how this de novo benzyne generation approach allows new modes of intrinsic reactivity to be revealed.
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spelling pubmed-35388452013-04-11 The hexadehydro-Diels–Alder reaction Hoye, Thomas R. Baire, Beeraiah Niu, Dawen Willoughby, Patrick H. Woods, Brian P. Nature Article o-Benzynes (arynes) are among the most versatile of all reactive (short-lived) intermediates in organic chemistry. These species can be trapped to give products that are valuable from the perspective of both fine (pharmaceuticals) and commodity (agrochemicals, dyes, polymers, etc.) chemicals. Here we show a fundamentally new strategy that unites a de novo generation of benzynes, through the title hexadehydro-Diels–Alder (HDDA) reaction, with their in situ elaboration into structurally complex benzenoid products. In the HDDA reaction a 1,3-diyne is engaged in a [4+2] cycloisomerization with a third (pendant) alkyne–the diynophile–to produce the highly reactive benzyne intermediate. The metal- and reagent-free reaction conditions for this simple, thermal transformation are notable. The subsequent and highly efficient trapping reactions increase the power of the overall process. Finally, we provide examples of how this de novo benzyne generation approach allows new modes of intrinsic reactivity to be revealed. 2012-10-11 /pmc/articles/PMC3538845/ /pubmed/23060191 http://dx.doi.org/10.1038/nature11518 Text en Users may view, print, copy, download and text and data- mine the content in such documents, for the purposes of academic research, subject always to the full Conditions of use: http://www.nature.com/authors/editorial_policies/license.html#terms
spellingShingle Article
Hoye, Thomas R.
Baire, Beeraiah
Niu, Dawen
Willoughby, Patrick H.
Woods, Brian P.
The hexadehydro-Diels–Alder reaction
title The hexadehydro-Diels–Alder reaction
title_full The hexadehydro-Diels–Alder reaction
title_fullStr The hexadehydro-Diels–Alder reaction
title_full_unstemmed The hexadehydro-Diels–Alder reaction
title_short The hexadehydro-Diels–Alder reaction
title_sort hexadehydro-diels–alder reaction
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3538845/
https://www.ncbi.nlm.nih.gov/pubmed/23060191
http://dx.doi.org/10.1038/nature11518
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