Radical zinc-atom-transfer-based carbozincation of haloalkynes with dialkylzincs

The formation of alkylidenezinc carbenoids by 1,4-addition/carbozincation of dialkylzincs or alkyl iodides based on zinc atom radical transfer, in the presence of dimethylzinc with β-(propargyloxy)enoates having pendant iodo- and bromoalkynes, is disclosed. Formation of the carbenoid intermediate is...

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Detalles Bibliográficos
Autores principales: Chemla, Fabrice, Dulong, Florian, Ferreira, Franck, Pérez-Luna, Alejandro
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Beilstein-Institut 2013
Materias:
Full Research Paper
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3566799/
https://www.ncbi.nlm.nih.gov/pubmed/23399921
http://dx.doi.org/10.3762/bjoc.9.28
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author Chemla, Fabrice
Dulong, Florian
Ferreira, Franck
Pérez-Luna, Alejandro
author_facet Chemla, Fabrice
Dulong, Florian
Ferreira, Franck
Pérez-Luna, Alejandro
author_sort Chemla, Fabrice
collection PubMed
description The formation of alkylidenezinc carbenoids by 1,4-addition/carbozincation of dialkylzincs or alkyl iodides based on zinc atom radical transfer, in the presence of dimethylzinc with β-(propargyloxy)enoates having pendant iodo- and bromoalkynes, is disclosed. Formation of the carbenoid intermediate is fully stereoselective at −30 °C and arises from a formal anti-selective carbozincation reaction. Upon warming, the zinc carbenoid is stereochemically labile and isomerizes to its more stable form.
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spelling pubmed-35667992013-02-11 Radical zinc-atom-transfer-based carbozincation of haloalkynes with dialkylzincs Chemla, Fabrice Dulong, Florian Ferreira, Franck Pérez-Luna, Alejandro Beilstein J Org Chem Full Research Paper The formation of alkylidenezinc carbenoids by 1,4-addition/carbozincation of dialkylzincs or alkyl iodides based on zinc atom radical transfer, in the presence of dimethylzinc with β-(propargyloxy)enoates having pendant iodo- and bromoalkynes, is disclosed. Formation of the carbenoid intermediate is fully stereoselective at −30 °C and arises from a formal anti-selective carbozincation reaction. Upon warming, the zinc carbenoid is stereochemically labile and isomerizes to its more stable form. Beilstein-Institut 2013-02-04 /pmc/articles/PMC3566799/ /pubmed/23399921 http://dx.doi.org/10.3762/bjoc.9.28 Text en Copyright © 2013, Chemla et al. https://creativecommons.org/licenses/by/2.0https://www.beilstein-journals.org/bjoc/termsThis is an Open Access article under the terms of the Creative Commons Attribution License (https://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. The license is subject to the Beilstein Journal of Organic Chemistry terms and conditions: (https://www.beilstein-journals.org/bjoc/terms)
spellingShingle Full Research Paper
Chemla, Fabrice
Dulong, Florian
Ferreira, Franck
Pérez-Luna, Alejandro
Radical zinc-atom-transfer-based carbozincation of haloalkynes with dialkylzincs
title Radical zinc-atom-transfer-based carbozincation of haloalkynes with dialkylzincs
title_full Radical zinc-atom-transfer-based carbozincation of haloalkynes with dialkylzincs
title_fullStr Radical zinc-atom-transfer-based carbozincation of haloalkynes with dialkylzincs
title_full_unstemmed Radical zinc-atom-transfer-based carbozincation of haloalkynes with dialkylzincs
title_short Radical zinc-atom-transfer-based carbozincation of haloalkynes with dialkylzincs
title_sort radical zinc-atom-transfer-based carbozincation of haloalkynes with dialkylzincs
topic Full Research Paper
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3566799/
https://www.ncbi.nlm.nih.gov/pubmed/23399921
http://dx.doi.org/10.3762/bjoc.9.28
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