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A Pd-catalyzed highly selective three-component protocol for trisubstituted allenes

Herein we report the first example of a Pd-catalyzed highly selective three-component reaction of alkynyl-1,4-diol dicarbonates, organoboronic acids, and malonate anions for the efficient synthesis of trisubstituted 2,3-allenyl malonates not readily available by the known protocols. The reaction dem...

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Detalles Bibliográficos
Autores principales: Li, Can, Zhou, Zhengnan, Ma, Shengming
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10355113/
https://www.ncbi.nlm.nih.gov/pubmed/37476716
http://dx.doi.org/10.1039/d3sc01849k
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author Li, Can
Zhou, Zhengnan
Ma, Shengming
author_facet Li, Can
Zhou, Zhengnan
Ma, Shengming
author_sort Li, Can
collection PubMed
description Herein we report the first example of a Pd-catalyzed highly selective three-component reaction of alkynyl-1,4-diol dicarbonates, organoboronic acids, and malonate anions for the efficient synthesis of trisubstituted 2,3-allenyl malonates not readily available by the known protocols. The reaction demonstrates an excellent regio- and chemo-selectivity for both the oxidative addition referring to the two C–O bonds and the subsequent coupling with the nucleophile with a remarkable functional group compatibility. A series of control experiments confirm a unique mechanism involving β-O elimination forming alka-1,2,3-triene and the subsequent insertion of its terminal C[double bond, length as m-dash]C bond into the Ar–Pd bond.
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spelling pubmed-103551132023-07-20 A Pd-catalyzed highly selective three-component protocol for trisubstituted allenes Li, Can Zhou, Zhengnan Ma, Shengming Chem Sci Chemistry Herein we report the first example of a Pd-catalyzed highly selective three-component reaction of alkynyl-1,4-diol dicarbonates, organoboronic acids, and malonate anions for the efficient synthesis of trisubstituted 2,3-allenyl malonates not readily available by the known protocols. The reaction demonstrates an excellent regio- and chemo-selectivity for both the oxidative addition referring to the two C–O bonds and the subsequent coupling with the nucleophile with a remarkable functional group compatibility. A series of control experiments confirm a unique mechanism involving β-O elimination forming alka-1,2,3-triene and the subsequent insertion of its terminal C[double bond, length as m-dash]C bond into the Ar–Pd bond. The Royal Society of Chemistry 2023-06-22 /pmc/articles/PMC10355113/ /pubmed/37476716 http://dx.doi.org/10.1039/d3sc01849k Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Li, Can
Zhou, Zhengnan
Ma, Shengming
A Pd-catalyzed highly selective three-component protocol for trisubstituted allenes
title A Pd-catalyzed highly selective three-component protocol for trisubstituted allenes
title_full A Pd-catalyzed highly selective three-component protocol for trisubstituted allenes
title_fullStr A Pd-catalyzed highly selective three-component protocol for trisubstituted allenes
title_full_unstemmed A Pd-catalyzed highly selective three-component protocol for trisubstituted allenes
title_short A Pd-catalyzed highly selective three-component protocol for trisubstituted allenes
title_sort pd-catalyzed highly selective three-component protocol for trisubstituted allenes
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10355113/
https://www.ncbi.nlm.nih.gov/pubmed/37476716
http://dx.doi.org/10.1039/d3sc01849k
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