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Pd(ii)-catalyzed β- and γ-C-(sp(3))–H dienylation with allenyl acetates

Recent years have seen the emergence of transition metal catalyzed C–H activation as a powerful synthetic tool in organic chemistry. Allenes have fascinated synthetic chemists due to their unique reactivity. While directing group assisted functionalization of C(sp(2))–H bonds with allenes is well do...

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Detalles Bibliográficos
Autores principales: Shukla, Rahul K., Nair, Akshay M., Volla, Chandra M. R.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9890605/
https://www.ncbi.nlm.nih.gov/pubmed/36755729
http://dx.doi.org/10.1039/d2sc05188e
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author Shukla, Rahul K.
Nair, Akshay M.
Volla, Chandra M. R.
author_facet Shukla, Rahul K.
Nair, Akshay M.
Volla, Chandra M. R.
author_sort Shukla, Rahul K.
collection PubMed
description Recent years have seen the emergence of transition metal catalyzed C–H activation as a powerful synthetic tool in organic chemistry. Allenes have fascinated synthetic chemists due to their unique reactivity. While directing group assisted functionalization of C(sp(2))–H bonds with allenes is well documented in the literature, their coupling with more challenging aliphatic C(sp(3))–H bonds remains elusive. In this regard, we hereby report a Pd(ii) catalyzed 8-aminoquinoline directed aliphatic C(sp(3))–H dienylation protocol using allenyl acetates. A variety of carboxylic acids including fatty acids and amino acids were efficiently functionalized at β and γ-positions to afford diversely functionalized 1,3-dienes. Preliminary mechanistic studies revealed the crucial role of the base in the success of the transformation. The reaction proceeds via regioselective 2,3-migratory insertion of the allene with the alkylpalladium(ii) species followed by β-acetoxy elimination.
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spelling pubmed-98906052023-02-07 Pd(ii)-catalyzed β- and γ-C-(sp(3))–H dienylation with allenyl acetates Shukla, Rahul K. Nair, Akshay M. Volla, Chandra M. R. Chem Sci Chemistry Recent years have seen the emergence of transition metal catalyzed C–H activation as a powerful synthetic tool in organic chemistry. Allenes have fascinated synthetic chemists due to their unique reactivity. While directing group assisted functionalization of C(sp(2))–H bonds with allenes is well documented in the literature, their coupling with more challenging aliphatic C(sp(3))–H bonds remains elusive. In this regard, we hereby report a Pd(ii) catalyzed 8-aminoquinoline directed aliphatic C(sp(3))–H dienylation protocol using allenyl acetates. A variety of carboxylic acids including fatty acids and amino acids were efficiently functionalized at β and γ-positions to afford diversely functionalized 1,3-dienes. Preliminary mechanistic studies revealed the crucial role of the base in the success of the transformation. The reaction proceeds via regioselective 2,3-migratory insertion of the allene with the alkylpalladium(ii) species followed by β-acetoxy elimination. The Royal Society of Chemistry 2022-12-20 /pmc/articles/PMC9890605/ /pubmed/36755729 http://dx.doi.org/10.1039/d2sc05188e Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Shukla, Rahul K.
Nair, Akshay M.
Volla, Chandra M. R.
Pd(ii)-catalyzed β- and γ-C-(sp(3))–H dienylation with allenyl acetates
title Pd(ii)-catalyzed β- and γ-C-(sp(3))–H dienylation with allenyl acetates
title_full Pd(ii)-catalyzed β- and γ-C-(sp(3))–H dienylation with allenyl acetates
title_fullStr Pd(ii)-catalyzed β- and γ-C-(sp(3))–H dienylation with allenyl acetates
title_full_unstemmed Pd(ii)-catalyzed β- and γ-C-(sp(3))–H dienylation with allenyl acetates
title_short Pd(ii)-catalyzed β- and γ-C-(sp(3))–H dienylation with allenyl acetates
title_sort pd(ii)-catalyzed β- and γ-c-(sp(3))–h dienylation with allenyl acetates
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9890605/
https://www.ncbi.nlm.nih.gov/pubmed/36755729
http://dx.doi.org/10.1039/d2sc05188e
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