Access to a Catalytically Generated Umpolung Reagent through the Use of Cu-Catalyzed Reductive Coupling of Ketones and Allenes for the Synthesis of Chiral Vicinal Aminoalcohol Synthons

[Image: see text] We report the development of a stereoselective method for the allylation of ketones utilizing N-substituted allyl equivalents generated from a chiral allenamide. By employing N-heterocyclic carbenes as ligands for the Cu catalyst, good branched selectivity can be obtained with high...

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Autores principales: Gargaro, Samantha L., Klake, Raphael K., Burns, Kevin L., Elele, Sharon O., Gentry, Skyler L., Sieber, Joshua D.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2019
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6902281/
https://www.ncbi.nlm.nih.gov/pubmed/31769994
http://dx.doi.org/10.1021/acs.orglett.9b03937
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author Gargaro, Samantha L.
Klake, Raphael K.
Burns, Kevin L.
Elele, Sharon O.
Gentry, Skyler L.
Sieber, Joshua D.
author_facet Gargaro, Samantha L.
Klake, Raphael K.
Burns, Kevin L.
Elele, Sharon O.
Gentry, Skyler L.
Sieber, Joshua D.
author_sort Gargaro, Samantha L.
collection PubMed
description [Image: see text] We report the development of a stereoselective method for the allylation of ketones utilizing N-substituted allyl equivalents generated from a chiral allenamide. By employing N-heterocyclic carbenes as ligands for the Cu catalyst, good branched selectivity can be obtained with high diastereocontrol. This methodology allows access to a catalytically generated, polarity-reversed (umpolung) allyl nucleophile to enable the preparation of chiral 1,2-aminoalcohol synthons containing a dissonant functional group relationship.
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spelling pubmed-69022812019-12-11 Access to a Catalytically Generated Umpolung Reagent through the Use of Cu-Catalyzed Reductive Coupling of Ketones and Allenes for the Synthesis of Chiral Vicinal Aminoalcohol Synthons Gargaro, Samantha L. Klake, Raphael K. Burns, Kevin L. Elele, Sharon O. Gentry, Skyler L. Sieber, Joshua D. Org Lett [Image: see text] We report the development of a stereoselective method for the allylation of ketones utilizing N-substituted allyl equivalents generated from a chiral allenamide. By employing N-heterocyclic carbenes as ligands for the Cu catalyst, good branched selectivity can be obtained with high diastereocontrol. This methodology allows access to a catalytically generated, polarity-reversed (umpolung) allyl nucleophile to enable the preparation of chiral 1,2-aminoalcohol synthons containing a dissonant functional group relationship. American Chemical Society 2019-11-26 2019-12-06 /pmc/articles/PMC6902281/ /pubmed/31769994 http://dx.doi.org/10.1021/acs.orglett.9b03937 Text en Copyright © 2019 American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
spellingShingle Gargaro, Samantha L.
Klake, Raphael K.
Burns, Kevin L.
Elele, Sharon O.
Gentry, Skyler L.
Sieber, Joshua D.
Access to a Catalytically Generated Umpolung Reagent through the Use of Cu-Catalyzed Reductive Coupling of Ketones and Allenes for the Synthesis of Chiral Vicinal Aminoalcohol Synthons
title Access to a Catalytically Generated Umpolung Reagent through the Use of Cu-Catalyzed Reductive Coupling of Ketones and Allenes for the Synthesis of Chiral Vicinal Aminoalcohol Synthons
title_full Access to a Catalytically Generated Umpolung Reagent through the Use of Cu-Catalyzed Reductive Coupling of Ketones and Allenes for the Synthesis of Chiral Vicinal Aminoalcohol Synthons
title_fullStr Access to a Catalytically Generated Umpolung Reagent through the Use of Cu-Catalyzed Reductive Coupling of Ketones and Allenes for the Synthesis of Chiral Vicinal Aminoalcohol Synthons
title_full_unstemmed Access to a Catalytically Generated Umpolung Reagent through the Use of Cu-Catalyzed Reductive Coupling of Ketones and Allenes for the Synthesis of Chiral Vicinal Aminoalcohol Synthons
title_short Access to a Catalytically Generated Umpolung Reagent through the Use of Cu-Catalyzed Reductive Coupling of Ketones and Allenes for the Synthesis of Chiral Vicinal Aminoalcohol Synthons
title_sort access to a catalytically generated umpolung reagent through the use of cu-catalyzed reductive coupling of ketones and allenes for the synthesis of chiral vicinal aminoalcohol synthons
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6902281/
https://www.ncbi.nlm.nih.gov/pubmed/31769994
http://dx.doi.org/10.1021/acs.orglett.9b03937
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