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Silyl Imine Electrophiles in Enantioselective Catalysis: A Rosetta Stone for Peptide Homologation, Enabling Diverse N-Protected Aryl Glycines from Aldehydes in Three Steps

[Image: see text] We report that N-(trimethylsilyl)imines serve in the Bis(AMidine)-catalyzed addition of bromonitromethane with a high degree of enantioselection. This allows for the production of a range of protected α-bromo nitroalkane donors (including Fmoc) for use in Umpolung Amide Synthesis (...

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Autores principales: Makley, Dawn M., Johnston, Jeffrey N.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2014
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4059254/
https://www.ncbi.nlm.nih.gov/pubmed/24828455
http://dx.doi.org/10.1021/ol501297a
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author Makley, Dawn M.
Johnston, Jeffrey N.
author_facet Makley, Dawn M.
Johnston, Jeffrey N.
author_sort Makley, Dawn M.
collection PubMed
description [Image: see text] We report that N-(trimethylsilyl)imines serve in the Bis(AMidine)-catalyzed addition of bromonitromethane with a high degree of enantioselection. This allows for the production of a range of protected α-bromo nitroalkane donors (including Fmoc) for use in Umpolung Amide Synthesis (UmAS). Hence, peptide homologation with nonnatural aryl glycine amino acids is achieved in three steps from aromatic aldehydes, which are plentiful and inexpensive. Epimerization during the homologation step is circumvented by avoiding an α-amino acid intermediate.
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spelling pubmed-40592542015-05-14 Silyl Imine Electrophiles in Enantioselective Catalysis: A Rosetta Stone for Peptide Homologation, Enabling Diverse N-Protected Aryl Glycines from Aldehydes in Three Steps Makley, Dawn M. Johnston, Jeffrey N. Org Lett [Image: see text] We report that N-(trimethylsilyl)imines serve in the Bis(AMidine)-catalyzed addition of bromonitromethane with a high degree of enantioselection. This allows for the production of a range of protected α-bromo nitroalkane donors (including Fmoc) for use in Umpolung Amide Synthesis (UmAS). Hence, peptide homologation with nonnatural aryl glycine amino acids is achieved in three steps from aromatic aldehydes, which are plentiful and inexpensive. Epimerization during the homologation step is circumvented by avoiding an α-amino acid intermediate. American Chemical Society 2014-05-14 2014-06-06 /pmc/articles/PMC4059254/ /pubmed/24828455 http://dx.doi.org/10.1021/ol501297a Text en Copyright © 2014 American Chemical Society
spellingShingle Makley, Dawn M.
Johnston, Jeffrey N.
Silyl Imine Electrophiles in Enantioselective Catalysis: A Rosetta Stone for Peptide Homologation, Enabling Diverse N-Protected Aryl Glycines from Aldehydes in Three Steps
title Silyl Imine Electrophiles in Enantioselective Catalysis: A Rosetta Stone for Peptide Homologation, Enabling Diverse N-Protected Aryl Glycines from Aldehydes in Three Steps
title_full Silyl Imine Electrophiles in Enantioselective Catalysis: A Rosetta Stone for Peptide Homologation, Enabling Diverse N-Protected Aryl Glycines from Aldehydes in Three Steps
title_fullStr Silyl Imine Electrophiles in Enantioselective Catalysis: A Rosetta Stone for Peptide Homologation, Enabling Diverse N-Protected Aryl Glycines from Aldehydes in Three Steps
title_full_unstemmed Silyl Imine Electrophiles in Enantioselective Catalysis: A Rosetta Stone for Peptide Homologation, Enabling Diverse N-Protected Aryl Glycines from Aldehydes in Three Steps
title_short Silyl Imine Electrophiles in Enantioselective Catalysis: A Rosetta Stone for Peptide Homologation, Enabling Diverse N-Protected Aryl Glycines from Aldehydes in Three Steps
title_sort silyl imine electrophiles in enantioselective catalysis: a rosetta stone for peptide homologation, enabling diverse n-protected aryl glycines from aldehydes in three steps
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4059254/
https://www.ncbi.nlm.nih.gov/pubmed/24828455
http://dx.doi.org/10.1021/ol501297a
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