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Asymmetric Synthesis of α-Allyl-α-Aryl α-Amino Acids by Tandem Alkylation/π-Allylation of α-Iminoesters

[Image: see text] The first asymmetric synthesis of α-allyl-α-aryl α-amino acids by means of a three-component coupling of α-iminoesters, Grignard reagents, and cinnamyl acetate is reported. Notably, the enolate from the tandem process provides a much higher level of reactivity and selectivity than...

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Autores principales: Curto, John M., Dickstein, Joshua S., Berritt, Simon, Kozlowski, Marisa C.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2014
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3983326/
https://www.ncbi.nlm.nih.gov/pubmed/24666394
http://dx.doi.org/10.1021/ol500506t
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author Curto, John M.
Dickstein, Joshua S.
Berritt, Simon
Kozlowski, Marisa C.
author_facet Curto, John M.
Dickstein, Joshua S.
Berritt, Simon
Kozlowski, Marisa C.
author_sort Curto, John M.
collection PubMed
description [Image: see text] The first asymmetric synthesis of α-allyl-α-aryl α-amino acids by means of a three-component coupling of α-iminoesters, Grignard reagents, and cinnamyl acetate is reported. Notably, the enolate from the tandem process provides a much higher level of reactivity and selectivity than the same enolate generated via direct deprotonation, presumably due to differences in the solvation/aggregation state. A novel method for removal of a homoallylic amine protecting group delivers the free amine congeners. The α-allyl group offers a means to generate further valuable α-amino acid structures as exemplified by ring closing metathesis to generate a higher ring homologue of α-aryl-proline.
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spelling pubmed-39833262015-03-25 Asymmetric Synthesis of α-Allyl-α-Aryl α-Amino Acids by Tandem Alkylation/π-Allylation of α-Iminoesters Curto, John M. Dickstein, Joshua S. Berritt, Simon Kozlowski, Marisa C. Org Lett [Image: see text] The first asymmetric synthesis of α-allyl-α-aryl α-amino acids by means of a three-component coupling of α-iminoesters, Grignard reagents, and cinnamyl acetate is reported. Notably, the enolate from the tandem process provides a much higher level of reactivity and selectivity than the same enolate generated via direct deprotonation, presumably due to differences in the solvation/aggregation state. A novel method for removal of a homoallylic amine protecting group delivers the free amine congeners. The α-allyl group offers a means to generate further valuable α-amino acid structures as exemplified by ring closing metathesis to generate a higher ring homologue of α-aryl-proline. American Chemical Society 2014-03-25 2014-04-04 /pmc/articles/PMC3983326/ /pubmed/24666394 http://dx.doi.org/10.1021/ol500506t Text en Copyright © 2014 American Chemical Society
spellingShingle Curto, John M.
Dickstein, Joshua S.
Berritt, Simon
Kozlowski, Marisa C.
Asymmetric Synthesis of α-Allyl-α-Aryl α-Amino Acids by Tandem Alkylation/π-Allylation of α-Iminoesters
title Asymmetric Synthesis of α-Allyl-α-Aryl α-Amino Acids by Tandem Alkylation/π-Allylation of α-Iminoesters
title_full Asymmetric Synthesis of α-Allyl-α-Aryl α-Amino Acids by Tandem Alkylation/π-Allylation of α-Iminoesters
title_fullStr Asymmetric Synthesis of α-Allyl-α-Aryl α-Amino Acids by Tandem Alkylation/π-Allylation of α-Iminoesters
title_full_unstemmed Asymmetric Synthesis of α-Allyl-α-Aryl α-Amino Acids by Tandem Alkylation/π-Allylation of α-Iminoesters
title_short Asymmetric Synthesis of α-Allyl-α-Aryl α-Amino Acids by Tandem Alkylation/π-Allylation of α-Iminoesters
title_sort asymmetric synthesis of α-allyl-α-aryl α-amino acids by tandem alkylation/π-allylation of α-iminoesters
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3983326/
https://www.ncbi.nlm.nih.gov/pubmed/24666394
http://dx.doi.org/10.1021/ol500506t
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