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Catalytic Asymmetric Synthesis of Unprotected β(2)-Amino Acids

[Image: see text] We report here a scalable, catalytic one-pot approach to enantiopure and unmodified β(2)-amino acids. A newly developed confined imidodiphosphorimidate (IDPi) catalyzes a broadly applicable reaction of diverse bis-silyl ketene acetals with a silylated aminomethyl ether, followed by...

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Autores principales: Zhu, Chendan, Mandrelli, Francesca, Zhou, Hui, Maji, Rajat, List, Benjamin
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7953379/
https://www.ncbi.nlm.nih.gov/pubmed/33645969
http://dx.doi.org/10.1021/jacs.1c00249
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author Zhu, Chendan
Mandrelli, Francesca
Zhou, Hui
Maji, Rajat
List, Benjamin
author_facet Zhu, Chendan
Mandrelli, Francesca
Zhou, Hui
Maji, Rajat
List, Benjamin
author_sort Zhu, Chendan
collection PubMed
description [Image: see text] We report here a scalable, catalytic one-pot approach to enantiopure and unmodified β(2)-amino acids. A newly developed confined imidodiphosphorimidate (IDPi) catalyzes a broadly applicable reaction of diverse bis-silyl ketene acetals with a silylated aminomethyl ether, followed by hydrolytic workup, to give free β(2)-amino acids in high yields, purity, and enantioselectivity. Importantly, both aromatic and aliphatic β(2)-amino acids can be obtained using this method. Mechanistic studies are consistent with the aminomethylation to proceed via silylium-based asymmetric counteranion-directed catalysis (Si-ACDC) and a transition state to explain the enantioselectivity is suggested on the basis of density functional theory calculation.
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spelling pubmed-79533792021-03-12 Catalytic Asymmetric Synthesis of Unprotected β(2)-Amino Acids Zhu, Chendan Mandrelli, Francesca Zhou, Hui Maji, Rajat List, Benjamin J Am Chem Soc [Image: see text] We report here a scalable, catalytic one-pot approach to enantiopure and unmodified β(2)-amino acids. A newly developed confined imidodiphosphorimidate (IDPi) catalyzes a broadly applicable reaction of diverse bis-silyl ketene acetals with a silylated aminomethyl ether, followed by hydrolytic workup, to give free β(2)-amino acids in high yields, purity, and enantioselectivity. Importantly, both aromatic and aliphatic β(2)-amino acids can be obtained using this method. Mechanistic studies are consistent with the aminomethylation to proceed via silylium-based asymmetric counteranion-directed catalysis (Si-ACDC) and a transition state to explain the enantioselectivity is suggested on the basis of density functional theory calculation. American Chemical Society 2021-03-01 2021-03-10 /pmc/articles/PMC7953379/ /pubmed/33645969 http://dx.doi.org/10.1021/jacs.1c00249 Text en © 2021 The Authors. Published by American Chemical Society This is an open access article published under an ACS AuthorChoice License (https://creativecommons.org/licenses/by/4.0/) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
spellingShingle Zhu, Chendan
Mandrelli, Francesca
Zhou, Hui
Maji, Rajat
List, Benjamin
Catalytic Asymmetric Synthesis of Unprotected β(2)-Amino Acids
title Catalytic Asymmetric Synthesis of Unprotected β(2)-Amino Acids
title_full Catalytic Asymmetric Synthesis of Unprotected β(2)-Amino Acids
title_fullStr Catalytic Asymmetric Synthesis of Unprotected β(2)-Amino Acids
title_full_unstemmed Catalytic Asymmetric Synthesis of Unprotected β(2)-Amino Acids
title_short Catalytic Asymmetric Synthesis of Unprotected β(2)-Amino Acids
title_sort catalytic asymmetric synthesis of unprotected β(2)-amino acids
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7953379/
https://www.ncbi.nlm.nih.gov/pubmed/33645969
http://dx.doi.org/10.1021/jacs.1c00249
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