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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...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical
Society
2021
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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. |
format | Online Article Text |
id | pubmed-7953379 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | American Chemical
Society |
record_format | MEDLINE/PubMed |
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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