Cargando…
Unified Approach to Imidodiphosphate-Type Brønsted Acids with Tunable Confinement and Acidity
[Image: see text] We have designed and realized an efficient and operationally simple single-flask synthesis of imidodiphosphate-based Brønsted acids. The methodology proceeds via consecutive chloride substitutions of hexachlorobisphosphazonium salts, providing rapid access to imidodiphosphates (IDP...
Autores principales: | , , , , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2021
|
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8447263/ https://www.ncbi.nlm.nih.gov/pubmed/34478297 http://dx.doi.org/10.1021/jacs.1c07067 |
_version_ | 1784569017901514752 |
---|---|
author | Schwengers, Sebastian A. De, Chandra Kanta Grossmann, Oleg Grimm, Joyce A. A. Sadlowski, Natascha R. Gerosa, Gabriela G. List, Benjamin |
author_facet | Schwengers, Sebastian A. De, Chandra Kanta Grossmann, Oleg Grimm, Joyce A. A. Sadlowski, Natascha R. Gerosa, Gabriela G. List, Benjamin |
author_sort | Schwengers, Sebastian A. |
collection | PubMed |
description | [Image: see text] We have designed and realized an efficient and operationally simple single-flask synthesis of imidodiphosphate-based Brønsted acids. The methodology proceeds via consecutive chloride substitutions of hexachlorobisphosphazonium salts, providing rapid access to imidodiphosphates (IDP), iminoimidodiphosphates (iIDP), and imidodiphosphorimidates (IDPi). These privileged acid catalysts feature a broad acidity range (pK(a) from ∼11 to <2 in MeCN) and a readily tunable confined active site. Our approach enables access to previously elusive catalyst scaffolds with particularly high structural confinement, one of which catalyzes the first highly enantioselective (>95:5 er) sulfoxidation of methyl n-propyl sulfide. Furthermore, the methodology delivers a novel, rationally designed super acidic catalyst motif, imidodiphosphorbis(iminosulfonylimino)imidate (IDPii), the extreme reactivity of which exceeds commonly employed super-Brønsted acids, such as trifluoromethanesulfonic acid. The unique reactivity of one such IDPii catalyst has been demonstrated in the first α-methylation of a silyl ketene acetal with methanol as the electrophilic alkylating reagent. |
format | Online Article Text |
id | pubmed-8447263 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-84472632021-09-20 Unified Approach to Imidodiphosphate-Type Brønsted Acids with Tunable Confinement and Acidity Schwengers, Sebastian A. De, Chandra Kanta Grossmann, Oleg Grimm, Joyce A. A. Sadlowski, Natascha R. Gerosa, Gabriela G. List, Benjamin J Am Chem Soc [Image: see text] We have designed and realized an efficient and operationally simple single-flask synthesis of imidodiphosphate-based Brønsted acids. The methodology proceeds via consecutive chloride substitutions of hexachlorobisphosphazonium salts, providing rapid access to imidodiphosphates (IDP), iminoimidodiphosphates (iIDP), and imidodiphosphorimidates (IDPi). These privileged acid catalysts feature a broad acidity range (pK(a) from ∼11 to <2 in MeCN) and a readily tunable confined active site. Our approach enables access to previously elusive catalyst scaffolds with particularly high structural confinement, one of which catalyzes the first highly enantioselective (>95:5 er) sulfoxidation of methyl n-propyl sulfide. Furthermore, the methodology delivers a novel, rationally designed super acidic catalyst motif, imidodiphosphorbis(iminosulfonylimino)imidate (IDPii), the extreme reactivity of which exceeds commonly employed super-Brønsted acids, such as trifluoromethanesulfonic acid. The unique reactivity of one such IDPii catalyst has been demonstrated in the first α-methylation of a silyl ketene acetal with methanol as the electrophilic alkylating reagent. American Chemical Society 2021-09-03 2021-09-15 /pmc/articles/PMC8447263/ /pubmed/34478297 http://dx.doi.org/10.1021/jacs.1c07067 Text en © 2021 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Schwengers, Sebastian A. De, Chandra Kanta Grossmann, Oleg Grimm, Joyce A. A. Sadlowski, Natascha R. Gerosa, Gabriela G. List, Benjamin Unified Approach to Imidodiphosphate-Type Brønsted Acids with Tunable Confinement and Acidity |
title | Unified
Approach to Imidodiphosphate-Type Brønsted
Acids with Tunable Confinement and Acidity |
title_full | Unified
Approach to Imidodiphosphate-Type Brønsted
Acids with Tunable Confinement and Acidity |
title_fullStr | Unified
Approach to Imidodiphosphate-Type Brønsted
Acids with Tunable Confinement and Acidity |
title_full_unstemmed | Unified
Approach to Imidodiphosphate-Type Brønsted
Acids with Tunable Confinement and Acidity |
title_short | Unified
Approach to Imidodiphosphate-Type Brønsted
Acids with Tunable Confinement and Acidity |
title_sort | unified
approach to imidodiphosphate-type brønsted
acids with tunable confinement and acidity |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8447263/ https://www.ncbi.nlm.nih.gov/pubmed/34478297 http://dx.doi.org/10.1021/jacs.1c07067 |
work_keys_str_mv | AT schwengerssebastiana unifiedapproachtoimidodiphosphatetypebrønstedacidswithtunableconfinementandacidity AT dechandrakanta unifiedapproachtoimidodiphosphatetypebrønstedacidswithtunableconfinementandacidity AT grossmannoleg unifiedapproachtoimidodiphosphatetypebrønstedacidswithtunableconfinementandacidity AT grimmjoyceaa unifiedapproachtoimidodiphosphatetypebrønstedacidswithtunableconfinementandacidity AT sadlowskinataschar unifiedapproachtoimidodiphosphatetypebrønstedacidswithtunableconfinementandacidity AT gerosagabrielag unifiedapproachtoimidodiphosphatetypebrønstedacidswithtunableconfinementandacidity AT listbenjamin unifiedapproachtoimidodiphosphatetypebrønstedacidswithtunableconfinementandacidity |