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  Unified Approach to Imidodiphosphate-Type Brønsted Acids with Tunable Confinement and Acidity

Schwengers, S. A., De, C. K., Grossmann, O., Grimm, J. A. A., Sadlowski, N. R., Gerosa, G. G., et al. (2021). Unified Approach to Imidodiphosphate-Type Brønsted Acids with Tunable Confinement and Acidity. Journal of the American Chemical Society, 143(36), 14835-14844. doi:10.1021/jacs.1c07067.

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Unified Approach to Imidodiphosphate-type Bronsted Acids with Tunable Confinement and Acidity.pdf (Publisher version), 2MB
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Unified Approach to Imidodiphosphate-type Bronsted Acids with Tunable Confinement and Acidity.pdf
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 Creators:
Schwengers, Sebastian A.1, Author              
De, Chandra Kanta1, Author              
Grossmann, Oleg1, Author              
Grimm, Joyce A. A.1, Author              
Sadlowski, Natascha R.1, Author              
Gerosa, Gabriela G.1, Author              
List, Benjamin1, Author              
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1Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445585              

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 Abstract: 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 (pKa 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.

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Language(s): eng - English
 Dates: 2021-07-072021-09-032021-09-15
 Publication Status: Published in print
 Pages: 10
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacs.1c07067
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Title: Journal of the American Chemical Society
  Other : JACS
  Abbreviation : J. Am. Chem. Soc.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 143 (36) Sequence Number: - Start / End Page: 14835 - 14844 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870