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

MPG-Autoren
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Schwengers,  Sebastian A.
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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De,  Chandra Kanta
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Grossmann,  Oleg
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Grimm,  Joyce A. A.
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Sadlowski,  Natascha R.
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Gerosa,  Gabriela G.
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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List,  Benjamin
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Zitation

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.


Zitierlink: https://hdl.handle.net/21.11116/0000-0009-40F6-9
Zusammenfassung
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.