Switchable Organocatalysis from N ‐heterocyclic Carbene‐Carbodiimide Adducts with Tunable Release Temperature **
Abstract: N‐Heterocyclic carbenes (NHCs) are powerful organocatalysts, but practical applications often require in situ generation from stable precursors that “mask” the NHC reactivity via reversible binding. Previously established “masks” are often simple small molecules, such that the NHC structure is used to control both catalytic activity and activation temperature, leading to undesirable tradeoffs. Herein, we show that NHC‐carbodiimide (CDI) adducts can be masked precursors for switchable organocatalysis and that the CDI substituents can control the reaction profile without changing the NHC structure. Large electronic variations on the CDI (e.g., alkyl versus aryl) drastically change the catalytically active temperature, whereas smaller perturbations (e.g., different para‐substituted phenyls) tune the catalyst release within a narrower window. This control was demonstrated for three classic NHC‐catalyzed reactions, each influencing the NHC‐CDI equilibrium in different ways. Our results introduce a new paradigm for controlling NHC organocatalysis as well as present practical considerations for designing appropriate masks for various reactions.
- Location
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Deutsche Nationalbibliothek Frankfurt am Main
- Extent
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Online-Ressource
- Language
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Englisch
- Bibliographic citation
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Switchable Organocatalysis from N ‐heterocyclic Carbene‐Carbodiimide Adducts with Tunable Release Temperature ** ; day:25 ; month:10 ; year:2023 ; extent:6
Angewandte Chemie ; (25.10.2023) (gesamt 6)
- Creator
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Pham, Le Dung
Smith‐Sweetser, Red O.
Krupinsky, Briana
Dewey, Carolyn E.
Lamb, Jessica R.
- DOI
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10.1002/ange.202314376
- URN
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urn:nbn:de:101:1-2023102515404033874769
- Rights
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Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
- Last update
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14.08.2025, 10:48 AM CEST
Data provider
Deutsche Nationalbibliothek. If you have any questions about the object, please contact the data provider.
Associated
- Pham, Le Dung
- Smith‐Sweetser, Red O.
- Krupinsky, Briana
- Dewey, Carolyn E.
- Lamb, Jessica R.
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Switchable Organocatalysis from N ‐heterocyclic Carbene‐Carbodiimide Adducts with Tunable Release Temperature **
N‐Heterocyclic Carbene Organocatalysis: With or Without Carbenes?
N‐Heterocyclic Carbene Acyl Anion Organocatalysis by Ball‐Milling
N‐Heterocyclic Carbene and Cyclic (Alkyl)(amino)carbene Adducts of Antimony(III)
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Desymmetrization of N-Cbz glutarimides through N-heterocyclic carbene organocatalysis
The Mechanism of N‐Heterocyclic Carbene Organocatalysis through a Magnifying Glass
Copper and Silver Complexes of N‐Heterocyclic Carbene‐Parent Phosphinidene Adducts
Mechanical force-switchable aqueous organocatalysis
N-heterocyclic carbenes in organocatalysis
Cooperative catalytic systems based on N-heterocyclic carbene (NHC) organocatalysis and transition metal catalysis