An organophotocatalytic late-stage N-CH 3 oxidation of trialkylamines to N -formamides with O 2 in continuous flow

We report an organophotocatalytic, N-CH -selective oxidation of trialkylamines in continuous flow. Based on the 9,10-dicyanoanthracene (DCA) core, a new catalyst (DCAS) was designed with solubilizing groups for flow processing. This allowed O to be harnessed as a sustainable oxidant for late-stage p...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:Chemical science (Cambridge) 2022-02, Vol.13 (7), p.1912-1924
Hauptverfasser: Mandigma, Mark John P, Žurauskas, Jonas, MacGregor, Callum I, Edwards, Lee J, Shahin, Ahmed, d'Heureuse, Ludwig, Yip, Philip, Birch, David J S, Gruber, Thomas, Heilmann, Jörg, John, Matthew P, Barham, Joshua P
Format: Artikel
Sprache:eng
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
Beschreibung
Zusammenfassung:We report an organophotocatalytic, N-CH -selective oxidation of trialkylamines in continuous flow. Based on the 9,10-dicyanoanthracene (DCA) core, a new catalyst (DCAS) was designed with solubilizing groups for flow processing. This allowed O to be harnessed as a sustainable oxidant for late-stage photocatalytic N-CH oxidations of complex natural products and active pharmaceutical ingredients bearing functional groups not tolerated by previous methods. The organophotocatalytic gas-liquid flow process affords cleaner reactions than in batch mode, in short residence times of 13.5 min and productivities of up to 0.65 g per day. Spectroscopic and computational mechanistic studies showed that catalyst derivatization not only enhanced solubility of the new catalyst compared to poorly-soluble DCA, but profoundly diverted the photocatalytic mechanism from singlet electron transfer (SET) reductive quenching with amines toward energy transfer (E T) with O .
ISSN:2041-6520
2041-6539
DOI:10.1039/D1SC05840A