127955-44-6Relevant articles and documents
An organophotocatalytic late-stage N-CH3 oxidation of trialkylamines to N-formamides with O2 in continuous flow
?urauskas, Jonas,Barham, Joshua P.,Birch, David J. S.,Edwards, Lee J.,Gruber, Thomas,Heilmann, J?rg,John, Matthew P.,MacGregor, Callum I.,Mandigma, Mark John P.,Shahin, Ahmed,Yip, Philip,d'Heureuse, Ludwig
, p. 1912 - 1924 (2022/02/25)
We report an organophotocatalytic, N-CH3-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 O2 to be harnessed as a sustainable oxidant for late-stage photocatalytic N-CH3 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 (EnT) with O2
